Ullmann's Encyclopedia of Industrial Chemistry. Textile Dyeing 2012
Ullmann's Encyclopedia of Industrial Chemistry. Textile Dyeing 2012
Textile Dyeing
HERBERT LEUBE (RETIRED), BASF Aktiengesellschaft, Ludwigshafen, Federal Republic
of Germany
WILHELM RÜTTIGER (RETIRED), BASF Aktiengesellschaft, Ludwigshafen, Federal
Republic of Germany
GERD KÜHNEL, BASF Aktiengesellschaft, Ludwigshafen, Federal Republic
of Germany
JOACHIM WOLFF, Bayer AG, Leverkusen, Federal Republic of Germany
GÜNTHER RUPPERT, BASF Aktiengesellschaft, Ludwigshafen, Federal Republic
of Germany
MICHAEL SCHMITT, BASF Aktiengesellschaft, Ludwigshafen, Federal Republic
of Germany
CHRISTIAN HEID (RETIRED), Cassella AG, Frankfurt, Federal Republic of Germany
MAX HÜCKEL (RETIRED), Hoechst Aktiengesellschaft, Offenbach, Federal Republic
of Germany
HANS-JOACHIM FLATH, Dresden, Federal Republic of Germany
WOLFHARD BECKMANN (RETIRED), Bayer AG, Leverkusen, Federal Republic
of Germany
ROLF BROSSMANN (RETIRED), Bayer AG, Leverkusen, Federal Republic of Germany
MANFRED S€oLL (RETIRED), Bayer AG, Leverkusen, Federal Republic of Germany
ULRICH SEWEKOW, Bayer AG, Leverkusen, Federal Republic of Germany
7.2. Dyeing Processes for Polyester Fibers . 279 11.2.3. Auxiliaries . . . . . . . . . . . . . . . . . . . . . . 299
7.2.1. Requirements to Be Met by Dyes and 11.3. Polyamide – Cellulose Blends . . . . . . . 299
Auxiliaries . . . . . . . . . . . . . . . . . . . . . . 279 11.4. Polyacrylonitrile – Cellulose Blends . . 300
7.2.2. Dyeing from Aqueous Dye Baths . . . . . . 280 11.5. Polyacrylonitrile – Wool Blends . . . . . 301
7.2.3. Special Dyeing Processes. . . . . . . . . . . . 280 11.6. Blends of Synthetic Fibers . . . . . . . . . . 301
7.2.4. Continuous and Semicontinuous Dyeing 12. Characterization of Textile Dyes . . . . . 302
Processes . . . . . . . . . . . . . . . . . . . . . . . 281 13. Testing of Colorfastness . . . . . . . . . . . 304
7.2.5. Dyeing of Microfibers . . . . . . . . . . . . . . 282 13.1. Organization . . . . . . . . . . . . . . . . . . . . 304
7.2.6. Dyeing of Modified Polyester Fibers . . . 283 13.2. Standard Test Methods . . . . . . . . . . . . 304
7.3. Aftertreatment. . . . . . . . . . . . . . . . . . . 283 13.2.1. Group A: General Principles . . . . . . . . . 304
8. Dyeing of Cellulose Acetate . . . . . . . . . 283 13.2.2. Group B: Colour Fastness to Light and
8.1. Dyeing Processes for Cellulose Acetate 284 Weathering . . . . . . . . . . . . . . . . . . . . . . 305
8.2. Dyeing Processes for Cellulose Triacetate 284 13.2.3. Group C: Colour Fastness to Washing and
8.3. Aftertreatment, S-Finish . . . . . . . . . . . 285 Laundering . . . . . . . . . . . . . . . . . . . . . . 306
9. Dyeing of Acrylic (Polyacrylonitrile and 13.2.4. Group D: Colour Fastness to Dry Cleaning 306
Modacrylic) Fibers . . . . . . . . . . . . . . . 285 13.2.5. Group E: Colour Fastness to Aqueous
9.1. Economic Aspects . . . . . . . . . . . . . . . . 285 Agencies . . . . . . . . . . . . . . . . . . . . . . . . 306
9.2. Principles . . . . . . . . . . . . . . . . . . . . . . . 285 13.2.6. Group G: Colour Fastness to Atmospheric
9.2.1. Disperse Dyes . . . . . . . . . . . . . . . . . . . . 286 Contaminants . . . . . . . . . . . . . . . . . . . . 308
9.2.2. Cationic Dyes . . . . . . . . . . . . . . . . . . . . 286 13.2.7. Group J: Measurement of Colour and
9.3. Exhaustion Process . . . . . . . . . . . . . . . 289 Colour Differences . . . . . . . . . . . . . . . . 308
9.4. Dyeing of Special Fiber Types According 13.2.8. Group N: Colour Fastness to Bleaching
to the Exhaustion Process . . . . . . . . . . 290 Agencies . . . . . . . . . . . . . . . . . . . . . . . . 309
9.5. Continuous Processes. . . . . . . . . . . . . . 291 13.2.9. Group P: Colour Fastness to Heat
10. Dyeing of Other Synthetic Fibers . . . . 292 Treatments . . . . . . . . . . . . . . . . . . . . . . 309
10.1. Poly(Vinyl Chloride) Fibers . . . . . . . . . 292 13.2.10. Group S: Colour Fastness to Vulcanization 309
10.2. Elastomeric Fibers . . . . . . . . . . . . . . . . 292 13.2.11. Group X: Colour Fastness to Miscellaneous
10.3. Polypropylene Fibers . . . . . . . . . . . . . . 293 Agencies . . . . . . . . . . . . . . . . . . . . . . . . 310
10.4. Poly(Vinyl Alcohol) (PVA) Fibers . . . . 293 13.2.12. Group Z: Colourant Characteristics . . . . 311
10.5. Aramid Fibers . . . . . . . . . . . . . . . . . . . 294 14. Legal Aspects, Toxicology, and Ecology 312
11. Dyeing of Fiber Blends . . . . . . . . . . . . 294 14.1. Water Consumption. . . . . . . . . . . . . . . 312
11.1. Polyester – Cellulose Blends . . . . . . . . 295 14.2. Legal Regulations . . . . . . . . . . . . . . . . 312
11.1.1. General Finishing Information . . . . . . . . 295 14.3. Components of Textile Wastewater . . . 314
11.1.2. Dyeing Processes. . . . . . . . . . . . . . . . . . 296 14.4. Reduction of Wastewater Load by
11.1.2.1. Dyeing with Disperse and Vat Dyes or Special Preventive Measures . . . . . . . . 314
Appropriate Mixed Dyes . . . . . . . . . . . . 296 14.5. Special Methods of Wastewater
11.1.2.2. Dyeing with Disperse and Reactive Dyes 297 Treatment . . . . . . . . . . . . . . . . . . . . . . 316
11.1.2.3. Dyeing of the Cellulose Component with 14.6. Recycling of Water and Valuable
other Dyes . . . . . . . . . . . . . . . . . . . . . . 298
Substances . . . . . . . . . . . . . . . . . . . . . . 318
11.2. Polyester – Wool Blends . . . . . . . . . . . 298
14.7. Ecotoxicology of Textile Dyes . . . . . . . 319
11.2.1. Dyes . . . . . . . . . . . . . . . . . . . . . . . . . . . 298
References . . . . . . . . . . . . . . . . . . . . . . 320
11.2.2. Dyeing Processes. . . . . . . . . . . . . . . . . . 298
carboxylic acid as the principal dye. These sub- of the dyeing methods commonly used at the end
stances are obtained from insects and require a of the 19th century is given in [10] together with
metallic mordant for dyeing. many individual recipes based on publications in
Dyes isolated from plants, such as indigo from Reimanns F€ arbezeitung (1872 – 1879).
the Indian indigo plant or dyer’s woad (! Indigo
and Indigo Colorants) and Turkey red, alizarin
(! Anthraquinone Dyes and Intermediates), 1.2. Economic Importance of Textile
from the root of the madder plant, were of greater Dyeing
significance. Dyeing black with iron salts and
tannic acid from the bark of oak was important. The worldwide consumption of fibers by the
Until recently, campeachy wood black, a pyrone textile industry is shown in Table 1 (see also,
dye that occurs in a special Brazilian wood, was ! Fibers, 1. Survey, Chap. 7.). The importance
used because of its rich hue. Yellow was fre- of regenerated cellulose fibers has decreased and
quently produced by using dyes of the flavone that of polyester fibers has clearly increased.
family, which occur in flowers and roots, e.g., Developments since the mid 1970s show that
weld (Reseda luteola L.), or carotinoids, e.g., Europe and North America are losing their share
crocin from saffron. Dyes from red berries (an- of the textile finishing industry and East Asia’s
thocyans) and the orchella weed (archil) gave share is becoming more significant (Table 2). The
dyeings that were less fast. Plant extracts were growing industrialization of China will enhance
also used to produce the color green. this trend.
Apart from the actual dyeing process, the The amount of fiber apportioned to dyeing is
work of the dyer often included isolation and closely connected to the consumer and fashion
preparation of dyes from plants that were either habits of the population. It can be assumed that ca.
imported or grown locally. As a chemical reac- 75 – 80 % of the world fiber consumption con-
tion with rather impure raw materials, the dyeing sists of colored materials; the rest remains undyed
process was complicated and unclear. In fact, or is used for technical articles. Sulfur and reac-
dyeing was an art. Indigo was produced by tive dyes for cellulose fibers and disperse dyes
fermentation from plants and had to be applied especially for polyester fibers are quantitatively in
to the fiber in the reduced form. The reduction the lead. The estimated world consumption of
step was performed in a fermentation vat with
putrefied urine and later with iron sulfate and
Table 1. World fiber consumption
lime (vitriol vat). Turkey red gave especially fast
dyeings as a lake (metal complex) only when the Type of fiber 1980 1992
fabric was pretreated with metallic salts. Alum,
106 t % 106 t %
tin, iron, and copper salts were most commonly
used as mordants. The colors obtained depended Cotton 14.1 47 18.7 47
on the skill and dexterity of the dyer. The old Viscose 3.2 11 2.4 6
Wool 1.6 5 1.6 4
dyeing processes are still being used in the arts Polyamide 3.2 11 3.9 10
and crafts, the substrate being mainly sheep’s Polyester 5.1 17 8.3 21
wool [7], [8]. For ecological reasons, particular- Polyacrylonitrile 2.1 7 2.2 5
ly, the old dyeing processes do not meet the Polypropylene 1.8 4
Others 0.5 2 1.3 3
requirements of modern industrial production. (silk, linen etc.)
In the 18th century, chemical studies dealt
with the nature of color lake formation, the
processes involved in vatting, the suitability of
Table 2. Regional distribution of textile processing, %
individual coloring substances for certain fibers,
and making up recipes for particular shades with Region 1976 1992
different dyes. Furthermore, new dyeing and
Western Europe 17 12
printing techniques were developed in the 18th Eastern Europe 19 11
and early 19th centuries. Apart from providing East Asia 35 44
new color effects, these techniques focused on North America 19 16
producing fast dyeings and largely contributed to South America 6 6
Africa, West Asia 4 7
the upswing in textile manufacture [9]. A review
Vol. 36 Textile Dyeing 193
Clothing 11 60
Outer clothing 42 33 31
Lining materials 17
Furnishings 43 16 28 33
Underwear 4 3 34
Industrial textiles, especially
automotive 41 11 15 23 4
Others 5 27 5 12 3
synthetic textile dyes for dyeing and printing in and fat or glue as the binder) [12], [13]. During
1992 (in 103 t) is given below: Old Testament times dyebaths were used, dyeing
was performed partly in open lead vessels with
Indigo 12
fires underneath to heat the liquor [14].
Vat dyes 26 For a long period, the main method of dyeing
Reactive dyes 108 was in open stone or wood vessels in which the
Direct dyes 45 yarn was agitated in hank form. The use of a
Naphtols 19
Sulfur dyes 100
hand-operated rotating mechanism (reel) over
Cationic dyes 21 the dyebath facilitated the dyeing of fabrics
Anionic dyes 74 (piece goods).
Disperse dyes 102 The use of power driven equipment to move
Pigment preparations 40
Total 547 (for comparison 1980: 450)
the goods and to drive liquor pumps began in the
early 19th century. Also, the first continuous
dyeing plants were built at this time, these being
More than 80 % of the total consumption of in principle identical to those still in operation
547 000 t of dye is used for dyeing and the rest today [15].
for printing.
In textile finishing in Germany (west), the
quantitative importance of individual products 2.1.2. The Field of Dyeing Technology
was shown by an investigation made by the
University of Münster [11] (Table 3). Dyeing technology matches a dyeing process to
The methods and processes of the textile finish- the goods and the dyeing machines. Dyeing
ing industry must adapt to these market require- technology also includes laboratory work, nec-
ments. As a result of increasingly shorter yardages, essary not only for the development of formula-
the trend is toward batchwise production and away tions (sometimes an extremely difficult task), but
from the more economical continuous methods. also contributing to the development and reali-
However, cotton and polyester – cotton fabrics as zation of dyeing processes.
well as certain carpet grades are still dyed in large Color measurement for research and produc-
quantities in continuous processes. tion has become an important and quite separate
The theoretical principles of dyeing are dis- part of dyeing technology. Color measurement is
cussed with individual dye and fiber types. mainly used as an aid in the development of
formulations and for the measurement of unde-
sired color variations of the textile material.
2. Dyeing Technology Another important aspect of dyeing technology
is automatic metering. Although the metering of
2.1. General auxiliaries is already widely used, the consider-
ably more difficult metering of dyes is much less
2.1.1. History widespread.
Dyeing technology is a rapidly expanding
The very first method used to dye clothing was area of textile dyeing. Suitable dyeing technolo-
probably with pigments (clay or ocher as the dye gy can determine not only the feasibility of
194 Textile Dyeing Vol. 36
manufacturing a new article but also its produc- the surface of the fiber and into its interior. The
tion costs, and can be essential for the continued dye is usually in a liquid medium (the liquor),
existence of some business enterprises. which also contains the textile material [17].
The exhaustion dyeing process can be divided
into three phases (Fig. 1). Each phase is charac-
2.1.3. Fundamental Principles of Dyeing terized independently of the other phases as far as
possible:
2.1.3.1. Dyeing Systems
1. The dyeing phase (exhaustion and absorp-
In the field of dyeing technology no generally tion) Diffusion of the dye into the fiber (dye-
accepted system of classification exists as yet. ing kinetics)
Based on the method of introducing the dye into 2. The equilibrium phase The final dye concen-
or onto the textile fiber three methods of dyeing tration on the fiber (dye yield) is nearly
can be distinguished: reached; leveling and dye penetration occur
at this stage
1. Exhaustion dyeing Diffusion of the dissolved 3. The dye fixation phase Chemical processes,
dye into the fibers (batch and continuous diffusion or ‘‘desolvation’’ of the dye, fastness
dyeing) [16] improvements
2. Pigment dyeing Deposition of insoluble dye
onto the fiber, and fixation with a binder [17] 2.1.3.3. Dyeing Phase (Dyeing Kinetics)
3. Mass and gel dyeing Incorporation of the dye
during production of synthetic fibers In this phase, the dye diffuses from the liquor into
the textile fiber. In most cases, soft water is used as
The market share of exhaustion dyeing ex- the liquid medium. Despite intensive research,
ceeds that of mass dyeing, which in turn is more organic solvents (chlorinated hydrocarbons) have
important than pigment dyeing. not become established as dyeing media, and
As exhaustion dyeing is the most important air – water foam systems have been even less
process in terms of market share, the discussion successful [18]. However, some interesting ex-
of fundamental principles is limited to this pro- periments to use supercritical CO2 as liquor have
cess. Continuous pigment dyeing is mentioned in been carried out (see Section 7.2.3) [19], [20].
Section 2.3. There are essentially two techniques available
for dyeing the textile material:
2.1.3.2. Phases of Exhaustion Dyeing
1. Batch Technique: The liquor and the textile
In exhaustion dyeing, a dye which must be at least are placed together in a vessel, and the re-
partially dissolved migrates by diffusion through quired amount of dye is added.
Type of dyeing Loose stock (also Yarn (bobbins, Textiles (woven, Finished garments
equipment card sliver and tow) hanks) knitted)
Circulating machines package dyeing bobbin, hank, and beam dyeing machines hosiery dyeing
(Section 2.2.3) machines warp beam dyeing machines
machines
Circulating-goods ma- hank dyeing winch and jet dyeing paddle and drum dye-
chines (Section 2.2.4) machines machines, jiggers ing machines
Bath dyeing has the great advantage that it can lated from the absorption curve [21]. The further
be used at any stage of textile production, i.e., on the dyeing rate of the textile – equipment system
the fiber, the yarn, the textile, or the finished lies above the (critical) dyeing rate, the more
garment. Approximately since the International severe is the unlevelness. Correction of unlevel-
Textile Machinery Exhibition (ITMA) 91 there ness is usually carried out by a cumbersome and
has been a tendency to carry out the dyeing as expensive leveling operation, by bleaching and
near to the end of the production chain as possi- redyeing, or simply by dyeing black.
ble, i.e., moving in the direction of the finished Unlevelness is one of the major problems of
manufactured garment. A general overview of short dyeing processes, because these require the
forms of textile goods with the appropriate dye- use of high dyeing rates [35].
ing equipment is given in Table 5. Since the dyeing rate depends on diffusion, it
is controlled by the concentration of the dye in the
liquor. A high liquor ratio (low dye concentra-
2.2.2. Theoretical and Technical tion) leads to a low dyeing rate. For example, to
Fundamental Principles produce a concentration of red dye in the goods of
2 % (20 g per kilogram fiber), the starting con-
A particular advantage of bath dyeing is that wet centration of the dye can be 4 g/L (for a liquor
goods can be treated in the dyebath. For example, ratio 5 : 1) or 1.33 g/L (for a liquor ratio 15 : 1).
woven textiles can be (continuously) desized, However, if the system used forms a dye
and can then be charged, while still wet, to the reservoir, the concentration in the liquor remains
dyeing equipment, avoiding drying costs. constant as long as the dye is supplied quickly
enough (an ‘‘infinite’’ bath). For example, the
Absorption of the Dye (Dyeing Kinetics). dispersed dye particles in polyester dyeing act as
Here, the dyeing rate is the dominant parameter a reservoir that maintains a constant concentra-
(see Section 2.1.3.3). The dye must be absorbed tion of dissolved dye independently of the liquor
uniformly to give a level result [22]. Two basi- ratio [36].
cally different strategies can be used to achieve In general dyeing rate can be controlled by,
this. These must be optimized, also in quite e.g., heating profiles (time – temperature curves),
different ways: addition of leveling agents, carriers, and retarders
and by pH – time and metering – time profiles.
1. Accelerated absorption, giving unlevel dye- When these control tools are used, the most
ing of the goods, followed by accelerated favorable shape of the absorption curves shown
leveling (temperature, auxiliaries, pH). Thus, in Figure 2 is linear, S-shaped curves being the
the absorption phase and the leveling in the most critical. Further details are given in Chap-
dyeing equilibrium are controlled. ters 4, 5, 6, 7, 8, 9, 10, 11.
2. Retarded absorption (the dyed product is al-
ways level, and longer times are required for Dyeing Equilibrium in Bath Dyeing. The
the absorption phase). dyes used for textile dyeing are mostly strongly
substantive, i.e., they form a strong bond to the
To predict the unlevelness in the absorption textile substrate. Thus high dye concentration in
phase, the significant dyeing rate can be calcu- the fiber CF is in equilibrium with a low residual
200 Textile Dyeing Vol. 36
dye concentration in the liquor CL. The simplest ous classes of dyes and methods of obtaining the
indicator of substantivity is the distribution required colorfastness are dealt with in Chapters
coefficient KD ¼ CF/CL (see Section 2.3.1.4). 4, 5, 6, 7, 8, 9, 10, 11. Tests for colorfastness are
Other substantivity parameters also exist. given in Chapter 13.
This is illustrated by the following examples:
Bath Dyeing Technology. The most impor-
Red R 2 %, distribution coefficient ¼ 170 L/kg
tant part of the process is the interaction between
Liquor ratio 5:1 15 : 1 the textile and the dye liquor, especially as this is
Dye concentration in the textile (CF) 19.44 18.38 g/kg influenced by the design of the equipment. It
Dye concentration in the liquor (CL) 0.114 0.108 g/L characterizes the types of dyeing equipment,
Dye yield 97.2 % 91.9 %
Dye losses (wastewater) 2.8 % 8.1 %
which are described in more detail here.
Yellow 2G 1 %, distribution coefficient ¼ 400 L/kg As some dyeing processes are performed
Dye yield 98.8 % 96.4 % above the boiling point of water, high pressure
Dye losses (wastewater) 1.2 % 3.6 % dyeing equipment has been designed in which
dyeing can be carried out up to ca. 140 C [high
In a combination dyeing operation, a change temperature (HT) equipment] [37]. Since the
to a higher liquor ratio (5 : 1 ! 15 : 1) would vapor pressure of water is 2.7 bar at 130 C and
cause more red dye to remain in the liquor 3.6 bar at 140 C, the safety valves are usually
(8.1 % compared with 3.6 %), and would shift set at 6 – 7 bar.
the shade towards yellow. To allow for thermal expansion of the dye
The factors influencing the position of the liquor (ca. 6 % between 20 and 100 C), either a
equilibrium (distribution) (see Section 2.1.3.4) gas cushion is used in the dyebath or an overflow
can also be used for control purposes. with a cooler and an open collection vessel which
The results of a bath dyeing process are easily can then also be used to hold the additives (d in
corrected if necessary. At the end of the process, Fig. 4).
the dyeing result can still be adjusted (shading)
by making further additions. Also, time can be
saved by interrupting the exhaustion process 2.2.3. Circulating Machines (Stationary
early, before a close approach to equilibrium Goods, Circulating Liquor)
(99.0 – 99.9 %) is achieved. The following typi-
cal figures illustrate this: 2.2.3.1. Systems and Functions
Dyeing of Flock. Flock consists of random- formation. In modern apparatus, the liquor ex-
ly oriented fiber which is packed (wet) into a pansion is taken up by means of a gas cushion.
cylindrical container with central tube [40]. Package dyeing often allows sampling of the
Only the coarser and more stable types of fiber yarn for color evaluation through a pressure lock
can be dyed as flock without damage. The pack- during dyeing.
ing density of flock is in the range of 200 – The yarns (fine to coarse) are often wound
400 g/L. It increases when water and auxiliaries from the spinning bobbins onto dyeing bobbins
are added. The liquor flow rate is in the region of (metal or plastic). For this, cross winding is
10 L kg1 min1, and the liquor ratio is usually preferable (weight of yarn per package: 0.5 –
in the range 5 : 1 – 20 : 1. 2.5 kg). The packages are either wound in a
It is difficult to pack and densify the loose conical shape (for easier unwinding of the yarn)
stock uniformly, so that unlevelness can easily and then stacked with separator plates, or are
occur, especially because of the long flow paths wound cylindrically, and then usually com-
in the packed material. However, subsequent pressed (elastic tubes). Very high package densi-
spinning (followed by doubling) of the fibers ties (ca. 800 g/L) are obtained with polyester
often evens out unlevelness mechanically. sewing yarns (compressed), and very low values
Loose stock dyeing apparatus is usually con- (ca. 200 g/L) with polyacrylonitrile packages
structed to hold up to 1 t material, so that not too (risk of deformation because of thermoplasticity).
many dyeing batches are necessary for each The cross-wound packages are held in place in
batch of spun yarn. Loose stock dyeing com- the apparatus by placing them on spindles, and
prises ca. 1 % of all bath dyeing. the columns of packages so formed are closed off
at the top by a spring-loaded plate. The spindles
Dyeing of Card Sliver. Card sliver consists are metal rods (with a star section) or perforated
of a long strip of any kind of staple fiber, the fibers tubes through which the dye liquor is pumped
being mainly parallel. Fiber dyeing is necessary (i ! o and o ! i). The spindles are mounted on
in the production of melange (blended) yarns. floor plates which provide both the support and
The slivers are placed in dyeing baskets or the connection to the liquor supply.
coiled into bundles (wool ‘‘tops’’ having a maxi- Quantities loaded by this method into package
mum weight of 25 kg) [40], [41]. The slivers are dyeing machines can be large or small. Normal
sometimes wound onto a beam for dyeing (see loads for production equipment are between 50
Section 2.2.3.5). and 500 kg. For larger batches, two pieces of
dyeing equipment are joined together (tandem
Dyeing of Tow. Monofilament material pro- operation).
duced during the manufacture of synthetic fibers Occasionally, package dyeing is used with
(primary spinning) is formed into strips (tow), parallel wound yarns (rocket packages, thermo-
which is packed into large containers or carriers fixation packages) or with narrow ribbons instead
[40]. The filled containers are then placed in the of yarns (e.g., lace, zippers).
dyeing apparatus. The liquor ratio can range from ca. 4 : 1 (short
liquor ratio dyeing machine) to ca. 15 : 1 (open
2.2.3.3. Package Dyeing Machines winding, older dyeing machine).
(Cross-Wound Packages) The short liquor dyeing machine is usually
only partially flooded, and permits liquor circu-
The schematic shown in Figure 4 also applies to lation only from the inside to the outside (i ! o,
package dyeing machines, which are usually foaming tendency). The equipment must be spe-
operated at high temperature. In the (obsolete) cially designed to give a high enough pressure on
overflow cooling system, the liquor that over- the suction side of the circulation pump to pre-
flows due to expansion collects in the additives vent cavitation (Fig. 8).
(or expansion) vessel. The advantage of this Higher dyeing rates can often be obtained by
system is the ease of sampling and manual addi- reversing the direction of circulation, usually
tion of products, and the disadvantage is a high every 3 – 8 min. The time required for this re-
energy consumption, air oxidation of the reduc- versal process (dead time) is usually ca. 10 –
ing agents in vat dyeing, and increased foam 100 s.
204 Textile Dyeing Vol. 36
Auxiliaries can be added to the additives In contrast to the apparatus described in the
container manually or automatically. The aux- previous sections, the dyeing vessel in beam
iliaries are pumped from here by the pressure dyeing is normally arranged horizontally.
pump into the dyebath.
Package dyeing equipment has a high share of Piece Beams. In piece dyeing by the beam
the market. Most yarns for color weaving and method, the woven textile (piece), which must
knitting are dyed by this method. not be affected by pressure on the surface (wo-
ven, knitted, or nonwoven material), is evenly
wound onto a beam (perforated tube) in full
width. The interior diameter of the beam is
usually 0.3 – 0.5 m, and the thickness of mate-
rial on the beam is usually 10 – 40 cm, depend-
ing on the type of fabric and size of the batch.
Since the density of the roll of textile on the beam
is similar to the density (g/L) measured on a
single layer sample of textile, it can be predicted
in this way.
Because dyeing with piece beams is so im-
portant, calculation methods have been devel-
oped based on simple measurements on a single
Figure 9. Special valve system for reversing the direction of
flow in a dyeing machine with monodirectional circulation layer sample to calculate the number of layers,
pump (courtesy of Thies) the length in meters, the roll diameter, and the
Vol. 36 Textile Dyeing 205
outside diameter. Measurement of the flow rate All the fundamental principles of exhaustion
through a sample enables even the flow resis- dyeing described in Section 2.1 apply to this
tance of the roll of textile to be accurately pre- dyeing technique, and especially bath dyeing as
dicted [34]. In practice, the calculation of the described in Section 2.2.1.
liquor – textile interaction is most advanced in Dyeing machines with storage devices (rope
the dyeing of piece goods by the beam method. dyeing machines) consist basically of a means of
The direction of flow of the liquor is normally transporting the textile and a storage zone into
from the inside to the outside of the roll of textile. which it is transported. Movement of the textile
The ends of the beam are covered with metal can be achieved
sheets (sleeves) before the fabric is wound on, to
prevent a short circuit of the liquor. 1. Mechanically by a rotating body (winch, i.e. a
Although a high liquor flow rate is desirable, a rotating body with an elliptical section) and
limit is imposed by the resulting high differential electric motor
pressure, which causes the fabric to ‘‘lift’’ from 2. Hydraulically by a jet
the beam, often at a differential pressure of only 3. By a hydraulic lifting pipe and the force of
1 bar. This disturbs the controlled flow of the gravity in a propelling system (overflow)
liquor. A possible preventive measure is to wind 4. Pneumatically (Airflow)
the fabric under high tensile load, which, how-
ever, is problematical for certain fabrics. Batch In the region of the drive unit, an intensive
sizes can be 500 – 3000 m. An open (permeable) mass transfer occurs between the free liquor and
fabric is usually more suitable than a dense (low the liquor in the interstitial volume of the textile,
permeability) fabric. Also, significant swelling of although only very briefly.
the fabric reduces its permeability to the liquor In the storage region, the dye has time to
(greater pressure buildup). diffuse out of the interstitial spaces of the textile
The piece beam process has a market share of and into the interior of the fibers. The depleted
ca. 10 % of circulating machines. liquor in the interstitial volume must then be
replenished.
Warp Beam Dyeing is similar to piece The number of cycles of the textile per minute
beam dyeing. Here, the warp or a part of it is is usually in the range 0.2 – 1, with velocities of
wound onto the beam. The yarns are parallel to ca. 30 – 600 m/min and batch sizes usually
each other, and have a relatively high flow resis- < 1000 m. The relationship between these pro-
tance as the threads support each other. If the cess parameters is shown in Figure 10.
differential pressure becomes too high, a roll of If the load in the dyeing machine is too high,
this type cannot lift, but the threads ‘‘part’’. the dwell times in the storage region become too
Warp beam dyeing is mainly important for the
process of multicolored weaving with a plane-
dyed warp, it accounts for < 10 % of all circu-
lating machines.
2.2.5. The Dyeing Jigger Generally woven textiles are dyed by the jig
process. The textiles must not be sensitive to
2.2.5.1. Normal (Direct) Jig Dyeing tension (e.g., texturized warp) or pressure (e.g.,
bulked material). However, fabrics susceptible to
The batch of fabric is drawn into the jigger, creasing can be dyed, as dyeing is exclusively
through a dyebath, and is taken up by a roll on performed in full width. The jigger is the most
the other side of the bath (Fig. 15) [24, p. 701, suitable dyeing machine for thin and imperme-
Fig. 6.], [47–49]. able woven textiles, e.g., lining materials. High
Vol. 36 Textile Dyeing 209
temperature jiggers have been available since the of dyeing at the ends of the fabric is reduced
1980s, so that all fiber substrates, from cellulose because of short dwell times, and this must be
to polyester garments, can be dyed in these leveled by an increased number of passes. To
machines. reduce the unlevelness of the ends, the dye is
The fabric can be loaded either dry or wet, usually added during the first two passes (1 : 1).
e.g., after a continuous desizing operation. The The dyeing process is controlled by the number
fabric velocity is ca. 50 – 130 m/min. The liquor of passes (exhaustion time, final concentration
ratio is usually 3 : 1 – 5 : 1, i.e., very short. The in the bath) and by means of temperature, pH,
size of the batch is usually 300 – 400 kg. So- salt concentration, etc. (see Sections 2.1.3
called jumbo jiggers also exist in which a batch of and 2.2.1).
almost 1 t textile can be dyed. The passes are necessary to achieve intense
The fabric passes through the dyebath in interchange of the fabric with the liquor and to
which only a limited amount of liquor exchange provide sufficient time for penetration of the dye.
occurs. A complete passage of a batch is known The overall dyeing time, determined by the
as a pass. During the time that the fabric is in the number of passes, varies with the fabric velocity
bath (ca. 0.5 – 1 s), the free liquor in the bath is (usually constant) and the length of the batch
exchanged with the depleted liquor in the textile. (usually variable) (see Fig. 16).
The exhaustion of the liquor begins in the wound Minimum dyeing times (exhaustion times)
up batch of fabric, where the fabric remains for a and minimum numbers of passes required to give
considerably longer time. This can lead to non- level dyeing are given in Figure 16. These figures
uniformity between the ends of the fabric. are valid for a batch of 1000 m; for shorter
During one pass, the dye content of the batches (500 m), the number of passes must be
liquor becomes much depleted. The intensity doubled; and for batches 2000 m in length, only
210 Textile Dyeing Vol. 36
the radial metal rods, set at an angle of ca. 30 , This helps considerably to avoid flattening of the
there are small hooks (ca. 1 cm apart) on which yarn [42].
the goods (woven or knitted) are hung. These are The Colourdry dyeing machine by MCS is an
sometimes also pinned on one side only (usually interesting further development [50]. The hanks
for pretreatment, allowing free shrinkage). The are placed loosely on triangles of tubing. The
star framework is an old type of dyeing equip- liquor is sprayed from the tubing onto the yarn
ment. The goods form a spiral cylinder and do not (liquor ratio < 15 : 1). Centrifuging and drying
touch each other, i.e., dyeing is very gentle. are carried out in the same equipment without
The star-shaped hanging frame, also known additional handling of the yarn.
as a vertical star, is suspended in the bath. The The very gentle treatment is advantageous,
goods are normally completely immersed. but the space – time yield is low, so that these
The star is sometimes moved up and down machines are usually limited to special appli-
(high liquor volumes and a liquor ratio of ca. cations.
20 : 1 – 30 : 1) or it can be fixed in the dyebath
and the liquor movement can be produced by a 2.2.6.3. Paddle Dyeing Machine
circulation pump (low liquor volumes and a
liquor ratio of ca. 12 : 1 – 25 : 1). In neither case This machine, also known as a paddle tank, is
longitudinal tension occurs in the goods, and any used for dyeing finished garments (sweaters,
transverse tension is usually due only to their pants and trousers, etc.). The textile goods
weight. ‘‘float’’ in the dyebath. The goods are vigorously
In horizontal star suspension systems, the agitated by:
spacer tube can be rotated, and is located above
the dyebath. The star is rotated by a motor. Only 1. Motor driven mechanical paddles.
part of the star is immersed in the liquor along 2. Injection nozzles (tangential and radial)
with the goods (short liquor ratio). The liquor is through which the liquor is pumped. This
taken up when the goods are rotated. The spiral produces the necessary relative movement of
shape of the goods ensures that the inner parts are the textile and the liquor.
also fully supplied with liquor.
The star with the goods can be very easily These dyeing machines are also constructed
transferred into other vessels, after dyeing in a for high temperature operation. They have a large
stationary bath, e.g., into an aftertreatment bath market share of the dyeing of ready-made goods,
or in a star steamer. although this is a relatively small part of the total
The space – time yields are low, so that this market [51].
dyeing technique, which is now only seldom
used, is expensive. However, the very gentle 2.2.6.4. Rotary Dyeing Machine
treatment of the goods can justify the process
for textiles made from velvet and silk. The rotary dyeing machine resembles a domestic
washing machine. It can contain ca. 50 – 300 kg
2.2.6.2. Machines for Dyeing Hanks of Yarn goods. It is mainly used for dyeing ready-made
garments, and can also be constructed for high
Spray dyeing machines have been used for a long temperature operation [51], [52].
time for dyeing hanks of yarn, but tubular knitted The drum dyeing machine is very suitable for
goods can also be dyed by this method in some producing wash-out effects. A high proportion of
cases. jeans are so treated. Various processes exist, e.g.,
The hanks are placed on a perforated tube. The stone washing (stones and chlorine-based bleach).
liquor is then pumped through this tube, sprays
out of the perforations onto the goods and runs 2.2.6.5. Cabinet Dyeing
off. Normally, the hank does not dip into the
liquor, so that there is some freedom of choice of The cabinet apparatus resembles a cabinet
liquor volume (liquor ratio can be between 10 : 1 through which liquor is pumped (Fig. 17). If the
and 40 : 1). A carrier arm moves the hank a short apparatus is used for dyeing hanks of yarn, the
distance into a new position from time to time. cabinet contains poles that carry the hanks.
212 Textile Dyeing Vol. 36
1. Description of the dyeing process in text form produces operations planning, usage of the
2. Tables of the control functions required equipment (with or without shading), and batch
3. Process diagram with symbols for the indi- control.
vidual functions in the apparatus [38], [56] Data for cost calculations are sometimes also
produced. The evaluation of color shading addi-
The instructions for a dyeing operation are tions, dyeing rate, effects of auxiliaries, unlevel-
usually rather generalized, so that the program- ness, etc. is at an early stage of development. The
mer has some degrees of freedom, e.g., with preparation of dyeing programs by the dyehouse
respect to liquor draining times during bath with the aid of software is described in, e.g., [26].
changes. Experienced dyers very familiar with In all kinds of bath dyeing, i.e., in circulat-
automatic control and the dyeing process can ing – goods or circulating – liquor dyeing ma-
often utilize the available degrees of freedom to chines, or special equipment, the requirements
achieve considerable process optimization. A are similar. Therefore the automatic control de-
dyeing diagram is shown in Figure 18. vices are essentially similar for the various tasks
and are adapted to the specific tasks by additional
2.2.7.2. Functions of Automatic Control modules. The control devices are made compati-
ble with the software. Also, the same kind of
The automatic control of the charging of dyeing personal supervision is applicable to all these
equipment with the textile goods (robot systems) control systems.
is described in [47], [57], [58]. This can include The requirements of an automatic control
automatic recognition of the batch number (stage system cover a very wide spectrum today. How-
3 in list provided in Section 2.2.7.1) [47]. ever, a true process control system based on
The basic classification is into (1) direct and artificial intelligence is still awaited.
(2) indirect effects of the control program on the
process (local, decentralized) and (3) an intelli- 2.2.7.3. Equipment Requirements
gent control of the entire process, which is usu-
ally carried out centrally in a computer [32], [59]: Automatic process control usually has two
components:
1. Direct control of the process elements by the
stored program (stages 1 and 2, Section 1. The control computer with the dyeing pro-
2.2.7.1), occurs by control of valves and gram and the operator’s console (company-
motors or pumps (e.g., flow direction i ! o, specific, Fig. 19)
o ! i), alarm indicators for product addi- 2. A control system with programmable memo-
tions, i.e., process control. ry, a so-called stored program controller
2. Indirect effect of the stored program on the (SPC), constructed from universal low cost
process (stages 1 and 2). The set points are fed components (modules) which carries out in-
to the local control systems as a function of dividual functions
time. The control systems, which have local
intelligence, carry out measurements (e.g., The individual functions are programmed into
temperature, differential pressure, pH [60]), the SPC, and are called by the control computer
compare with the current set point, and issue as required. Likewise, the different closed-loop
the necessary control command to the actuat- control systems are usually formed and backed
ing device, e.g., steam or metering valve, up by the memory.
pump which is usually continuously con- The programs stored in the memory of the
trolled, use of feedforward and closed-loop SPC are completely adapted to the individual
control, i.e., program control (time – temper- parts of the dyeing plant, and cannot be altered by
ature program). the user.
3. Intelligent control of the entire process (stage The control computer contains the actual dye-
4). ing program. This is either entered at its console
or on a PC, and is then loaded down to the control
The data of the dyeing operation are usually computer. It is usually specific to the dyeing
fed into a central computer. The central computer equipment and not directly transferable. Only
214 Textile Dyeing Vol. 36
Figure 18. Process diagram for dyeing [38], [55], [77, p. 331]
A) Dyeing with vat dyes by the pre-pigmentation process; B) Table of process symbols
a) Preparing the dyeing liquor; b) Dyeing; c) Rinsing, oxidizing soaping; d) Rinsing neutralization
Vol. 36 Textile Dyeing 215
Important values for closed-loop control Mass dyeing is in principle carried out by the
Liquor temperature (dyebath) fiber producer, > 95 % of polypropylene fibers
Liquor differential pressure (dyebath) are dyed in this way. Mass dyeing is not described
pH (dyebath, auxiliaries vessel) here, as this dyeing technique mainly lies outside
Salt concentration the area of textile finishing.
The continuous dyeing of warp yarn is the
Important feedforward control functions main technique used for dyeing with indigo (!
Filling (water, auxiliaries vessel) Indigo and Indigo Colorants, Chap. 9.). Contin-
Emptying (to drain or recycle) uous dyeing of flock and monofilament yarns is
Flow direction (i ! o, o ! i) described in Section 2.3.3.
Metering (linear, nonlinear) The main topics of Section 2.3 are the contin-
Time – temperature profiles uous and semicontinuous dyeing of fabrics in
pH and redox profiles dyeing lines, using the technique of exhaustion
dyeing. Pigment dyeing, which represents a
Some devices are specifically necessary for small market volume, is described in [62].
the dyeing equipment, e.g., cycle detectors for jet Special processing units were developed for
and overflow dyeing machines; and passage continuous dyeing, most of them in the 19th
counters to record the number of passes and century, and these are assembled to form the
devices to measure longitudinal tension for dyeing lines [15].
jiggers. Some general rules and relationships apply to
The control computer is often connected to a the fully continuous and semicontinuous dyeing
PC for transfer of process data. technique:
In general, modern equipment for controlling
dyeing machinery gives better reliability than 1. Fabrics are treated in open width (not in rope
good manual control. form, because crease marks cannot be re-
Certainly the increase in production over moved in a continuous system).
recent years would not have been possible with- 2. Fabrics are passed through a processing line at
out automatic process control. Moreover, in view a constant speed of ca. 20 – 200 m/min. Pos-
of the excellent durability of stainless steel dye- sible stretching or shrinking of the fabric is
ing equipment, the cost of installing or modern- compensated for by longitudinal tension sen-
izing automatic control equipment can in many sors and speed controllers. The longitudinal
216 Textile Dyeing Vol. 36
tension on the fabric is in general adjustable. It up to 5 m in width. A small number of fabrics can
usually causes a reduction in the width of the be uniformly charged with dye liquor by a squee-
goods of several percent and leads to minimi- gee operation. Fashion effects can be achieved
zation of longitudinal creases [47]. by printing the fabric on both sides in a uniform
3. The running speed of the fabric determines the color (! Textile Printing). In all continuous
(usually short) dwell time in the individual techniques, uniform application of the dye liquor
treatment units (ca. 5 – 120 s, depending on can only be achieved on a dry fabric. Therefore,
the length of fabric in the unit). In semicon- in contrast to the batch dyeing process, the wet
tinuous processes, i.e., continuous processes fabric must be dried before treatment which
in the course of which the goods are batched increases the costs of the process.
up, dwell times of several hours are possible
[63]. Padding Process. In the padding process
4. In all continuous processes, interruptions the dry fabric passes through the pad trough,
cause significant staining. where it picks up the dye liquor. Good wetting
5. Any unevenness in the equipment across the of the textile is therefore important. With suitable
width of the goods leads to unlevel dyeing auxiliaries it is often possible to pad even gray
(streaks and middle-to-edge unlevelness). cloth (! Textile Auxiliaries, 5. Dyeing Auxili-
aries). After leaving the pad trough, the fabric is
2.3.1. The Principal Stages of Continuous squeezed between rubber rolls. The liquor pick-
Dyeing up, i.e., the resulting liquor charge, varies accord-
ing to the fabric material (40 – 100 %).
2.3.1.1. Dye Pickup The amount of dye liquor picked up (liquor
charge or padding effect) strongly depends on the
In this treatment stage, the dye liquor is taken up squeeze pressure produced by the two rolls (pad
(continuously) by the fabric. Two groups of mangle). Figures for the liquor pickup are usually
application techniques exist: expressed as wt % based on dry fabric (at ambient
atmospheric humidity). The curve of the liquor
1. Direct application of the required quantity of pickup plotted against squeeze pressure is non-
dye liquor to the fabric, i.e., application of the linear (Fig. 20).
liquor with a metering device. These techni- A low liquor pickup is often desirable to
ques are of little industrial importance. Ap- minimize both migration effects and the cost of
plication techniques with direct pickup of the an interim drying stage. A higher liquor pickup is
dye liquor include: pouring [64], kiss pad-
ding, spraying, foam application by doctor
blade [18], and printing (1000-point roll).
2. Immersion of the fabric in the dye liquor. In
this case an excess of dye liquor is taken up by
the fabric. This is followed by removal of the
excess to give the required charge of dye
liquor on the fabric. This group of processes
is of great industrial importance. Application
techniques with immersion of the fabric and
removal of the excess liquor include: squeez-
ing off (padder) [66], squeegee (Flexnip),
suction [65], and free runoff [BDA (British
Dyer’s Association) System].
1. Swimming rolls (‘‘S’’ pad rolls, Küsters see Figure 22. Pad rolls with dye liquor trough; the squeeze
Fig. 21). Variation of the squeeze pressure is pressure adjustable across the width of the roll by inflated air
achieved by varying the oil pressure [15], cushions (supervision) (BICOFLEX system, courtesy of
[66]. Ramisch – Kleinewefers)
A) Distribution of the squeeze pressure over the width;
2. The air cushion control method (the Bicoflex B) Inflated air cushions; C) Dye liquor trough (cross-section)
Foulard system of Ramisch – Kleinewefers)
in which a tubular squeeze roll body slides on
a tube which bears on a stator, by means of air 3. The wave profile of the pad rolls (Matex
cushions inflated to various extents. This en- system, Monfort). Two squeeze rolls whose
ables the squeeze roll to be bent in various diameters vary over the width are arranged
ways (see Fig. 22). adjustably in opposition to one another. This
enables any desired pressure distribution over
the width to be produced [67].
4. Sectional rolls (Nipco rolls, Escher – Wyss).
The squeeze pressure needed at particular
points is obtained by varying the hydrostatic
pressure of individual elements [24, p. 702].
dye content of the padding liquor. Possible coun- Section 7.1.2). In other cases intermediate drying
termeasures include: can be a cost saving, especially with dark color
shades. During drying the dye migrates to the
1. Low immersion volumes (rapid attainment of surface of the fabric, which results in a consider-
equilibrium) able increase in the ‘‘visual dye yield’’ (up to ca.
2. Low temperature, ca. 15 C (often higher 30 %, see Chap. 11).
substantivity but lower absorption rate) In the vat dyeing (see Section 4.3.4), the
3. Control of liquor concentration (e.g., water application of liquor chemicals (reducing agents,
addition at the start of the batch) alkali) on a predried fabric proceeds better, and,
in particular, is less dependent on the material
Problems are also caused by instability of the than a wet-in-wet process.
pad liquor which mainly results from: The drying process takes a very characteristic
course (see Fig. 23) which is largely independent
1. Chemical conversions in the pad liquor, e.g., of the type of dryer [69], at least as long as the
reaction of reactive dyes with alkali, inactiva- drying intensity is uniform along the length of the
tion of dyes by hydrolysate formation (see equipment. The drying process can be divided
Sections 4.1), or reaction of vat dyes with into the following stages:
reducing agents (see Sections 4.3, 4.4) [68].
2. Gradual precipitation of the dye if it is present Stage 1. Water evaporates from the surface
at too high a concentration (higher than its of the fabric in a way largely independent of the
solubility), mutual interaction of various dyes nature of the fabric. Migration of the dye occurs,
used for mixed fabrics (cotton – polyester caused by flow of the dye liquor out of the interior
dyeing), or transfer of sizing or harmful im- of the fabric. The dye contained in the liquor is
purities from the gray cloth into the pad deposited in the surface zones of the fabric. This
liquor. process ends when the liquor charge is ca. 30 %.
3. Buildup of foam and lint (stippling due to
deposition or resist effects, or printing effects Stage 2. Water evaporates from the inter-
due to small masses of lint). stices in the yarns and fibers. Dye deposition
occurs in the interior of the fabric where the
Pickup of the dye is of great importance in evaporation occurs. During this stage, there is
continuous and semicontinuous processes, as very little danger of unlevelness due to migration
defects that occur are extremely difficult to rec- during drying. Dryeing conditions being equal,
tify or repair. Color intensity is determined not the drying rate is much lower than that in Stage 1.
only by the amount of dye applied, but also by the
dye penetration, which determines the ‘‘visual
dye yield’’.
A theoretical treatment of pad dyeing is still a
long way off. In particular, it cannot be predicted
whether a fabric will be dyed lighter or darker at
the edges even if squeezing-off is uniform. The
dyeing practice is determined by the experience
of the specialist, who decides on formulations,
settings of the padding equipment, and on on-line
measurements during production (see Section
2.3.4).
Figure 23. Drying curve of a hot flue dryer for hygroscopic
2.3.1.2. Intermediate Drying fiber material
Decrease of water content with increasing drying time at
After padding the fabric is often dried (pad dry 130 C for a dryer length of 34 m. The initial linear section
corresponds to Stage 1 drying
process). In some cases this is absolutely un- a) Cotton, 100 %, 200 g/m2, initial moisture content 80 %;
avoidable, e.g., when dyeing polyester of poly- b) PES – cotton 67 : 33, 156 g/m2, initial moisture content
ester mixtures by the thermosol process (see 55 %
Vol. 36 Textile Dyeing 219
Predrying with a radiation dryer has become Reduction in water content ¼ 35 % of 6.6 kg/
widely established, although uniform migration min ¼ 2.3 kg/min. This is a gentle drying oper-
can be disturbed, leading to unlevelness (Stage ation. For a soundly based assessment, figures for
1). For pigment dyeing with a binder, a tentering the ‘‘energy impact’’ on the fabric are also im-
frame is often used for drying before the fixation portant (e.g., length of the drying zone, drying
stage. times).
Drying Capacity. The drying capacity Levelness. Both when drying with hot air
(evaporation rate) can be characterized in various and with radiation (steam production), differ-
ways, in which the rate can refer to either the ences in flow rate occur between the middle
dryer or the fabric. and the edges of the fabric. These can lead to
220 Textile Dyeing Vol. 36
Figure 25. Continuous steamer; fabrics inlet and water seal specially designed for vat and sulfur dyes (courtesy of Babcock)
A) Entire machine; B) Fabric inlet
on a fabric guide roll system, and has a fabric The combination of dye and (reactive) binder is
capacity of ca. 30 – 60 m. If atmospheric oxygen first applied to the fabric by a pad dry process.
has to be excluded from the steamer during a dye The fixation stage is described in [17], [62], [73]
reduction process, a steam blanket is provided at and in Section 4.7.
the inlet point and a water seal at the exit.
Other processes include the ‘‘Standfast’’ dye- Fixation by Oxidation. Dyes that have been
ing process in which the fabric is passed through chemically reduced before applying them to the
molten metal (Wood’s metal), heating the fabric fabric must afterwards be reoxidized to achieve
in the liquor with the Williams Unit [24], and fixation (see Sections 4.3.4, 4.5.3).
high frequency heating [71], [72]. The oxidation is normally carried out in spe-
cially designed washing equipment (see Fig. 27).
The Thermosol Process (see Section 7.1.2). Excess alkali is first washed out of the fabric [74].
The dry fiber, loaded with dyestuff, is heated to The most important oxidizing agent used today is
around its glass transition temperature. The pro- hydrogen peroxide [61].
cess is used with thermoplastic fibers, especially
polyester, and sometimes also with polyacrylics.
The fabric, whose fibers are covered with a dried
film of disperse dye and auxiliary, is held at ca.
210 – 220 C for 0.5 – 1 min. This causes the
dye to diffuse into the interior of the fiber,
although it is not clear whether this transfer takes
place mainly by sublimation (gas phase) or
whether the dye ‘‘dissolved’’ in the film of aux-
iliary exhausts from this film. Dye fixation of
disperse dyes on polyester fibers as a function of
time and temperature is shown in Figure 26. The
thermosol process is often used for dyeing the
polyester component in polyester – cotton
blends (see Section 11.1). Dark shades require
subsequent washing to remove residual dye on
the surface to improve fastness properties.
Figure 26. Fixation of disperse dyes on polyester fibers as a
Fixation of the Dye in Pigment Dyeing by function of time and temperature (Rapid thermosol (RT) unit,
Chemical Condensation of the Binder System. courtesy of Fleissner)
222 Textile Dyeing Vol. 36
Figure 27. The oxidation stage in two sections of a washing plant with metering of hydrogen peroxide (sometimes also with
acid or buffering agent) (courtesy of Babcock)
A) Metering section with buffering vessels for products and dispensing valves; B) Dyeing line with dosing controller working
with running impulses and level control of the oxidation bath (movement of goods from left to right)
A typical example of the oxidizing conditions Some process steps that have already been
used in a vat dyeing operation is as follows: treated in Section 2.3.1.3, e.g., the fixation of
hydrogen peroxide (100 %) 1 g/L, pH 10 – most vat or sulfur dyes by oxidation, are often
8.5, oxidation time 0.5 – 1 min, temperature classified as aftertreatment or finishing processes.
50 – 80 C. If the liquor is too alkaline, this can Wet-in-wet methods are always used for after-
lead to decomposition of the hydrogen peroxide treatment. Aftertreatment is performed in the
[75], [76]. For deeper shades, the oxidation is continuous open-width washing machine [74]
sometimes completed in the subsequent soaping (Fig. 28) or some of its units.
stage (95 C), by entrained oxidant.
The dyeing produced is often dependent on Application of Dye Fixation Agents. Dur-
the pH of the oxidation liquor. ing the final wash cationic auxiliaries (to fix
substantive dyes) and reactive hydrolysates (to
2.3.1.4. Aftertreatment of the Dyed Fabric improve wetfastness properties) are applied. The
(Finishing) auxiliaries are metered into a section of the
washing equipment or a special trough. Good
Aftertreatment has the following main objec- squeezing-off is required before treating the fab-
tives: ric and aftertreatment must be carried out in a
standing bath to prevent products from entering
1. To improve or complete the fixation of the dye the countercurrent washing stream.
2. To ‘‘develop’’ the shade, i.e., to adjust it to the
original pattern card Soaping of the Fabric is carried out in the
3. To improve fastness properties soaping liquor close to boiling temperature. In the
4. To wash out residual chemicals or auxiliaries case of reactive dyes the dyeings are rinsed with
5. To improve hand (feel) pure water to remove hydrolysate residues.
Vol. 36 Textile Dyeing 223
Figure 28. Continuous open-width washing machine for the aftertreatment of dyed fabrics (equipment especially for vat
aftertreatment; courtesy of Benninger)
a) Padder; b) Rinsing; c) Oxidation; d) Soaping, near boil; e) Final rinsing
During vat dyeing soaping occurs in a quasi- Generally the dyeing process can be carried out
standing bath to complete fixation and to develop consistently and at a high production rate using
the color. (It is claimed that soaping also improves the classes of dye for which the plant was de-
rubbing resistance but this is questionable.) signed, whereas improvisation may be necessary
The addition of auxiliaries, methods of im- for other classes of dye. In some cases, tasks
proving colorfastness, and the problems that arise involving certain fabrics or classes of dye may be
are described in Chapters 4, 5, 6, 7, 8, 9, 10, 11. impossible.
For control of dyeings and dyeing results see A continuous dyeing plant must provide for
Chapter 13. continuous fabric supply including:
Neutral Washing. In this last treatment step Three typical plants are described as an example:
product residues (especially alkali) are removed
from the fabric [74]. During washing the liquor is Thermosol Pad Steam Plant for Polyester –
often neutralized with acid, with pH control. Cotton Blends (Fig. 29). In the following
example a mixture of dispersion and vat dyes is
first padded on the fabric. The fabric is then dried
2.3.2. Dyeing Plants by IR shaft and hot flue dryer and subsequently
treated in the thermosol unit to fix the disperse
In dyeing plants the individual stages of a dyeing dye. This is performed in hot flue or perforated
operation are assembled of different machine drum equipment. The reducing agent and alkali
parts (units) to form a station or production line. are then padded on the fabric and steamed. This
causes reduction of the vat dye to the leuco form This dyeing technique only requires a small
which is absorbed by the cotton, and also reduc- amount of machinery and little drying energy.
tion of the unfixed disperse dye as a part of the The individual process steps are:
aftertreatment of the polyester component (re-
ductive cleaning). 1. Dye application (absorbent fabric, padding to
Aftertreatment of the dyed cotton component give ca. 60 – 80 % pickup)
is then carried out by: 2. Application of chemicals, i.e., reducing agent
and alkali (padding, kiss padding, wet-in-wet,
1. Cooling (to ca. 30 C, water seal on the ca. 100 % total liquor pickup)
steamer) 3. Steaming (vat dye steamer, saturated steam,
2. Cold rinsing (for alkali removal, in washing air-free, duration ca. 1 – 2 min)
equipment) 4. Cooling (water seal), rinsing, oxidation, and
3. Oxidation (at ca. 65 C in washing equipment aftertreatment as in the thermosol pad steam
with metering of additives) plant
4. Soaping (at ca. 95 C in special washing
equipment) Cold Pad-Batch Process for Reactive Dyes
5. Neutral washing (ca. 60 C, in 2 – 3 washing on Cellulose Fabrics (see Fig. 31). In this typ-
sections) ical semicontinuous process, the short duration
6. Cooling and final squeezing-off (in squeeze steam treatment is replaced by long storage at
rolls) room temperature.
The dye and alkali (reaction accelerator) are
Wet-Steam Vat Dyeing of Cellulose Fab- first padded on the fabric [78], [79]. The fabric is
rics (Fig. 30). First the vat dye is padded on the wound onto a roll and stored for ca. 5 – 10 h in
dry fabric. The liquor that contains the reducing the cold where reactive dye fixation occurs. The
agent is then applied to the fabric while it is still fabric is then washed and finished (see Section
wet. The usual intermediate drying is omitted. 4.1).
The dye is then fixed by steaming and oxidation The individual process steps are:
(see Section 4.3.4) [77, pp. 319, 357]. The term
‘‘wet-steam’’ here indicates the wet-in-wet dye- 1. Preparation of the dye liquor: addition of a
ing technique and not the condition of the steam. weighed amount of dye followed by addi-
In this technique, the fabric which is fed into tion of the alkali shortly before use to
the steamer is charged with a large amount of prevent undesired hydrolysis of the dye in
liquor, so that there is a danger of streaking if the the trough
liquor runs back. This depends very much on the 2. Application of the dye (cold padding at ca.
fabric. Fabrics with a high capacity for liquor 15 C to give ca. 55 – 80 % liquor pickup)
often give no problems. 3. Winding (cold, onto a roll)
4. Storage (cold, rotating batch, ca. 5 – 10 h)
Figure 30. A wet-steam plant for dyeing with vat dyes (courtesy of Ramisch – Kleinewefers)
A) Padding of liquor (Bicoflex foulard) and air passage; B) Kiss padding of chemicals; C) Steaming and aftertreatment
Vol. 36 Textile Dyeing 225
5. Washing cold (ca. 15 C) and hot (60 – and is then fixed in special yarn storage systems
90 C), washing machine or washing beam, [80].
preliminary rinsing and soaping
6. Aftertreatment (cold, wet-in-wet, with addi-
tion of auxiliaries) 2.3.4. Automatic Operation of Continuous
Dyeing Plants
2.3.3. Continuous Dyeing of Yarn and
Fiber The state of automation in the fabric finishing
industry has overall reached a high level.
By far the most important continuous dyeing The automation of continuous dyeing plants
process for yarn is that for dyeing with indigo differs from the automation of bath dyeing (see
[dyeing of warp yarns (slasher, rope lines) for Section 2.2.7), mainly in that constant condi-
denim material, ! Indigo and Indigo Colorants, tions are involved – requiring constant adjust-
Chap. 9.]. Dyeing with other dyes (vat and reac- ments – and that no time programs are
tive dyes) can be also performed on these plants, required.
the dyes are used alone or as additions to indigo. Measurement and control equipment exist to a
Dyeing with dyes other than indigo is, however, much greater extent in other industries, and the
rather unimportant. equipment used in fabric finishing represents
The continuous dyeing of flock is occasionally only a part of the wide range available. There
carried out, e.g., in a ‘‘steamer tube’’ (Seracant is no uniformity in the equipment used.
equipment for polyacrylic fiber), or by a padding Computer-integrated manufacturing (CIM) is
process in high frequency fixation equipment (at not (yet) widely used, presumably because the
ca. 80 – 95 C) [72]. product information available to the dyeing in-
To obtain space dyeing effects (yarns with dustry is still too generalized and expensive [81].
local variations in the amount of dye), the yarn The complex subject of the automation of
can be knitted to tubes and locally printed (vig- continuous processes is here split up into two
oureux process, ! Textile Printing). After fixa- different aspects to facilitate the discussion:
tion of the dye, the knitted product is unravelled
(knit-de-knit process). Yarn is also continuously 1. Automation of individual items of equipment,
dyed with local variation of the amount applied, mainly to improve their effect on the fabric
226 Textile Dyeing Vol. 36
2. Automation of assemblies of equipment, charged. Here, the distribution of the dye in the
mainly to improve their performance and fabric material (dye penetration and migration to
their potential for working together as a large the fabric surface) is presumably the important
unit factor. Considerable research effort is needed to
elucidate this effect and the often puzzling mid-
dle-to-edge unlevelness before a truly reliable
2.3.4.1. Important Process Stages and their
automation process can be developed [83].
Automation
Control of the Treatment Bath (Continu-
Selected process stages – dye application, prepa-
ous Washing Units). Linked to the dyeing
ration of baths, drying after padding – are de-
processes, sections of open-width washing ma-
scribed below in tabular form.
chines are widely used in important continuous
Characteristic process parameter (for both
process operations [47].
the fabric and the process), together with the
measurement and control elements needed for
determining and setting these parameters and for Process characteristic parameter Measurement and control
keeping them constant are as follows: Bath temperature temperature control (heating,
cooling, water mixing)
Bath renewal control of feed rate (fresh water,
Dye Application (Padding of the Dye Liquor) countercurrent) or of amount of
liquor on the fabric
Bath volume level control (overflow flaps)
Process characteristic Measurement and control pH of the liquor pH controllers, addition of acid,
parameter alkali, and buffering agents
Liquor pickup control via squeeze pressure Concentration of reducing or titration with redox probes as in-
(continuously regulated) oxidizing agents dicators or direct measurement
Middle-to-edge unlevelness control via variation of with multiprobes to control addi-
squeeze pressure over the roll tion rates [61], [76]
width Salt content conductivity measurement (elec-
Dye concentration in the photometric measurements trodeless or 2, 3, and 4 electrode
trough (transmission) of dye solu- systems) and control of dilution or
tions and dispersions salt addition
Indicators of the amount of dye applied to the fabric: Concentration profile in the bath control via partition walls, circu-
Dye concentration in the sur- on-line reflection measure- lation pumps, or location of feed
face zones of the fabric ments on the fabric in the points
visible range
Amount of dye liquor on reflection or absorption of
fabric microwaves (cm range) [67]
In practice, treatment baths have not yet reached
or IR [82]
Total amount of fabric fibers absorption of b-rays [67] a high level of automation. One reason for this
and liquor on the fabric may be the buffering capacity of the large bath
Volume of dye liquor required measurement of liquor added volumes employed (ca. 0.5 – 2 m3), which near-
per running meter to the pad trough
ly levels out concentration changes and automat-
ic control is therefore less important. This is even
more significant because dyeing of small fabric
A complete list of characteristics of the pad- batches (pieces) is becoming increasingly impor-
ding process would contain still more items, e.g., tant. Simple and reliable metering devices are
signal generators and receivers to ensure uniform available which automatically adjust to the fabric
fabric running speed [47] and to determine resid- running speed (e.g., Polycomat, Babcock).
ual moisture on the fabric after predrying, and the The addition of acid or alkali is mainly carried
absorbency of the fabric. Control of dyeing pick- out under automatic pH control. However, dam-
up is only seldom achieved only by means of age to electrodes (e.g., poisoning) and the pres-
instrumentation. ence of nonlinear transition functions in control
Finally, the amount of dye liquor charged is of characteristics still present problems.
less interest than the dyeing produced on the Equipment for direct measurement of reduc-
fabric. This can easily deviate by 10 % from ing and oxidizing agents is in the development
the figure expected from the amount of dye liquor stage. The most reliable method is still titration.
Vol. 36 Textile Dyeing 227
The main problem for a continuous plant is the drying air (heavy fabric requires higher tem-
that a constant dwell time is necessary for a peratures than light fabric), which takes some
consistent dyeing operation, whether the fabric time. Alternatively, the heat transfer rate can be
is light or heavy. Therefore, all weights of fabric varied by varying the rotation rate of the fans,
pass through the plant at the same speed and which produces a rapid reaction. Other devices
differences in their dyeing characteristic must be automatically clean the idler rolls that sometimes
compensated by other process parameters. become smeared with dye liquor (thickened)
after the predrying stage.
If the drying is included in a dyeing line, the
Drying after Padding (Intermediate Drying) dye fixation (fixation time) determines the fabric
running speed, and the drying equipment must
Process characteristic Measurement and control
parameter
run at a needlessly slow speed even with light
fabrics.
Intermediate and residual measurement: electrical resistance However, if the dried fabric is batched up, the
moisture content of the fabric of the fabric, microwaves (cm dryer can be used efficiently, as the light fabric
range), electrical capacitance,
cooling of the drying air, fabric
can be run rapidly, and the heavy fabric more
surface temperature slowly.
Fabric running speed, drying measurement: speedometer, va-
intensity, drying stress on the lues derived from two sources
fabric 2.3.4.2. Technology of Automation
Drying temperature (temper- measurement: air temperature,
ature profile) fabric surface temperature (con- General Process Control. It is first neces-
ditions suitable for the use of
antimigration agents)
sary to have local measurement and control
Energy consumption water content of exhaust air, e.g., equipment at or inside each machine. The mea-
‘‘atmospheric humidity pipes’’ suring instruments (sensors) provide the infor-
(Mahlo) mation (measured data and signals), and the
control equipment makes it possible to influence
the operation by means of control commands
(actuators).
The following refers to the two-stage inter-
mediate drying process (see Section 2.3.1.2).
It is important that all measurements should be Local Measurement and Control Equip-
made without contacting the fabric (to avoid ment. The measuring instruments (tempera-
streaking effects). ture, pressure, fabric running speed, longitudinal
The predrying stage (IR radiation dryer) usu- tension) are located very close to the point of
ally leads to a moisture content of 25 – 35 %. The measurement, and are designed with a direct
moisture content is usually measured indirectly drive of the display equipment (pointer and
from the surface temperature of the fabric (ther- scale).
mal radiation measuring equipment). In this hu- The closed-loop controllers are also con-
midity range, nonuniform migration can occur structed on this principle. These have a (mechan-
(middle-to-edge unlevelness, streaks, two-sided- ical) means of storing the set points. Their control
ness). The drying is controlled by varying the commands mostly go to valves, which are often
radiation intensity of the dryer. The fabric run- pneumatically actuated. The necessary control-
ning speed must not be changed because this ling action (types of water, countercurrent flow,
would lead to marking. outflow, etc.) are usually carried out by lever
Second drying by the hot flue process is systems or pneumatically.
considerably less intense, and therefore more The advantage of local measurement and
uniform, with very little danger of migration. control equipment is the low costs, but there are
The fabric has a longer dwell time in the dryer. disadvantages:
The residual moisture content of the dried fabric
is usually 0.5 – 6 %, and this is often determined 1. Inadequate supervision and fact that only
from the electrical conductivity of the fabric. The some of the functions take place automatical-
drying controller can adjust the temperature of ly lead to faulty adjustment of machines.
228 Textile Dyeing Vol. 36
2. The investigation and repair of faults can be sensor and actuator signals to digital form (field
difficult. Equipment is very individual, and bus operation). At present, many types of field
know-how and replacement parts are difficult bus are used, leading to unclear and nonstandard
to obtain. This is also true for calibration. operating systems.
Continuous dyeing production lines with pro-
Measurement and Control Equipment at a cess computers sometimes afford the possibility
Central Operator’s Desk. The local sensors of changing over to a kind of hand operation for
and associated control instruments are connected controlling the plant and trouble shooting. A
to a central operation point. Amplifiers are pro- complete set of control instruments (usually cen-
vided to form a standard signal from the sensor tralized) exists for hand control of the plant in
output, and for transmission to the central display spite of the costs.
equipment. Really useful software tools for trouble shoot-
A disadvantage is that determination of the ing are usually in short supply (high program-
weight per running meter of fabric is not carried ming cost, small number of possible machine
out because this is still very expensive. Thus, combinations).
quantities associated with the weight per running
meter are not available, e.g., the water consump- Intelligent Process Control. A computer is
tion expressed as L/kg fabric (from the water flow now expected to provide also support for the
rate), and the moisture content of the fabric in management of the dyeworks. The computer
wt % (from the amount of water per unit of area in should provide information on:
grams per square meter) or the steam consump-
tion per kilogram fabric. 1. Cost reduction (cost reporting and control)
Some control equipment (actuators) is set at 2. Minimization of reject lots (reproducibility,
the start of the lot, e.g., liquor flow control or flap buffering effect)
valves. Also, the regulators which act on the 3. Shorter treatment time of the goods (optimi-
control equipment are given their set points. zation of operations planning)
The centralized arrangement is considerably 4. Less production of wastewater (independent
more expensive than the localized equipment, optimization, washing process)
but has the advantage of security of operation. 5. Optimization of product range (amount and
range of stored materials, standardization of
similar products)
Important Advantages: 6. Development of new methods, e.g., by calcu-
1. Control is mainly from the operator’s desk, lation of the relationships between dyeing
and there is little hand operation of the ma- behavior and process parameters
chines. Change-over to operation with differ-
ent dyes and fabrics is partly automatic, and Personal computer programs are only avail-
uses control programs that can be called up. able for some of these areas [31], [26]. They are
2. In trouble shooting, only standard electrical usually written by dyeworks staff for particular
and pneumatic signals are needed for control. types of dye. The information required is often
only available indirectly (see also Section
Process Computer as Control System. 2.1.3.6). The simulation of a dyeing process on
Sensors, regulators, and control equipment pro- the computer screen to enable different proce-
duce signals of a type (digital) that can be read by dures to be evaluated is still at an early stage of
a process computer. Conversely, the computer development [32], [33], [36].
sends signals (control commands, parameters)
that can be understood by the equipment. Also,
a PC can undertake a high proportion of the 2.4. Laboratory Dyeing Techniques
process computing tasks, if suitable software is
available (on-line operation) [84]. 2.4.1. Objectives
Developments are now in the direction of
local control equipment that provides the neces- An important task of the laboratory is to carry
sary digital signals or converts the analogue out preproduction tests, especially of new
Vol. 36 Textile Dyeing 229
formulations, to give an indication of the results amounts, the dyeing equipment in the labora-
to be expected [85]. The laboratory also helps in tory cannot adequately represent the full-scale
maintaining consistency of production. It plant. The main aim is to match the patterns
should also decide whether tolerance ranges provided and to produce dyed material for
should be wide or very narrow. Factors to be fastness tests.
considered include dyeing rate, batch time, and
cost. Rope Dyeing Machines. The textile mate-
rial (hanks of yarn, woven or knitted material)
Important Individual Tasks of the Dye- is mounted on a carrier, usually of the double-
works Laboratory forked type, and moved up and down in the
bath. The dyeing bath is placed in a large and
1. Determination of Formulations for Produc- sturdy test tube in a temperature- controlled
tion Dyeing. Searching in the pattern collec- bath at between room temperature and ca.
tion, feasibility of producing the color shade 95 C. Rope dyeing machines are a mechanized
on the given substrate, transfer to the produc- form of the early method of rope dyeing by
tion plant. hand. A typical example of this is the Ahiba
2. Shading Formulations. Determination of dye apparatus.
additions during dyeing.
3. Testing of Dyed Products. The various fast- Beaker Dyeing [High-Temperature (HT)
ness properties are most important. Very spe- Bomb]. The textile material and liquor are
cialized methods and equipment are some- placed in a narrow, cylindrical, pressure-tight
times required (see Chap. 13). Supporting steel container with a screw top. The container
tests of mechanical properties of textiles are is placed in a high temperature medium (oil,
also carried out (see Chap. 3). sand, air, glycol, aluminum block [47], or an
4. Dyeing of Samples for Color Measurement infrared field [86]) where it is kept in continuous
(calibration curves). Preparation of special motion, so giving good interaction between the
dyeings of new fabrics supplied by the fabric and the liquor. Dyeing temperatures of
customer. 140 C can be reached in the HT bomb. This
5. Investigation of Defects and Recommenda- system has found wide application.
tions for their Correction.
6. Optimization (cost minimization, reduction of Through Flow Dyeing Equipment. A cer-
water consumption, minimization of dye con- tain range of laboratory equipment is available in
centration in wastewater, etc., selection of which the liquor flows through the textile mate-
dyes with improved mutual compatibility rial. This equipment requires a larger quantity of
[79]; improved matching of the fastness of textile. These types of dyeing equipment are used
lighter or darker shades; statistical analyses). for special tasks, a typical example being the
7. Reclamation Analyses. Investigation of sam- ‘‘Colorstar’’ equipment.
ples of rejected materials for quality discre-
pancies. 2.4.2.2. Small-Scale Production Equipment
8. New Methods and New Developments. Devel-
opment of methods of dyeing and finishing Batch Dyeing (Bath Dyeing). To provide a
new materials with the available machinery. meaningful representation of the dyeing condi-
Ideas for new effects and transformations in tions in full-scale equipment, larger textile sam-
the finishing process. ples (in the range 100 g to 10 kg) are necessary,
which usually make it possible to work with
2.4.2. Laboratory Dyeing materials of the form used in full-scale produc-
tion. Dyeing equipment taking samples up to ca.
2.4.2.1. Typical Laboratory Equipment 50 kg in weight covers the size range between the
laboratory and the very small scale production
The amount of textile material available for a equipment. In general there are laboratory ver-
laboratory scale dyeing operation is often in the sions of the equipment described in Sections
region of a few grams. With such small 2.2.3 and 2.2.4 [87].
230 Textile Dyeing Vol. 36
common than color discrepancies, effecting re- it is advantageous to prepare stable masterbatches
pair costs), ‘‘transfer factors’’ enabling colori- which are mixed shortly before use. These are
metric formulations to be converted to laboratory almost exclusively used in reactive dyeing.
formulations and then production formulations, At the pad trough the dye solution and dilute
test dyeing methods [79], distribution of the alkali are delivered by a single metering pump
additives for color shading, substrate, dyeing with two heads. The finished liquor being fed into
equipment, and, of course, ‘‘substrate calcula- the pad trough via a mixer. In this way, the
tions’’, e.g., viscose ! cotton [90], [91]. volume ratio of the two components is kept
constant even if the total liquor consumption
varies.
2.5. Techniques of Dispensing Thus, highly reactive dyes can be used in the
Products used in Dyeing cold pad-batch process, in which a sufficiently
rapid reaction takes place on the fabric while it is
2.5.1. Dispensing of Dyes stored (see Section 4.1). The very short time for
which the dye liquor is stored at room tempera-
The dispensing of dyes forms an important part of ture is not long enough to lead to any significant
dyeing technology [47], [92]. hydrolysis of the dye.
Amounts required for a dyeing operation
range from ca. 5 g dye (small batch of 50 kg Batchwise Dispensing of Dyes. This in-
fabric and a very low dye content, 0.01 %) to ca. volves the preparation of measured amounts of
50 kg dye (large batch of 500 kg fabric and dark dye as required by a formulation. The most
dyeing, e.g., black, requiring 10 % dye). Hand important requirements in such a system are:
measurement is much more common than fully
automatic metering for dyes. 1. Quantity range ca. 5 g to 50 kg
2. Measuring accuracy ca. 1 – 2 % of amount
Hand Weighing of the Dye. Hand weighing dispensed
of the dye still has advantages with which auto- 3. Dispensing rate, e.g., 10 formulations per
mation is only slowly catching up: hour
is required if several dyes are metered per include products that modify the liquor, e.g.,
pump. Pumps are only suitable for liquid dyes surfactants, dispersants, leveling agents, or com-
and liquid masterbatches. plexing agents, which are thus also products with
3. Flowmeters in which measurement is per- an affinity for the dye. The amounts required in
formed by direct measurement of flow rate the formulation are usually given in g/L.
or a counter system (water meter principle). The metered volume (mL) is given by the
For dispensing, valve switching is necessary following equation:
between several flowmeters of various sizes to
Cg WTex LR
give accuracy and metering capacity. Flow- Volume ¼
D
meters are only suitable for liquid dye mix-
tures and masterbatches. where C g is the concentration of the auxiliary in
g/L, WTex the weight of fabric in kg, LR the liquor
In general, the range of dyes is selected so that ratio in L/kg, and D the density of auxiliary in
the concentrated dyes from the same manufac- g/mL.
turer can be mixed and therefore do not require Powdered products are often converted into
preliminary dilution. stable masterbatches in simple dissolving
Liquid dyes and masterbatches are used for stations.
liquid metering systems. The masterbatches of- The most important measuring devices are
ten require special formulation to ensure storage metering pumps, flowmeters, and measuring
stability (dye sedimentation). cylinders.
Powdered and granulated materials are still at
present only metered by weighing systems. The
dye is kept in a container (silo) from which it is 2.5.3. Dispensing of Chemicals
fed into a feeding device (vibratory chute).
The main chemicals used in dyeing are salt,
alkali, acid, reducing and buffering agents. These
2.5.2. Dispensing of Dye Auxiliaries are often required in large quantities, and are
stored separately. Salts and liquids (alkaline
Dye auxiliaries, which must be matched very solution) are metered directly, salts from the salt
specifically to the formulation, e.g., retarders for wagons (mobile containers with feeding equip-
dyeing polyacrylic fibers, are usually dispensed ment), alkaline solutions from the solution wa-
like the dye. The products usually have an affinity gons (mobile containers with delivery pumps).
to the fiber. The quantities of auxiliaries required Stock solutions, e.g., hydrosulfite and alkali (vat
for the formulation are usually expressed as wt % dyeing, reductive washing) are prepared in a
of the weight of the fabric. Their concentration in powder dissolving station. The measured amount
the liquor therefore varies as the liquor ratio of powder is fed into a mixer container by a screw
varies. The metered volume (mL) is given by conveyor. The solution of alkali is added, and the
the following equation: powder dissolved. The solution is then delivered
through pipework to the point of use. Acid and
C% WTex 10 alkali can be added under the control of a pH
Volume ¼
D meter [60]. Alternatively, the addition can follow
where C % is the concentration of the auxiliary in a predetermined program which specifies the
wt %, WTex the weight of fabric in kg, and D the (absolute) amount, the addition time, and the
density of auxiliary in g/mL. For example, if the metering characteristics (linear, increasing rate,
concentration of a retarder is 0.7 %, its density decreasing rate).
0.93 g/mL, and the weight of fabric 100 kg,
0:7 100 kg 10
Volume ¼ ¼ 753 mL: 2.5.4. Preparation of the Initial Liquor
0:93 g=mL
Charge and its Replenishment
The other auxiliaries are usually dispensed with The required measured amounts of products must
the aid of a liquid metering station. These mainly be dispersed, diluted, or mixed, and then added to
Vol. 36 Textile Dyeing 233
the dyeing equipment. Details vary according to The masterbatch liquor (replenishment li-
the dyeing technique. quor), containing ca. 50 – 70 g indigo, is pre-
pared from indigo (100 %), hydrosulfite (excess),
and sodium hydroxide solution.
2.5.4.1. Batch Dyeing Alternatively, grades of indigo are available
(BASF) that already contain the reduced dye.
Dyes. This considerably simplifies preparation of the
Initial Charge. The measured amounts of replenishment liquor (see Section 4.4.2).
dye must be predissolved or prediluted, either at In pad dyeing the total concentration of dye
a central location or in situ on or in the dyeing and auxiliary in the liquor must exactly meet the
equipment. The volume of the liquor and hence requirements of the formulation. Therefore the
the concentration do not need to be exact. To liquor volume must be determined as precisely as
achieve this, the dyes required for the dyeing possible and the rinsing water must be included in
operation are predissolved or dispersed in con- the final volume of liquor. The predicted con-
tainers fitted with stirring or mixing devices, using sumption of liquor is calculated from the weight
a volume of water equal to ca. 10 % of the final of the fabric and the pickup. This figure is
volume of dye liquor, and this is added to the bath. increased to allow for the liquor volume in the
Transport of the product is by pumping or trough (ca. 10 – 100 L) and a safety factor.
gravity in inert pipework, and distribution is by Photometric measurements for control of the
valves or swinging arm distributors [93]. liquor preparations are under discussion.
The finished batch of liquor is transferred to a
Replenishment. When dyeing with a standing storage container near the equipment, and is
bath, the dye used must be replenished batchwise transferred by pumping as required into the
before each new batch of fabric. Replenishment is trough.
carried out with dye masterbatch solutions and The dispensing and mixing of liquid additions
dispersions.Therequiredquantitiesarewithdrawn to the liquor is described in Section 2.5.1.
with pulsed metering pumps from the silo and
distributed via valves to the individual dyebaths. Dyeing Auxiliaries and Chemicals (e.g.,
wetting agents and defoamers) are added to the
Auxiliaries and Chemicals. All the auxili- dyebath along with the dyes, and are then applied
aries needed for a treatment stage are added to the to the fabric.
bath at the same time, either directly or via a Liquid chemicals and stock solutions are pre-
central metering and mixing station [93]. diluted, usually as a part of the metering process,
The quantities and addition of products are and are added to the liquor.
usually called up by the dyeing program control Powdered products can be weighed out and
system. Good communication between the control made up into masterbatches which are then me-
computer for the dyeing equipment and the central tered to the process. Alternatively, the powder
metering and control computer is necessary. can be dispensed directly at the point of use in the
process (usually by screw feeders).
2.5.4.2. Continuous Dyeing Replenishing solutions are usually made up at
the point of addition to the dyeing operation.
Dyes. In continuous dyeing of warp yarn
with indigo standing baths and special wet-
in-wet methods of application and fixation of the 2.6. Colorimetry (! Dyes, General
dye are used. Survey, Chap. 3.)
A masterbatch of replenishment liquor con-
taining reduced indigo (indigo white, leucoindi- Colorimetry means the measurement of the
go) is metered into the dyebath. The fabric itself reflection spectrum of a sample and the interpre-
in a way controls the replenishment rate via (1) tation of this with the aid of special software. This
the difference between the amounts of liquor on software calculates color coordinates (CIELAB
the fabric entering and fabric leaving the bath and tristimulus values) and color differences, usually
(2) via the evaporation per pass (‘‘skying’’). for comparison purposes (patterns/samples).
234 Textile Dyeing Vol. 36
Alternatively, the software can calculate dye Pass/fail formulae [100] enable somewhat
formulations based on calibration curves, and more reliable decisions to be made concerning
can indicate the quality of a calculated formula- the acceptability of dyed products from a given
tion. The most important uses of colorimetry are fabric.
listed below: Representation of results in tabular form is the
In the laboratory colorimetry is used to sup- most comprehensive system, but for some pur-
port preparation of formulations and to evaluate poses is too detailed. Figures usually quoted are
the addition of dye for color shade adjustment, the color coordinates X, Y, and Z, the absolute
for the investigation of defects, and for quality CIELAB values (coordinates):
control. In production on-line color measure- a* ¼ red – green (þ, )
ment is used for the control of dye pickup, and b* ¼ yellow – blue (þ, )
as an aid to inspection of the fabric. L* ¼ lightness (light ¼ 100)
Colorimetry has virtually replaced visual as- C * ¼ chroma
sessment by the dyer. However, it cannot ade- H * ¼ hue (angle of 0 ¼ red, 90 ¼
quately take account of secondary effects (luster, yellow . . .),
dichromaticity, moisture in the sample, nap ef- and the color differences DE *, DH *, DC *, DL*,
fects, optical color effects with samples sewn Da*, and Db*, together with an identification
together). number of the sample.
the pattern), þdb (more yellow than the pattern); ties of the textile, together with physicochemical
sample d lies in the sector þda (more red than the properties such as wetting and swelling.
pattern), db (more blue than the pattern). Information on the following physical prop-
Although results from colorimetric compari- erties can be found in the literature:
son measurements are useful for the quality
control of the fabric, they are less useful to the
dyer for defect analysis and prevention. For Thermal and calorific data [102–104]
defect analysis knowledge of the concentration Amorphous and crystalline regions [105–108]
defects is required; these provide information Frictional behavior [109], [110]
about the dyeing operation (e.g., unintentional Hairiness of yarns [111–113]
retention of a dye in the bath) [101]. Conductivity and electrostatic charge
Another important application is in the calcu- [114–116]
lation of formulations. With a new pattern, for- Stiffening and strengthening [111]
mulations are calculated with the aid of the Shrinkage behavior [117]
calibration curves. For this, K/S values (approxi- Surface appearance [118–120]
mately proportional to concentration; K is the
coefficient of absorption, S the coefficient of The chemical properties of the textile sub-
scattering, see Chap. 12) are calculated from the strate and the functional groups that cause bond-
measured reflection values. The K/S curves are ing of the dye are described in detail in Chap-
then superimposed until the K/S spectrum of ters 4, 5, 6, 7, 8, 9, 10, 11.
the pattern is matched. This enables an estimate
to be made of matching, fastness properties, and
costs, and a series of laboratory tests are carried 3.2. Fibers [121–125]
out until the pattern is matched with sufficient
accuracy. (see also, ! Fibers, 1. Survey, Chap. 3.; ! Fi-
bers, 16. Testing and Analysis, Section 2.3., !
Fibers, 16. Testing and Analysis, Chap. 3.)
2.6.3. Developments in Colorimetry The fineness (cross section) of the fiber is an
important geometrical parameter. The titer (mass
The development of colorimetric measuring in- per 10 km fiber length, unit dtex) is determined
struments is proceeding rapidly (e.g., hand-held from the fineness and the density of a fiber. The
instruments [47], [97] and photo-acoustic color specific surface area (ca. 50 – 300 m2/kg) is also
measurement). important for the dyeing process, indicating the
The development of the interpretation of mea- area of the surface into which the dye diffuses and
surements is remarkably stagnant. After a mea- the extent of the dyed layer (ring zone of the fiber
surement, the software should be able to provide impregnated with dye, Fig. 34). This determines
all possible interpretations, as with data-driven dye consumption: a thicker fiber takes up dye
expert systems. Thus, derivation of such infor- more slowly because the specific surface area for
mation as the characterization of unlevelness, the the entry of dye is smaller. It also consumes less
elucidation of variations in dye properties, and dye (formation of a ring zone [126], [127]),
the assessment of migration and two-sidedness is which partially compensates the lower dyeing
often desirable, but is still only at the develop- rate. This holds, especially for synthetics, when
ment stage. the orientation of the fibers is nearly the same.
For a uniform dye concentration in equally thick
ring layers of different fibers, the average dye
3. Physical Properties of Textiles concentration in the thicker fiber is lower, e.g.,
Important for Dyeing 75 % in the example given in Figure 34. If
the transparency of the fibers is not too high the
3.1. Classification of Textile Properties visual impression of both fibers should be
the same. Some physical properties of various
The physical properties described here include all textile fibers are given in Table 6. (The figures
the geometrical, mechanical, and optical proper- listed are mean values of those cited in [126],
236 Textile Dyeing Vol. 36
Type of fiber Density, g/cm3 Diameter, mm Titer a, dtex Surface b, m2/kg B c, g/dtex EB d, %
Figure 36. Reactivities of established anchor systems and optimum dyeing temperatures in exhaustion dyeing [153]
number, fewer than ten are currently of practical Hydrolysis and alcoholysis are competitive
importance for dyeing cellulose fibers (Fig. 36). processes, both being first-order reactions [149],
[150]. The ratio of the rate constants of the
Hydrolysis and Reactivity. Two possible reactions with cellulose and with hydroxide ions
reaction mechanisms exist: addition and sub- (ratio cellulose-O : OH) is termed selectivity
stitution. and can be determined easily in a homogeneous
Addition anchors include, for example, vinyl- medium by using model substances. For triazine
sulfones anchors, a decrease in selectivity depending on
the leaving group can be observed in the order
end of the dyeing process relative to the total cellulose fibers, which have a marked skin –
amount of dye employed) is important, particu- core structure, the outer parts of the fiber can act
larly for ecological and economic reasons. The as a diffusion barrier.
fixation yield depends on the chemical nature of
the anchor and many other factors [154]. Stability of the Dye – Fiber Bond. Be-
cause of the large variety of reactive dyes, gen-
Substantivity. Substantivity is given by the eralizing about colorfastness is difficult. While
ratio of the amount of dye in the fiber to the wetfastness is determined mainly by the anchor
amount in the dye liquor after chemical equilib- system used, most other fastness properties de-
rium has been reached (without chemical reac- pend on the dye as a whole or the chromophore
tion). In analogy to direct and vat dyes, the present. Most reactive dyes are azo or anthraqui-
adsorption properties of reactive dyes can be none derivatives whose standard of fastness var-
represented by the Freundlich relation. Substan- ies greatly. Phthalocyanine, formazan, and tri-
tivity is a necessary precondition for reaction phenyldioxazine derivatives are also very
with the fiber. Dye that has not become attached important.
to the fiber is hydrolyzed when the alkali is In addition, application conditions [155] and
added and lost to the dyeing process. For mono- finishing processes (! Textile Auxiliaries, 7.
anchor dyes, high substantivity correlates with Finishing Agents) can affect fastness. Thus, with
attainable fixation yields to a good approxima- some resin-finished textiles (dimethylolpropyle-
tion. Substantivity is influenced by the chemical nurea finish) a decrease in lightfastness is
constitution of the dye and the process para- observed.
meters. In general, high substantivity is ob- Significant differences in the stability of the
tained with low dyeing temperature, a low bond toward hydrolysis can be observed in the
liquor ratio, the addition of electrolytes (e.g., anchor systems listed in Figure 36. The ether
NaCl or Na2SO4) to the dyebath, and low dye bond to cellulose formed by addition anchors
concentration. An extended planar structure of (vinylsulfone dyes) is extremely stable to acid
the dye molecule is believed to favor high hydrolysis. Its instability in alkaline solutions is
substantivity. demonstrated by the poor fastness to hot sodium
The dyer must also consider the effect of the carbonate solution. In general, the stability of
substrate. Substantivities for mercerized cotton substitution anchors (fluorochloropyrimidines,
and regenerated celluloses are higher than those monochlorotriazines, and monofluorotriazines)
for cotton. is significantly higher in alkaline solution. How-
Limits to substantivity exist in practice. If the ever, fastness can be reduced considerably by the
substantivity is too high, problems can occur presence of electron-attracting substituents in the
with washing off of unfixed dye, wetfastness, or anchor. An example is provided by dichlorotria-
uneven final shade. In continuous processes, zines, which are more reactive than monochlor-
tailing can occur (see Section 4.1.2). otriazine dyes. The hydroxyl group formed by the
second chlorine atom after reaction of the first
Diffusion Rate. The diffusion rate is the rate with cellulose leads to a decreased electron den-
at which dye is transported to the interior of the sity in the heterocyclic nucleus and to a signifi-
fiber material. A high diffusion rate leads to rapid cant increase in the rate of cleavage of the dye –
establishment of dyeing equilibrium and rapid fiber bond.
leveling out of irregularities in the dyeing of the
substrate. It also facilitates washing off the hy-
drolyzed dye. Increased dye substantivity is fre-
quently combined with lower diffusibility. The
diffusion rate doubles with a temperature in-
crease of 10 – 20 C.
The substrate also has an important influence
on diffusion of the dye. The diffusion rate in-
creases with caustic soda treatment or merceri-
zation of cotton. However, with regenerated
Vol. 36 Textile Dyeing 241
One aim of the introduction of heterobifunc- process has advantages in dyeing materials that
tional anchor systems has been to combine the are difficult for liquid to penetrate (e.g., dyeing
good fastness profiles of different anchor systems wound packages in a circulating-liquor ma-
(! Reactive Dyes). chine). A preceding exhaustion step aids in pre-
venting an uneven final appearance. The exhaus-
tion step is usually started at 30 C. Dye and salts
4.1.2. Dyeing Techniques [148], [157] are added at the start or portionwise. The salt
concentrations employed depend on the substan-
A wide range of reactive dyes of varying consti- tivity of the dye and the dye concentrations used.
tution is available which are suitable for many For <0.5 % dye based on textile weight, salt
different applications. In most cases, dye is fixed concentrations of 10 – 30 g/L are recommended;
to the substrate under alkaline conditions. How- for less substantive dyes, up to 50 g/L NaCl. For
ever, dyes containing phosphonic acid groups deep shades with dye concentrations of >4 %, salt
and quaternary nicotinic acid derivatives (! Re- concentrations of ca. 50 g/L are used; with vi-
active Dyes) are exceptions to this rule. Dyes nylsulfone dyes having low substantivity, up to
with phosphonate groups are applied in an acid 80 g/L. After the dye absorption phase, and some-
dyeing bath, quaternary nicotinic acid deriva- times also an additional leveling step (at tempera-
tives require neutral conditions. These dyes are tures sometimes higher than the fixing phase),
applied under weakly acid or neutral dyeing alkali is added. With hot dyers, a uniform dye –
conditions and are used mainly for dyeing poly- fiber reaction can be obtained by controlled heat-
ester – cotton blends. ing. Heating rates are between 1 and 2 C/min. In
The suitability of a reactive dye for a particu- the case of cold dyers, fixing can be controlled
lar application depends not only on its reactivity, smoothly by means of pH. Alkali can be added
but also on properties that are determined by its either in portions or by metering. Sodium carbon-
overall structure, such as solubility, substantiv- ate or mixtures of sodium carbonate and sodium
ity, and diffusion. Special recommendations are hydroxide are used almost exclusively today as
therefore made by manufacturers for each type of the fixing alkali. Here, too, the amount of alkali
dye. is determined by the reactivity of the system and
About 20 % of reactive dyes are used in textile the depth of shade desired. Cold dyers are
printing, 30 % in pad dyeing, and 50 % in ex- applied at lower pH values. The pH is normally
haustion dyeing processes. adjusted with sodium carbonate. Warm and hot
dyers are usually fixed with mixtures of sodium
Exhaustion Dyeing. Exhaustion dyeing is a carbonate and sodium hydroxide. Typical con-
batch process. Loose stock, yarn, or piece goods centrations are 5 g/L of sodium carbonate and
can be dyed by this method. Equipment consists 1 – 2 mL/L of sodium hydroxide solution (con-
e.g., of package dyeing equipment, hank dyeing centration 38 Be or 440 g/L). The fixing time is
machines, jiggers, winch becks, or dye spraying 45 – 90 min.
machines (see Section 2.2.3). The general trend is After dyeing, the liquor is usually drained off;
toward the use of concentrated (‘‘short’’) liquors the material is rinsed and then washed off with
(i.e., toward dyeing with the smallest possible addition of auxiliaries. The washing intensity
volume of dyebath compared to the textile used). depends on the substantivity of the dye hydroly-
With woven textiles, liquor-to-goods ratios of sate. The more highly substantive hot dyers
3 : 1 can be achieved; with knitted goods, 5 : 1. require longer washing times or more wash cy-
In the exhaustion dyeing process, highly or cles at higher temperature. With alkali-sensitive
moderately substantive dyes are usually em- vinylsulfone dyes soaping at the boil must be
ployed. The two main processes are the ‘‘all-in’’ carried out in a neutral or weakly acidic liquor, to
process and the stepwise process. In the all-in prevent cleavage of the dye – fiber bond.
process, the dye, the salt, and the alkali are all
added to the dyeing bath at the start of dyeing. Pad Dyeing Process. In this so-called im-
The stepwise process consists of an exhaustion pregnating process the dye, additives, and alkali
and a fixing phase (i.e., alkali is added only after are applied to the textile by dipping followed by
the dye has absorbed to the fiber). The stepwise squeezing out (see Section 2.3.2). Fixing of the
242 Textile Dyeing Vol. 36
dye on the textile is carried out in a subsequent mixtures of sodium carbonate and sodium hy-
step. droxide are employed. If the batches are stored in
In these processes, dye and alkali can be the open, carbon dioxide from the air can cause a
applied together or separately. In the one-bath pH decrease and hence a lighter final shade at the
process, the so-called pad liquor stability is selvedges. A high process reliability can be
important. This term denotes the stability of the achieved by utilizing the buffering action of
dye to hydrolysis as a function of time. With waterglass (sodium silicate). In the past, additions
increasing reactivity of the dye (vinylsulfone < of up to 100 mL/L of waterglass (concentration of
dichloroquinoxaline < monofluorotriazine < di- waterglass solution 38 Be ¼ 1.35 g/mL) were
fluorochloropyrimidine<dichlorotriazine dyes), recommended. For environmental reasons, the
the risk of a loss in color strength with too long a trend today is toward lower concentrations or
dwell time in the pad box or replenishing tank complete avoidance of sodium silicate. By wrap-
increases. For this reason, metering equipment is ping the batches in plastic film, the negative
commonly used. Dye and alkali are metered sep- effects of carbon dioxide can be limited to the
arately into the padder, which means that the dwell actual padding time. If necessary, the solubility of
time in the pad box can be kept to a minimum. In the dyes can be increased by addition of urea (up
addition, pad boxes are now constructed so that the to 100 g/L). To obtain a level fabric appearance,
liquor volume is as low as possible, and is, on the fabric must be uniformly absorbent. The
average, replaced within 5 min. maximum possible liquor uptake for cotton (ca.
When selecting dyes, the dyer must consider 60 – 80 %) is ca. 10 % lower than the figure for
the possibility of so-called tailings. This refers to regenerated cellulose. To achieve evenness of
differences in shade and depth of shade between dyeing by means of higher liquor pickups, aux-
the beginning and end of the batch of fabric. With iliaries that reduce running-down and dripping-
highly substantive dyes, the liquor running back out of the liquor can be added. Rotating batches
into the padder from the squeezing rollers has a are then used. Nowadays, highly or moderately
lower dye concentration than the initial liquor. reactive dyes are used for the cold pad-batch
This causes a gradual depletion of dye in the process. For a complete dyeing reaction, 2 –
liquor. Also, especially with regenerated cellu- 8 h is required. However, this time is sometimes
lose fibers, so-called negative tailing occurs. The extended to 24 h for reasons of work organiza-
dye uptake calculated from the liquor pickup is tion. Storage at higher temperature, as in the pad
then greater than the actual figure. roll process, or the use of accelerators (e.g., 1,4-
In general, pad dyeing can be a semicontin- diazabicyclo[2,2,2]octane) for slow-reacting
uous or continuous process. dyes (e.g., monochlorotriazine anchor) has not
widely spread. After dyeing, the material is rinsed
Semicontinuous Processes. Semicontinuous and washed off in open-width or rope washing
retention processes were developed especially machines. Washing off directly on perforated
for reactive dyes. The cold pad-batch process is beams is sometimes employed for economic rea-
by far the most important. After the textile has sons. The material is then dried.
been padded with dye and alkali, the material is
either plaited down in a box wagon or rolled up Continuous Dyeing Processes. In continu-
into batches. Fixing takes place during storage. ous dyeing processes, padding, fixing, wash-
The cold pad-batch process is of special interest ing-off, and drying are carried out in one process
from an economic point of view. The amount of line. Two different types of processes exist: dry-
alkali and the dwell times required for dye fixa- heat and steaming processes. The dry-heat pro-
tion depend on the reactivity and quantity of the cess can be either the single-stage pad dry process
dye. With cold dyers, adequate fixation can be or the thermofixation process. Hot dyers are
achieved with sodium carbonate or bicarbonate; preferred for use in thermofixation. Advantages
with dichlorotriazine and monofluorotriazine of the thermofixation process include good color
dyes, sodium carbonate concentrations of 2 – yields and covering immature cotton. The dye
30 g/L are used. In these systems, ca. 10 g/L of and alkali are padded at the same time. The
trisodium phosphate can also be used. With less preferred alkali is sodium carbonate, used at a
reactive systems, sodium carbonate solution or concentration of 10 – 30 g/L. For less reactive
Vol. 36 Textile Dyeing 243
can significantly increase the degree of exhaus- (! Reactive Dyes) [161]. The main emphasis
tion and fixation yield of reactive dyes. If reactive of research was on the replacement of possibly
groups are introduced into cellulose, the possi- carcinogenic benzidine dyes (see Chap. 14) and
bility arises of bonding not only reactive dyes but on the improvement of pretreatment and after-
also nucleophilic direct dyes covalently to the treatment processes.
cellulose. Only in individual cases do direct dyes
Of the combined techniques (item 2 above), achieve the brilliance of reactive dyes. The light-
the system BASF Basazol was the first to be fastnesses of substantive dyes covers the entire
successful commercially. After finishing the cel- scale from 1 to 8, meeting the highest require-
lulose fiber with the trifunctional cross-linking ments. With increasing depth of color the wet-
agent 1,3,5-triacroylaminohexahydro-1,3,5-tri- fastnesses decrease to such an extent that direct
azine, dyes containing sulfonamide groups were dyeings must generally be aftertreated (see Sec-
applied with high fixation yields. The Indosol tion 4.2.7). Most direct dyes are characterized by
system (Sandoz) is still used today. Here, copper excellent affinity to the fiber (i.e., dye liquors
complex dyes are used that can form mixed contain very little dye at the end of the dyeing
complexes with aminated resins. The high wet- process). This is of great importance for ecologi-
fastness is explained by covalent bonds between cal reasons.
the resin and fiber.
However, the practical importance of this
technique is still relatively low. Possible reasons 4.2.2. Dyeing Principle
for this include the additional cost of applying the
dyes, changes in handling of the cellulose fiber, Dyeing with direct dyes is based on the affinity
occasionally unsatisfactory fastness properties, of the dye for the cellulose fiber (substantivity).
and ecological problems. This affinity depends on the type of chromo-
phore and can be influenced by the choice of
dyeing parameters (see Section 4.2.4). Chromo-
4.2. Dyeing with Direct Dyes phores are azo compounds (! Azo Dyes, 1.
General), stilbenes (! Azo Dyes, 3. Direct
Before the first synthetic dyes were made in (Substantive) Dyes), oxazines (! Azo Dyes,
1856, natural dyes of plant or animal origin were 2. Anionic Dyes), or phthalocyanines (!
used in the dyeing of textiles [160]. In most Phthalocyanines) [162]. They always contain
cases, the application of these dyes required solubilizing sulfonic acid groups that are ion-
time consuming process steps, e.g., mordanting ized in aqueous solution. The dye molecule is
or vatting. present as the anion. As a result, an electrolyte
Sun yellow (1883) and Congo red (1884), the must be added to the dye liquor because cellu-
first representatives of direct or substantive dyes lose fibers have a negative surface charge in
(! Azo Dyes, 3. Direct (Substantive) Dyes), can water, which repels the dye anion. The cations
be used on cellulose fibers ‘‘directly’’ (i.e., with- of the electrolyte neutralize the negative charge
out mordanting). Because of their easy handling a and favor the aggregation of dye ions on the fiber
variety of direct dyes has been developed. (salting-out effect). Exothermic adsorption can
be described with the help of Freundlich or
Langmuir adsorption isotherms [163]. After
4.2.1. Applications and Properties adsorption dye molecules diffuse from the sur-
face through the fiber pores to the amorphous
Direct dyes account for 11 % (1990) of the areas of the cellulose. The rate of diffusion can
worldwide consumption of textile dyes; 75 % of be controlled by the dyeing parameters. Dyes
this amount is used to dye pure cotton or viscose are bound to the fiber by hydrogen bonds or van
substrates, and the rest is employed in dyeing der Waals forces. Without additional measures
mixed fabrics (for use in paper dyeing, see ! (see Section 4.2.7), the strength of these bonds is
Paper and Board). so low that the dyes can be washed out of the
Substantive dyes were not developed further fiber again. At dyeing equilibrium, the rate of
as intensively as, for example, reactive dyes absorption is equal to the rate of desorption.
Vol. 36 Textile Dyeing 245
80 – 90 C and the dye continues to adsorb, proved by aftertreatment, giving fabrics that are
resulting in the same depth of color as in normal fairly fast to water and perspiration and, in ideal
dyeing processes. cases, washable up to 60 C. The improvement in
fastnesses is achieved by reducing the solubility
Pad Processes. In these continuous or semi- of the anionic dyes. This occurs by enlargement
continuous processes, the fabric is first soaked by of the molecules via the formation of saltlike
passing it through a trough filled with dye solu- compounds with cationic aftertreatment agents.
tion. Excess liquor is subsequently removed by The fixation of the saltlike compound can be
squeezing the fabric between rubberized rolls enhanced by cross-linking or by formation of
(padding). The substantive adsorption of dyes covalent bonds to the fiber (! Textile Auxili-
during padding is avoided by moving the material aries, 5. Dyeing Auxiliaries). For certain azo
rapidly, preferably at ambient temperatures, and dyes, substantial improvement in lightfastness
employing minimum amounts of pad liquor. Op- can be achieved by metal-complex formation
timal distribution of the dye is later obtained by (! Metal-omplex Dyes, Section 5.1.2.). A com-
either thermal treatment or longer storage. bination of these aftertreatments produces espe-
In thermal treatment, the material is passed cially good fastnesses.
through a steamer in 1 – 3 min without interme- Not only formaldehyde, one of the aforemen-
diate drying (pad steam process). Alternatively, it tioned cross-linking agents, but also metal com-
is heated to 80 – 85 C and rolled up in a closed plexes are discussed intensively because of the
chamber where it is kept for 2 – 8 h ( pad roll ecological aspects of these compounds. The im-
process). provement in fastness by means of diazotization
In the cold pad-batch process, the padded and coupling has decreased in importance be-
material is rolled without heating and stored at cause of the resulting changes in shade.
room temperature for 8 – 24 h.
The pad jig process represents the easiest type
of fixation of pad dyeings. The material padded 4.3. Dyeing with Anthraquinone Vat
with dye is passed through a salt liquor in a jigger Dyes
at 80 – 90 C, thus preventing desorption of the
dye. In this process, additional dye can be used Vat dyes are water-insoluble, organic pigments
for shading (see Section 2.2.5.2). that are used to dye cotton and other cellulose
All the processes mentioned above are fol- fibers. The principle of vat dyeing is based on
lowed by quick rinsing with cold water. chemical reduction of these dyes to the leuco
compounds (which are soluble in aqueous alkali
and exhibit fiber affinity), followed by reoxida-
4.2.6. Special Processes [[161] and tion to the water-insoluble starting dye within the
references cited therein] fiber.
Approximately 10 – 15 % of cellulose fibers
An established process is the simultaneous or cellulose-containing fiber blends are dyed with
bleaching and dyeing, permitting cost reduction vat dyes. The total consumption of vat dyes is
by combining two treatment steps. However, this about 22 000 t/a (1993) of commercial products,
process can be performed only with selected without indigo.
direct dyes. Dyeing processes with additional
energy fields (e.g., ultrasound, magnetic fields,
radioactive irradiation, or high-temperature 4.3.1. Chemistry of Vat Dyes
treatment) or with redox systems (persulfate or
periodate) have not yet proved useful in practice. Two main groups of vat dyes are distinguished
chemically:
4.2.7. Aftertreatment [161], [168] 1. Indigoid vat dyes are derivatives of indigo and
thioindigo (! Indigo and Indigo Colorants).
As a rule, the wetfastness of direct dyes does not Leucoindigo compounds have a comparative-
meet the demands of daily use. It can be im- ly low affinity for fibers. Thus, these dyes are
Vol. 36 Textile Dyeing 247
in wastewater must not exceed maximum per- In the initial phase of dyeing, vatted dye is
missible values stipulated by law. absorbed very quickly by the fiber. Extensive
Thiourea dioxide has a stronger reducing exhaustion of the bath is achieved after 10 to
effect (1100 mV) than hydrosulfite. Therefore, 15 min. The dye is then present in a high con-
with sensitive dyes, a risk of overreduction exists. centration in the outer regions of the fiber, but its
In addition, the oxidation products of thiourea distribution may still be entirely uneven (unle-
dioxide contribute to the nitrogen and sulfur vel). In the subsequent leveling phase, the dye
contamination of wastewater. diffuses into the fiber and the fiber becomes dyed
Organic reducing agents such as hydroxyace- uniformly. The more evenly the dye absorbs to
tone (Rongal 5242, BASF) do not contribute to the fiber and the stronger the diffusion, the more
the sulfur contamination of wastewater. Howev- level is the dyeing. Dyes that are less substantive
er, the reducing effect of hydroxyacetone is much absorb more slowly and evenly in the initial
weaker (810 mV), so it cannot replace hydro- phase and exhibit more favorable diffusion prop-
sulfite in all applications. For this reason, a erties. Diffusion can be improved by increasing
combination of hydrosulfite – hydroxyacetone the temperature. Leveling agents [176] can fa-
is recommended to lower the sulfur content in vorably influence absorptive behavior in the
wastewater. The use of hydroxyacetone is re- initial phase because they themselves possess a
stricted to closed systems because it forms high affinity for the dye and release it in a
strong-smelling condensation products in alka- controlled manner during the course of dyeing
line solution. (! Textile Auxiliaries, 5. Dyeing Auxiliaries)
Systems for electrochemical vatting by means [171], [176]. However, a certain amount of dye is
of electric current in the presence of a mediator, retained by the leveling agent, which results in
an electron carrier such as Fe2þ, or anthrahy- slightly weaker shade.
droquinones have been described [172]. Howev-
er, these methods have not yet been used in
practice. 4.3.4. Oxidation
The vat dyeing system is also supported by
auxiliary agents. Dispersing agents prevent the After absorption by the fiber, the leuco dye is
agglomeration of pigment particles or the floc- converted to the original pigment by oxidation
culation of slightly soluble components such as and, in this way, fixed to the fiber. Oxidation can
vat acids or the impurities in cotton. If the be achieved spontaneously with atmospheric
presence of alkaline-earth ions is expected be- oxygen or by the addition of oxidants, such as
cause of the use of hard water, the addition of hydrogen peroxide, perborate, or 3-nitrobenze-
complexing agents is required. nesulfonic acid, to the liquor.
After the dyeing process, the material is usu-
ally rinsed with water to remove unfixed dye and
4.3.3. Dye Absorption in the Exhaustion decrease the alkalinity of the liquor. Depending
Process [173], [174] on the oxidizing agent, oxidation is carried out at
pH 9 – 12 and 50 – 60 C.
In the dissolved form, the vatted dye is present as The leuco dye present in wastewater is also
the sodium leuco compound, either as a single converted to water-insoluble pigment, which can
molecule or as a complex of a few dye molecules easily be separated mechanically or adsorbed to
[175]. clarification sludge. Thus, colorization of the
In the exhaustion process, the higher the wastewater by vat dyes is negligible.
affinity, the more complete is the absorption of
the dye by the fiber. The degree of absorption of
dyes generally depends on dye concentration, 4.3.5. Aftertreatment (‘‘Soaping’’)
liquor ratio, temperature, and possibly the elec-
trolyte added [173]. Sodium salts of leuco vat After oxidation, all vat dyeings are subjected to
dyes have a high affinity for the fiber; the ex- heat treatment in the presence of water. As a rule,
haustion of the bath is generally between 80 and treatment is carried out in a weakly alkaline
90 % in exhaustion dyeing. detergent liquor (soap was used in the past) at
Vol. 36 Textile Dyeing 249
boiling temperature. The final shade is obtained bath after a vatting time of 10 min. Depending on
by this treatment, and the more important fast- the depth of shade, dyeing is performed for 30 –
ness ratings (e.g., light- and chlorine-fastness) 60 min and completed in the usual manner (rins-
are improved substantially. Thus, this soap ing, oxidation, soaping).
treatment is not restricted to the removal of
pigment particles adhering to the surface but is Preimpregnation Process. At first, the dye
an important individual step in vat dyeing. The liquor contains only the dye as a water-insoluble
processes occurring during soaping are un- dispersion. After the temperature is increased
known. Crystallization of amorphous dye par- and, if necessary, sodium hydroxide solution and
ticles or coarsening of primary particles by salt are added, the pigment partially deposits on
aggregation is assumed to occur [177]. If soap- the fiber. After the reducing agent is added,
ing takes too long, migration of the aggregates to vatting occurs rapidly and the dye is absorbed
the surface of the textile can cause deterioration by the fiber. As a result of partial deposition of the
of the rub-fastness. dye in the nonsubstantive form, the evenness
(levelness) of dyeing is improved. Prepigmenta-
tion is conducted in a jigger and is often used in
4.3.6. Dyeing Techniques [178] dye packages (cheese, warp, yarn, and piecedye-
ing beams).
Vat dyeing can be carried out by using various
techniques. Batch and continuous dyeing pro- Semipigmentation Process. Semipigmenta-
cesses can be used. The dyeing properties of vat tion is used preferentially for dyeing lighter
dyes enable the processes to be adapted to dif- shades. Dye, sodium hydroxide solution, and
ferent machines. reducing agent are added to the dyebath, and
dyeing begins immediately at room tempera-
Batch Processes. In batch processes, the ture. Depending on the vatting rate of the dyes,
dye must attach to the textile material from the only a small amount of substantive leuco dye is
dyebath. Therefore, the affinity and leveling-out present intially. For this reason, absorption
properties of the dyes are of special importance. proceeds more slowly and evenly. With in-
Dyeing is conducted in various circulatinggoods creasing dyeing temperature, more and more
machines (e.g., jigger, winch beck, jet, and over- dye is converted to the leuco form and can be
flow) and circulating-liquor machines (yarn, absorbed by the fiber.
piece, and package dyeing machines) (see Sec-
tion 2.2.4). High-Temperature Process. The leveling-
Vat dyes are divided into groups according to out properties of vat dyes can be improved by
their affinity for the fiber and the amount of alkali increasing dyeing temperature. In the high-tem-
required for dyeing: The following abbreviations perature process, dyeing is conducted at 90 –
are used: IK (I ¼ Indanthren, K ¼ cold), IW 115 C.
(W ¼ warm), and IN (N ¼ normal). The IK dyes In bath dyeing, the substrate can be dyed in
have a low affinity for the fiber; they are dyed at various processing forms. A distinction is made
20 – 30 C and require little alkali. Salt is added between loose material (flock, card sliver), yarn
to increase the absorption of these dyes. The IW (cheese, hank), garments (socks, pullovers, T-
dyes have a higher affinity than IK dyes. Dyeing shirts, etc.), and fabrics (wovens, knitwear) (see
is performed at 40 – 45 C with more alkali and Chap. 3).
little or no salt. The IN dyes are highly substan-
tive and applied at 60 C. They require much Continuous Processes. Vat dyes are espe-
alkali but no addition of salt. cially suitable for continuous dyeing because of
Dyeing with vat dyes is performed according their clearly defined configuration during the dye-
to the following processes: ing process (pigment form, leuco form). Dyeing is
performed according to the pad steam process or
Leuco Process. Auxiliaries, dye, sodium hy- the wet steam process. The continuous process is
droxide solution, and reducing agent are added to used almost exclusively for dyeing woven fabrics
the dyebath. The textile is introduced into the and to only a small extent for knitwear.
250 Textile Dyeing Vol. 36
In the pad steam process, which is most The indigoid colorant thioindigo and its
frequently applied, the textile is impregnated in derivatives are also important vat dyes.
a padder with the aqueous dye dispersion in the Because of the low affinity of vatted indi-
presence of an antimigration agent and a wetting goid dyes for the fiber, these dyes are used
agent, if required. The material is squeezed until mainly in textile printing. In comparison with
it has a specified residual moisture content and other dyes, indigo occupies a special position
then dried. Subsequently, the fabric is passed because it is used almost exclusively for dyeing
through a chemical padder, which contains the warp yarn in the production of blue denim.
required amounts of alkali and reducing agent, Being identical to the natural material, indigo
and is fed immediately to a steamer. In the has also been used in dyeing environmentally
steamer, the dye is fixed for 45 – 60 s under friendly clothing.
saturated steam conditions at a wet-bulb temper-
ature of 99 C at sea level pressure. After steam-
ing, the material is rinsed, oxidized, and soaped 4.4.2. Dyeing Technique
in an open-width washing machine.
To achieve maximum fixation yield and depth Indigo is available as a powder, granulate, or
of shade, dyes must be very finely dispersed. liquid preparation. The dyeing technique has not
However, fine dispersion also increases the mi- changed over the years and, like vat dyeing,
gration of dye particles during intermediate dry- involves the following steps (see Section 4.3):
ing. For this reason, antimigration agents are
used (polyacrylates, alginates, etc.), which have 1. Dissolving of the dye by reduction in alkaline
an agglomerating effect on the pigment particles medium
and thus restrict their mobility during the drying 2. Dyeing in the vat
process [179]. 3. Oxidation on exposure to air
The wet-steam process is used mainly for
voluminous open fabrics with a high liquor- The first step, dissolving of the dye, can now be
carrying capacity (e.g., toweling, cord, velvet). omitted by using solutions of pre-reduced indigo
Unlike the pad steam process, this process does (leucoindigo). In this way, about half of the
not require drying after dye application in the reducing agent (depending on the type of ma-
padder (energy savings). chine) required for dyeing can be saved.
The continuous dyeing process is especially As a result of the relatively low affinity of
advantageous economically in dyeing large indigo for the fiber, deep blue shades are attained
batches. only if dyeing and oxidation are repeated several
times. Thus, in the past, indigo dyeing took
several days.
4.4. Dyeing with Indigo (! Indigo and In modern indigo dyeing plants for dyeing
Indigo Colorants) warp yarn, several dyebaths and oxidation units
(usually up to five units) are arranged in a row for
4.4.1. Chemistry and Historical continuous operation [180–182] (see Fig. 38).
Development For blue denim articles, pronounced ring dyeing
of the yarn is desirable.
The chemical constitution of indigo was eluci- There are rope dyeing machines and slashers.
dated in 1883 by ADOLF VON BAYER. The first In rope dyeing machines, 300 to 400 warp threads
technically marketable syntheses were devel- are combined into a rope and, in this form, passed
oped by HEUMANN and PFLEGER. through the dyeing system. Slashers were devel-
As in the case of natural indigo, the dye is oped in the 1970s from sizing machines. In these
made by air oxidation of indoxyl (! Indigo and machines, the warp threads are dyed side by side,
Indigo Colorants, Chap. 4.). Natural and synthet- parallel to each other [183]. Both types of ma-
ic indigo are absolutely identical chemically. chines have advantages and disadvantages and
The demand for indigo depends greatly on should be assessed according to the specific
fashion; it amounted to about 11 000 t world- requirements (e.g., small or large batches, re-
wide in 1992. quired fastness of dyeing).
Vol. 36 Textile Dyeing 251
4.5. Dyeing with Sulfur Dyes [184–186] The main applications according to the textile
(! Sulfur Dyes) are:
The dyeing of cellulosic fibers, especially cotton 1. Piece dyeing: corduroy and velveteen, twill
and its blends with synthetic fibers, is the main for working clothes, leisurewear, tarpaulin
field of application of sulfur dyes. In addition, and rucksack fabrics, coat poplin, and lining
sulfur dyes such as Indocarbon are used in print- materials. The dyeing of the cellulose part of
ing these fibers. Sulfur dyes are also used to a blended fabrics containing polyester is be-
limited extent to dye polyamide fibers, silk, coming increasingly important.
leather, paper, and wood. 2. Yarn dyeing: sewing thread, warp yarn for
Although more brilliant sulfur dyes (red and denim fabric, yarn for colored woven goods.
green) have been put on the market in the 1950s 3. Dyeing of flock, card sliver, roving, etc., for
and 1960s, the strong point of these dyes still lies blend yarns with wool and man-made fibers.
in the deeper, muted shades, such as black, dark
blue, olive, brown, and green, where their favor- 4.5.1. Types and Mode of Reaction
able price has its full effect. [184], [187–190]
With respect to fastness, sulfur dyes are close
to vat dyes but not equal to them. They have For technical and applicatory reasons, sulfur dyes
varying lightfastness that is generally good in the are available in various modifications, which are
case of the blue, green, olive, and brown shades. classified in the Colour Index under the following
The lightfastness in presence of perspiration of general generic names:
sulfur black is very good. The washfastness of
Sulfur Dyes (C.I. Sulphur). Two types of
sulfur dyes at 60 C is good to very good, and
sulfur dyes exist:
their fastness to boiling water is moderate to
good. Wetfastness can sometimes be improved Amorphous Powders, which are insoluble or
substantially by aftertreatment of the dyeing with partially soluble in water. They must be brought
products of the Solidogen IH type. With a few into solution by boiling with sodium sulfide and
exceptions, sulfur dyeings are not fast to chlo- water, according to the following overall reaction
rine. Therefore, faulty dyeing can be stripped by scheme:
treatment with sodium hypochlorite bleach
liquor.
A high-grade finishing operation can also
improve the wetfastnesses. A decrease in light-
fastness, as in the crease resist finishing of ma-
terials dyed with other dyes, does not occur; in For the sake of simplicity, only one mercapto
fact, an improvement is frequently observed. group has been assumed per dye molecule (D). In
252 Textile Dyeing Vol. 36
strongly caustic alkaline liquors, the following only a dimerization but also cross-linking of dye
mode of reaction is possible: ‘‘monomers.’’ For sulfur cooked dyes, the qui-
nonimine group is also involved in the reaction.
4 DS SDþ2 S2 þ6 OH !8 DS þS2 O2
3 þ3 H2 O
This is clear from the change in shade that occurs
during reduction.
With respect to both application and fastness,
According to this equation, only one-quarter a distinction is made between sulfur dyes and
the amount of reducing agent normally used is sulfur vat dyes. The latter include dyes of the type
required. Hydron Blue (C.I. Vat Blue 43) and Indocarbon
With sulfur cooked dyes (i.e., quinonimine (C.I. Sulphur Black 11).
sulfur dyes, which are produced by water or
solvent reflux thionation), the reducing agent can
attack not only the disulfide groups but also the 4.5.2. Additives to the Dye Bath
quinonimine group (as in the case of vat dyes).
Reducing Agents. Ready-for-use sulfur
Dispersible Pigments, analogous to the Col- dyes contain the reducing agent required for
loisol or Microdisperse grades of vat dyes, are dyeing. Otherwise, the dye must be brought into
used particularly for pad dyeing. solution by the addition of a reducing agent or the
The dispersible, partly reduced pigments car- already water-soluble dye must be made to have
rying the name ‘‘Sol’’ represent a special case. an affinity for the fiber.
Apart from a dispersing agent, they contain a The reducing agents generally used are sodi-
certain amount of reducing agent. um sulfide or sodium hydrogensulfide in differ-
ent forms in the following ratio (parts by weight):
Leuco Sulfur Dyes (C.I. Leuco Sulphur).
These ready-for-use, liquid dyes already contain 100 parts of crystalline sodium sulfide
the reducing agent required for dyeing. They (Na2S 9 H2O; ca. 30 – 32 wt % Na2S)
must simply be diluted with water before appli- =50 parts of concentrated sodium sulfide (ca.
cation. Ecologically more favorable, low-sulfide 60 – 62 wt % Na2S)
types are now available. =65 parts of liquid sulfhydrate F 150
(31 wt % NaSH)
Water-Soluble Sulfur Dyes (C.I. Solubi- =25 parts of concentrated sodium sulfhydrate
lized Sulphur) [188]. Water-soluble sulfur powder (95 wt % NaSH)
dyes are available in the form of Bunte salts
(S-arylthiosulfuric acid salts) of sulfur dyes and The amount of reducing agent required to
can be dissolved in hot water. The addition of dissolve or color the sulfur dye (Na2S or NaSH)
alkali and reducing agent gives them an affinity is given on sample cards issued by dye producers.
for the fiber: In the dye liquor, the amount of concentrated
Na2S should be 2.5 g/L.
DSSO 2 2
3 þS !DS þS2 O3
In aqueous solution, the sulfide ion is largely
hydrolyzed according to
If NaSH or another reducing agent is used,
alkali must be added to trap Hþ ions resulting
from reduction. In the case of NaSH, H2S forma-
tion is avoided in the following manner:
The resulting caustic alkaline product is not
required at least for dyeing with water-soluble
DSSO 2 2
3 þSH þCO3 !DS þS2 O3 þHCO3
sulfur dyes.
If a combination of NaSH and soda is used, the
The leuco form DS is absorbed by the sub- lower alkalinity offers the following advantages:
strate and then oxidized to the fixed dye DS –
SD. Since in reality several mercapto groups are 1. The dyeing results in a better color yield and
present per dye molecule, oxidation causes not can be rinsed clear substantially faster
Vol. 36 Textile Dyeing 253
2. During dyeing and rinsing, the dyeing is much Wetting Agents. A wetting agent or pad-
less sensitive to undesirable oxidation effects ding auxiliary is usually added. Products based
(bronzing, rubbing-fastness) on sulfonated oleic acid amides give good results
3. In the case of regenerated cellulose (viscose), because they exert a certain leveling effect and
embrittlement of the material is avoided confer softness on the material. In comparison,
products based on ethoxylates are unsuitable
Sodium dithionite (hydrosulfite) is a proven because they have a retarding (equilibrium ‘‘dye
reducing agent for sulfur vat dyes, which is used dissolved in liquor: dye absorbed to fiber’’ is
together with alkali – usually sodium hydroxide shifted toward ‘‘dye dissolved in liquor’’), and
solution and occasionally soda. sometimes precipitating, effect on the dye.
The color yield of some sulfur dyes is
remarkably increased by the addition of hydro- Water Softeners. To exclude the negative
sulfite. With blue grades in particular, the effects of alkaline-earth ions on dyeing, seques-
addition of hydrosulfite ‘‘sharpens’’ the dye trants based on ethylenediaminetetraacetic acid
liquor, preventing bronzing. Glucose is em- (EDTA) or polyphosphates are used. Additives
ployed in one-phase printing with Indocarbon. of this type are required, especially in circulat-
As a result of possible ‘‘overreduction’’ or ing-liquor dyeing with hardness-sensitive dyes,
destruction of the dye chromophore, hydrosul- to prevent unevenness and the splitting of warp
fite and similar reducing agents can be used to beams. Acidic treatment of the material to be
only a limited extent and require a suitable dyed (1 – 5 g/L of HCl, HCOOH, or
selection of dye. CH3COOH) can often prevent the contamination
For the reduction of water-soluble sulfur dyes, of wastewater with sequestering agents.
the aforementioned reducing agents, glucose,
and hydroxyacetone are used [191].
In the case of water-soluble sulfur dyes and 4.5.3. Dyeing
low-sulfide leuco sulfur dyes, glucose-based
combinations of reducing agents (binary reduc- Absorption of Dyes. In the exhaustion pro-
ing agent systems) have gained acceptance for cess (in a jigger, circulating-liquor machine or
ecological, technical, and applicatory reasons winch beck), the dye generally absorbs at 60 –
[192]. The following substances can be consid- 110 C in 30 – 60 min and in the pad steam
ered binary reducing agent components: hydro- process, at ca. 102 – 105 C in 30 – 60 s.
sulfite, formamidinesulfinic acid, and with lim- Dyeing with reducing agents is always per-
itations, hydroxyacetone. Mixtures of sodium formed according to the exhaustion process. Pad
hydroxide solution and soda are used as alkali. dyeing processes, such as the pad steam and pad
The aforementioned reducing agent combina- roll process, use a very short liquor ratio (ca.
tions result in less pollution of wastewater. At 0.7 : 1). The dye is basically fixed at the place
the same time, glucose prevents or buffers where it has been padded. The fixing yield de-
possible overreduction or destruction of the pends greatly on the liquor ratio. Optimal fixation
dye chromophore by the reducing agent com- and dye penetration are achieved with the pad roll
ponent with a higher reduction potential. process.
Alkali polysulfides are added to stabilize
sulfur alkaline dye liquors against atmospheric Oxidation of Dyes [184], [189], [191–193].
oxygen. In jigger dyeing, dark and bronzed Sulfur colors are finally fixed on the substrate by
edges or seam marks can be avoided in this oxidation. Before this step, the reducing agent,
way. In the case of winch beck, jet, and con- salts, and alkali, as well as the unfixed dye, must
tinuous dyeing, undesirable oxidation during be removed by rinsing or washing to attain opti-
the absorption phase and rinsing is avoided, mal rubbing-fastness. The following methods of
improving rubbing-fastness. Problem-free dye- oxidation are common.
ing can be achieved with sulfur vat dyes of the
type Hydron Blue by using alkali sulfides and Air Oxidation or Acid Treatment. The dye-
alkali polysulfides, especially on the winch ings are subjected to cold and warm rinsing; the
beck. last rinse bath should generally be acidified with
254 Textile Dyeing Vol. 36
acetic acid (exception: sulfur black). In general, wetfastness can largely be avoided by oxidation
this process is used only for staple shades because in acetic acid medium (pH 4 – 4.5). Since oxi-
after-oxidation usually occurs on storage, result- dation then proceeds more slowly, the tempera-
ing in a change in shade. ture must be increased to 70 C. The resulting
shades are much duller than those obtained by
Bichromate – Acetic Acid Oxidation. The oxidation in the alkaline range. About 1 – 2 %
material is treated with ca. 0.5 % potassium or (based on the weight of the material) of 35 %
sodium bichromate (based on the weight of the H2O2 is used.
material) at pH 4 – 5 and ca. 70 – 80 C. Until
now, this process was common especially in piece Other oxidizing agents such as chlorite, bro-
dyeing. In the last years, however, it has been mite, chloramine T, and persulfate are not equal-
replaced increasingly by other types of oxidation ly suitable for all dyes and consequently are
for ecological reasons. In bichromate oxidation the seldom used. Sodium hypochlorite bleach liquor
material to be dyed becomes hydrophobic, evi- (hypochlorite) requires careful metering and can
dently because of the formation of dye – chromi- be used only with sulfur dyes that are relatively
um complexes. Although addition of copper sul- fast to chlorine.
fate (1 – 2 g/L CuSO4 5 H2O) to the oxidation
bath improves the lightfastness of the colors, it is Alkylation. With special alkylating agents,
hardly ever applied. This type of oxidation cannot DS groups can be converted to the thioether DS –
be used for articles to be rubberized. X – SD, where X is, e.g., – CHR – CHR –. In
this way, the color is stabilized against oxidative
Iodate Oxidation. Iodate oxidation [ca. 0.5 and reductive effects [194]. Bi- or polyfunctional
% potassium or sodium iodate (based on the alkylating agents are especially effective because
weight of the material) at pH 4.5 – 5 (acetic they lead to cross-linking and enlargement of the
acid) and >60 C] is used only occasionally. In dye molecule. Solidogen IH is an appropriate
comparison with bichromate – acetic acid oxi- product that at the same time exhibits substantiv-
dation, somewhat brighter shades are obtained. ity due to its cationic character. About 1 – 2 %,
based on the weight of the material, is used
Bromate Oxidation. To attain an adequate together with soda. In individual cases, the wet-
rate of oxidation, the addition of vanadate (ca. fastness of vat dyeing can be achieved by after-
0.05 % NaVO3 4 H2O with ca. 0.5 % NaBrO3, treatment with alkylating agents.
based on the weight of material) is required. In alkylation, care must be taken that only the
Oxidation proceeds at pH 4 – 4.5 (acetic acid) mercapto groups and not the quinonimine groups
and 70 C. of cooked dyes are alkylated; otherwise these
compounds are fixed in their leuco form, which
Hydrogen Peroxide Oxidation. With hydro- can lead to losses in coloring strength. Thus, in
gen peroxide oxidation, bright shades are ob- practice, dyeings are subjected to squeezing or
tained in the alkaline-to-neutral pH range. How- suction before aftertreatment so that the leuco vat
ever, wetfastness is reduced somewhat compared form is oxidized by air before alkylation. Alter-
with other oxidation processes because oxidation natively, the alkylating agent is used in combi-
with hydrogen peroxide is not specific. Thus, nation with specifically acting oxidizing agents
especially if the oxidation is not performed prop- such as chlorite.
erly [excessively high concentration of H2O2, In the case of sulfur black dyeing, cationic
excessively high temperature and pH (>50 C, alkylating agents can be used not only to improve
pH >7), and excessively long oxidation times], wetfastness, but also to produce a buffering
overoxidation occurs; i.e., the mercapto groups effect, whereby losses in tensile strength due to
of the sulfur dyes are oxidized not only to disul- fiber damage can be avoided.
fide groups, but also in part to sulfonic acid
groups. Wetfastness can be greatly improved by Rinsing or Washing. After oxidation or
aftertreatment of the dyeings with cationic aux- alkylation, the dyeing is rinsed or washed at
iliaries, which are partly used in combination 60 – 95 C to remove excess oxidation or
with oxidizing agents [194]. A deterioration of alkylating agent and, possibly, detached dye. A
Vol. 36 Textile Dyeing 255
soaping process, as in the case of vat dyes, is not wetting agent at 40 – 50 C. The dissolved, re-
common because a decrease in rubbing-fastness duced dye is then added, the bath is brought to
occurs and recrystallization cannot take place dyeing temperature, and salt is added. After 20 –
with the cross-linked sulfur dye molecule. 30 min, the material is rinsed clear by the influx
A disadvantage of sulfur black dyeings (C.I. of cold water and simultaneous overflow of the
Sulphur Black 1) is the elimination of sulfuric acid liquor. Dyeing is completed as usual.
on storage under unfavorable conditions (high
temperature and higher humidity) [195]. A reac- Circulating-Liquor Dyeing. The material is
tion of this type can even occur after a longer often boiled or subjected to an acidic pretreat-
drying period. Therefore, to avoid tendering and ment to eliminate hardness-producing sub-
losses in tensile strength, sulfur black dyeings stances. The dyebath contains wetting agent,
must be buffered in the last rinsing bath with soda chemicals, and the dissolved, reduced dye. After
or sodium acetate. A rather washfast buffering can 10 min of dye liquor circulation at 30 – 40 C,
be achieved by using special cationic auxiliaries, the dyeing temperature is adjusted, and the pro-
such as dicyandiamide – formaldehyde conden- cess is terminated after about 30 min by rinsing
sation products and alkylating agents. An im- clear and oxidation. The salt is added, in part, at
provement can also be obtained by anticipating the dyeing temperature.
the elimination of sulfuric acid by means of
oxidation with bichromate – acetic acid. Jet Dyeing [198]. Foam control is important
in the case of semiflooded jets. After wetting the
material (or predyeing the polyester part of poly-
4.5.4. Dyeing Techniques [184], [186], ester – cellulose fiber blends with disperse
[188–191], [196], [197] dyes), reducing agent (e.g., glucose – hydrosul-
fite) and chemicals are added at ca. 40 C, the
Batch Processes (Exhaustion Processes). dissolved dye being added after about 10 min. If
Jigger Dyeing. The dyebath is charged with all the jet contains a lot of air space compared to
the chemicals, and the dissolved dye is added in liquor, about 1.4 kg of concentrated hydrosulfite
two passages at the desired temperature. The salt and 1.4 L of sodium hydroxide solution 38 Be
is added after the third or fourth passage. After (ca. 32 wt %) must be added per cubic meter of
about six passages (or 60 min) and sampling, air. After heating to dyeing temperature, more
dyeing is completed by rinsing and oxidation. hydrosulfite is added, if necessary, and the mate-
rial is dyed for 30 min. Dyeing is completed by
Jigger Dyeing with Preimpregnation. In the rinsing clear, oxidation, and rerinsing.
case of water-soluble sulfur dyes, the material
can be impregnated at boiling temperature with Continuous Pad Dyeing Process. Ready-
dye, salt, and wetting agent in the shortest possi- for-use liquid or water-soluble sulfur dyes and
ble liquor ratio. The volume of dyebath is then dispersible pigments are employed preferentially
filled up with water, the reducing agent added, in continuous pad dyeing.
and the dyeing completed as usual. In compari- As a result of the (varying) substantivity of the
son with the normal jigger process, better pene- dyes in pad processes with reducing agents,
tration is achieved. tailing can occur. In this case a constant shade
is attained only after a certain yardage. This
Pad Jig Process. After the material is pad- problem can be avoided by taking into account
ded with dispersed or water-soluble dye and both the feeding liquor factors of the individual
wetting agent (possibly drying, which is gener- dyes and the substrate factors. The recipe of the
ally avoided because of the costs), it is placed in starting bath and of the feeding liquor can be
the liquor at the dyeing temperature. This liquor calculated [199].
contains the reducing agent, salt, and some pad-
ding liquor. The dyeing is completed as usual. Pad Steam Process. The following varia-
tions in the pad steam process are possible: In
Winch Beck Dyeing. The material is pre- the one-bath procedure, the material is impreg-
treated in a bath containing the chemicals and nated with dye, reducing agent, and wetting agent
256 Textile Dyeing Vol. 36
at 20 – 30 C and subsequently subjected to air- and sized in a continuous process. The warp is
free steaming at 102 – 105 C for 30 – 60 s. impregnated with dye, alkali, and reducing agent
Rinsing is followed by oxidation and rerinsing at 70 C and subsequently dried and sized (main-
in a washing machine. The material speed is ly with potato starch). After weaving, the mate-
40 – 100 m/min. Warp for denim articles can rial is treated with a cationic alkylating agent and
be dyed in the same manner. acetic acid in a padder and then rinsed. This
The two-bath procedure (for water-soluble process produces colored and black dyeings in
sulfur dyes and dispersible pigments) is preferred which mainly the outer layer of the fiber is dyed.
especially for mercerized material to obtain a The stone wash effect can be imitated in this
more even appearance. The material is padded at manner. A one-bath variant of this process gives
20 – 30 C with dye, wetting agent, and possibly poorer fastness properties, which correspond
antimigration agent. After intermediate drying, if roughly to those of indigo dyeing [201].
necessary, it is impregnated with reducing agent,
and the process is completed by steaming and
aftertreatment, as in the one-bath process. 4.5.5. Combination with other Dye Groups
Pad Air-Passage Process. For light to mod- Sulfur dyes are combined with other dyes for
erate shades, the material can be impregnated reasons of shade, fastness, and in the case of
with dye, reducing agent, and wetting agent at polyamide – cellulose blends, tone-in-tone dye-
elevated temperature (70 – 80 C). During air ing. Thus, combinations of sulfur vat dyes of the
passage for ca. 1 min, sufficient fixation is type Hydron Blue with dispersible vat dyes are
achieved. Dyeing is completed in washing ma- generally used in the two-bath process. For
chines as usual. stretch cord and similar articles made of poly-
The hot pad dry process is a variant of the pad amide – cellulose fibers, metal-complex dyes
air-passage process. After impregnation, the ma- that are resistant to reducing agents are added
terial is subjected to hot drying on a drying to dye the polyamide fibers because only a few
cylinder. For final fixation of the dye, the material sulfur dyes stain polyamide fibers sufficiently
is impregnated with a cationic alkylating agent compared to cotton fibers.
and redried. This process is used especially in the Water-soluble sulfur dyes can be combined
dying of warp yarns. with selected reactive dyes [202]. In this
manner, more brilliant shades are obtained.
Semicontinuous Padding Processes. Hydrosol Brilliant Red BCL, which is based
on monochlorotriazine, is a reactive dye of this
Pad Roll Process. After impregnation with type.
the pad liquor, the material is batched up and In jigger dyeing, sulfur colors are usually
stored in an air-free steam chamber (dry and wet brightened and shaded in a fresh bath with direct
temperature ca. 98 C) where it is rotated slowly. and basic dyes after oxidation.
After a rotation of about 1 h, dyeing is completed.
By this procedure, the dye is almost completely
fixed. Excellent penetration is obtained. 4.5.6. Wastewater [203]
Special Dyeing Processes [184], [190], Normal wastewater from sulfur dyeing contains
[200]. Dyeing with water-soluble sulfur dyes can sulfides in addition to dye residues and salts.
be performed without reducing agents according Since sulfides are toxic to aquatic organisms and
to a pad thermofixing process. After padding and form hydrogen sulfide with acids, they must be
drying, the dye is fixed by heat treatment in the eliminated or their concentration reduced, at
presence of acid-donating catalysts, urea, and least. To avoid these problems, low-sulfide and
thiourea. In this way, the water-solubilizing sulfide-free dyeing methods have increasingly
Bunte salt groups are split off. An excellent gained acceptance [192], [204]. Since the pres-
appearance is obtained in this process. ence of chromium in water is restricted because it
For denim articles, the warp yarns can be dyed is ecologically harmful, oxidation with bichro-
with sulfur vat dyes or water-soluble sulfur dyes mate, which was used widely in the past, has been
Vol. 36 Textile Dyeing 257
replaced in many cases by other types of oxida- fide sulfur. Oxidation is accelerated by residues
tion. According to appendix 38 of the general of sulfur dyes, which generally make the addition
wastewater regulations, the draft of which should of catalysts such as Mn2þ unnecessary. By air or
come into force shortly, the presence of chromi- oxygen injection or by the action of air in trickle
um(VI) compounds from the use of oxidizing plants, the sulfides are oxidized in a few hours at
agents for sulfur dyes is not permitted in Ger- room temperature in the presence of the dye
many. In the United States no national standards residues.
for wastewaters from the textile industry exist. The second stage involves chemical treatment
Minimum requirements are stipulated by the local by the addition of iron salts alone or together with
authorities or the local public treatment plants. Ca(OH)2 and flocculation auxiliaries, if neces-
Limits for indirect discharge are generally sary. Sulfide and dye residues are eliminated by
0.5 ppm for chromium and 5 ppm for sulfides precipitation and sedimentation.
[205]. In Japan the national wastewater standards The third stage involves biological treatment,
can be adapted by the local prefectures to local primarily using the activated sludge process with
requirements. Relevant values for Osaka are giv- the addition of oxygen (usually air, seldom pure
en as a typical example: total chromium 2 mg/L, O2). The activated sludge is separated in a sec-
chromium(VI) 0.5 mg/L (see Section 14.2). ondary tank.
In the Katox process [204], [206], the main
Indirect Discharge. For indirect discharge, purification is performed in the Katox stage by
the conditions to be obeyed for components that means of accelerated oxidation in the presence of
are not dangerous depend on the municipality activated carbon. This is followed by a final
and the state. After appendix 38 of the general purification, which involves chemical precipita-
wastewater regulations comes into force, the tion with iron sulfate, calcium hydroxide, and
requirements for dangerous components stipu- flocculation auxiliaries.
lated in these regulations must be fulfilled. This If no sulfides at all are allowed to be dis-
means that in textile finishing companies, sulfide charged into the wastewater, water-soluble sulfur
values must be decreased to 1 mg/L, as in the dyes with sulfide-free reducing agents are an
case of direct discharge. Wastewater of this type alternative [192].
can be treated without problems together with
municipal wastewater in municipal sewage treat-
ment plants. However, mixing with acidic waste- 4.6. Dyeing with Naphtol AS Dyes
water and the resulting formation of hydrogen
sulfide in the sewage system must be prevented. An azo dye is formed from a Naphtol AS cou-
Contaminations of this type must be kept as low pling component and a diazotized base (devel-
as possible because H2S is oxidized microbially oping component) under suitable conditions (!
to sulfuric acid, which attacks concrete. Azo Dyes, 5. Developing Dyes, Chap. 1.). This
Wastewater from dyeworks can be collected coupling can be carried out on the fiber itself. If
in mixing and balancing tanks. Mixing with components without solubilizing groups are
wastewater from a bleaching plant is of advan- used, the dye formed is an insoluble pigment,
tage. If possible, the wastewater should be oxi- and washfast dyeing is achieved. This possibility
dized by aeration or detention or by the addition was exploited quite early. A cotton fabric was
of oxidizing agents, such as H2O2 or ozone. first impregnated, for example, with a solution of
sodium b-naphtholate and, after drying, was
Direct Discharge. For official require- passed through a solution of diazotized p-nitroa-
ments, toxicological, and ecological aspects, see niline to give an attractive deep red dyeing with
Chapter 14. marked fastness (Para Red). A large number of
In general, wastewater is purified in several modified naphthols and suitable diazotizable
stages. The first stage is a mixing and balancing bases (fast bases) were marketed by the then
tank with aeration, pH regulation, and cooling. I.G. Farbenindustrie (now Hoechst and Bayer).
During aeration, sulfide and polysulfide react to By employing similar methods, these compo-
form thiosulfate. At the same time, the dye nents can be used to produce dyeing and printing
becomes insoluble and precipitates with polysul- with excellent fastness in the most widely
258 Textile Dyeing Vol. 36
differing shades. The classic Turkey Red (Aliza- ice, by using a solution of sodium nitrite in
rin Red) has been replaced by the combinations hydrochloric acid. Alternatively the base and the
Naphtol AS-TR/Fast Red TR base and Naphtol nitrite are made into a paste and stirred into the
AS-ITR/Fast Red ITR base, in particular, which hydrochloric acid solution. To increase the cou-
have good fastness. Besides bases that need to be pling capacity, excess mineral acid must be
diazotized before use in dyeings, diazotized dia- neutralized or buffered by the addition of sodium
zonium compounds in stabilized form have also acetate, disodium phosphate, or similar com-
been marketed as fast color salts (! Azo Dyes, pounds. The textile impregnated with naphthol
5. Developing Dyes). Similar ranges later came is passed through the cold developing bath con-
on the market from most of the other large dye taining the diazotized base so that the dye is
producers. formed rapidly. In dyeing machines the develop-
Nearly all cellulosic fibers can be dyed in ing solution circulates through the stationary
every processing state by using Naphtol AS textile. Alkali carried over from the padding bath
combinations. Other dyes can rarely give the must be neutralized by the addition of an alkali-
same depth of color and shade. Handling these binding agent (e.g., acetic acid, aluminum sul-
combinations is safe and relatively simple. fate) to the developing bath to prevent decompo-
Therefore, Naphtol AS dyes have been intro- sition of the diazonium salt.
duced into the textile industry on a wide basis. The use of naphthols and bases in solution was
Colorations with outstanding fastness have been introduced in the 1970s. These formulations are
achieved, which in some cases are of the same safer and simpler to apply. Diazotization of the
standard as those using Indanthren. liquid bases generally does not require the addi-
tion of ice. After development, the textile is
Dyeing Process. In the impregnating pro- rinsed and subjected to careful aftertreatment in
cess the cotton fiber is treated first with Naphtol which excess color lake is removed from the fiber
AS, which is dissolved by boiling with caustic surface. Otherwise, it severely impairs the rub-
soda and a protective colloid (hot solution pro- bing-fastness of the dyeing. In addition, through
cess) (for details of additives, see ! Textile the change in pigment crystal structure occurring
Auxiliaries, 5. Dyeing Auxiliaries). Most Naph- during aftertreatment, a stable final shade with
tol AS types can also be solubilized readily with enhanced fastness is achieved.
alcohol and caustic soda by using the cold solu- The possibility of producing fast, substantive,
tion process. The concentrated sodium naphtho- and bright dyeings on the textile from two dif-
late solution is added to the impregnating bath. ferent components has led to a large number of
For certain naphthols the addition of formalde- special processes and articles, characteristic of
hyde to stabilize the naphthol on the fiber (air different geographical areas. Naphtol AS com-
stability) is also necessary; otherwise, coupling binations that can be used at low temperature are
capacity is impaired. By addition of sodium extremely suitable for dyeing cellulose fiber
chloride a rather substantive attachment of the materials that are partially coated with wax. After
naphthol to the fiber is achieved. On dyeing from dyeing the wax is washed out by boiling. This
a long liquor a lower temperature is used for technique is still popular as batik, mainly in
impregnating the fabric, followed by rinsing and Southeast Asia.
development. The use of a padding machine The use of Naphtol AS dyes for the production
requires a higher temperature and, in general, of denim articles is of industrial and commercial
intermediate drying. interest. The cotton warps are simultaneously
Hank yarn is impregnated in a long liquor, for sized and padded with a coupling component.
example, in a trough or on hank yarn dyeing After weaving the impregnation is developed
machines. Wound yarn can be impregnated in the with a fast salt or a diazotized base and subjected
usual mechanical dyeing machines. Piece dyeing to the usual aftertreatment. The process was
is carried out on the winch beck and the jigger introduced as the warp sizing padding process.
or, preferably, continuously on the padding Another variant is known as the warp sizing and
machine. dyeing process in which the warp is padded,
For developing, the base must first be diazo- dried, and developed immediately with a diazo-
tized in the cold, if necessary with the addition of tized base.
Vol. 36 Textile Dyeing 259
4.7. Dyeing with Pigments feel of the product, and limits to the rubfastness
and wetfastness.
Being insoluble products, pigments can only be Pigment dyeing is used commonly for heavy
fixed to the surface of the fiber. For pigment textiles (e.g., canvas), light printing grounds,
coloring, very fine (particle size 0.5 mm) inor- dress materials, shirting, bed linen, and furnish-
ganic or organic pigments are used in a nonionic ing articles.
preparation (! Pigments, Inorganic, 1. General;
! Pigments, Organic). They are fixed with the
help of a binder. The binder is an aqueous 4.8. Other Dyeing Methods
dispersion of cross-linkable mixed polymers (co-
polymers or polymer blends, basis polyacrylate, 4.8.1. Dyeing with Leuco Esters of Vat
polystyrene, polyurethane). A film, in which the Dyes
pigment particles are embedded, is formed on
the fiber. Cross-linking occurs during heating. The leuco esters of vat dyes are anthraquinoid or
The binder film must adhere firmly to the substrate indigoid vat dyes that have been made water
without the material becoming too stiff or sticky. soluble by reduction and esterification of the
The type and amount of binder used depend on the hydroxyl groups with sulfuric acid.
amount of pigment and determine not only the After application to the fiber, the ester is
feel, but also the rubfastness and wetfastness of hydrolyzed, usually with sulfuric acid at room
the dyeing [207]. Usually, only light shades are temperature or slightly elevated temperature (up
produced by pigment dyeing. Common trade to 70 C), and the original vat dye is recovered by
names for pigment – binder combinations are oxidation (e.g., with sodium nitrite).
Acramin (Bayer) and Helizarin (BASF). Polyure- The advantages of dyeing with the leuco esters
thane-based binders (Perapret PU, BASF) form of vat dyes are not only good levelness (even-
elastic films that can bind large amounts of pig- ness) and penetration but also the excellent fast-
ment, making deep coloration possible. ness of vat dyes. The low affinity of the leuco
Since pigments show no substantivity for ester for the cotton fiber and the relatively high
textile fibers, piece goods are impregnated con- dye costs are obstacles to wide application. These
tinuously with a liquor that contains the pigment, dyes are used mainly for dyeing high-quality
the binder, an antimigration agent, a cross-link- articles of cellulose fibers in light colors and
ing agent if necessary, an acid donor, and a polyester – cellulose blends to moderate depths
softener. The pieces are dried at 90 – 120 C of color [209], [210], [211, p. 568].
and fixed at 160 – 180 C. No afterwash is re-
quired. A resin finish can be carried out at the Batch Dyeing. Because of the low substan-
same time (e.g., a crease-resistant and antishrink tivity of leuco esters of vat dyes for cellulose,
finish, hydrophobing or a soil release finish). batch processes (exhaustion processes) are rather
Nowadays, a washout effect is produced with unimportant. The usual systems are used, e.g.,
pigments in an exhaustion process. In this pro- jigger and winch beck for piece goods and pack-
cess, cotton is impregnated with a cationic age dyeing machine for fabric and yarn. One- or
product so that pigments can attach. A reduced two-bath processes exist. In the two-bath mode of
amount of binder is applied and fixation is dyeing, the dye is first allowed to strike (bottom-
carried out at low temperature (120 – 130 C). ing) in the presence of salt in a weakly alkaline
The disadvantage of the process is that a lot of medium (e.g., on the jigger). The liquor is then
pigment is lost, which contaminates the waste- removed, and the color is developed with a liquor
water [208]. containing sulfuric acid and nitrite at room tem-
Pigment dyeing offers the advantages of uni- perature. If high-temperature development is
versal applicability to all fibers (including glass required (70 C), nitrite is added to the bottom-
fibers). It is a single-stage process, even for fiber ing bath. The one-bath mode is usually used in
mixtures (i.e., an energy-saving process). After- winch becks; i.e., the same bath is used for both
treatment is not required. Raw cotton is covered bottoming and development. Packages are sub-
well. The resistance to light is very good; the jected to one-bath or two-bath dyeing, depending
disadvantages are limited depth of color, stiffer on the affinity of the dye.
260 Textile Dyeing Vol. 36
Continuous Processes [212]. Continuous ing, treatment with rancid olive oil, leaching,
processes yield more favorable dye yields. The treatment with a tanning agent, mordanting with
most important processes are: alumina, dyeing in hard water, reviving, acidifi-
cation, and soaping. In the new process, treat-
1. Processes without intermediate drying: pad- ment with Turkey red oil (sulforicinoleic acid)
ding (dye, soda, nitrite), air passage, develop- has replaced the oiling step. The light- and
ment (dipping at 70 C in acid), air passage, wetfastnesses obtained are excellent.
and aftertreatment In the past, this method was used to dye, e.g.,
2. Processes with intermediate drying: padding cambric and bunting. Today, easier methods
(dye, soda, nitrite), drying, development (dip- using developing dyes and vat dyes have re-
ping at 70 C in acid), air passage, and after- placed this process.
treatment (this process gives a higher fixing
yield than the first method)
3. Pad steam development process without in- 4.8.3. Dyeing with Acid Dyes [211, p. 580]
termediate drying: padding (dye, soda, ni-
trite), steaming (1 min, saturated steam, Acid dyes (i.e., azo or anthraquinone dyes that
103 C), development (dipping at 70 C in are made water soluble by sulfonic acid groups)
acid), air passage, and aftertreatment were occasionally used for dyeing cotton; how-
ever, they are no longer important. They do not
As a result of their high price, low substan- have sufficient substantivity for cellulose. Only
tivity, and toxicological problems during produc- those dyes are usable that can form a metal
tion, the importance of the leuco esters of vat complex on the fiber when applied together with
dyes is decreasing. Remaining producers and a metallic salt. Excess heavy metal contaminates
trade names include Hoechst (Anthrasol Blue wastewater.
IBC), Ciech (Helasol), and Mitsui (Mikethren). Acid dyes can attach directly to vegetable
Dyeing with leuco esters of vat dyes can be hard fibers (jute, sisal) by salt formation because
replaced easily by pigment coloring, by reactive the fiber companion substances contain basic
or vat dyes. groups.
4.8.5. Dyeing with Mineral Dyes [211, formed on heating (150 C) in the presence of
p. 584], [213, p. 520], [214, p. 395] weak reducing agents (e.g., glycols). This is
followed by aftertreatment with hydrochloric
In a pad process, inorganic metallic salts can be acid, with the addition of sodium nitrite to
applied to cotton and then converted in an alka- remove secondary products. The most impor-
line medium to the corresponding oxide by treat- tant aminoiminoindolenine is: C.I. Ingrain Blue
ment with steam. Brown and khaki shades (min- 2 : 1, 74160 (trade names, e.g., Phthalogen
eral khaki) are obtained with chromium and iron Brilliant Blue IF3GM, Bayer or Sumilogen
salts. This dyeing is inexpensive, lightfast, and Brilliant Blue, Sumitomo).
weather- and rotproof. The disadvantages are
wastewater contamination and definite harden- High Molecular Phthalogen Developer.
ing of the fabric. This method is still important in Polyisoindolenines, which are complexes of
some countries for dyeing tarpaulin and uniform heavy metal and indolenine, are developed with
materials. reducing agents in a wet treatment. The poly-
isoindolenine complexes (trade names, e.g.,
Phthalogen Brilliant Blue IF3GK, Cu complex
or Phthalogen Turquoise IFBK, Ni complex) are
4.8.6. Dyeing with Oxidation Dyes [213,
fiber affinitive and can be applied by using the
pp. 437 – 439]
exhaustion process. Their substantivity is, how-
ever, low but can be increased by pretreating the
In the application of oxidation dyes, aromatic
cellulose with anionic products (e.g., Phthalofix
amines form insoluble polyazine derivatives in
FN). Reductive development is performed in an
the fiber (! Azine Dyes). Synthesis proceeds in
alkaline medium with hydrosulfite. For details,
several steps in a hydrochloric acid medium by
see [215], [216].
oxidation (e.g., with dichromate). For the chief
Dyeings made by phthalogen developers are
representative of this group, aniline black, the
characterized by high brilliance and excellent
chromophore consists of dibenzopyran rings.
fastness. Thus, they are suitable for washfast and
Oxidation dyes are rapidly decreasing in impor-
weatherproof articles. No danger of photochro-
tance because aniline and other aromatic amines
mism exists if a finishing operation is performed
as well as the bichromate used for oxidation are
with synthetic resin products.
toxicologically hazardous. The colors produced
by aniline black are characterized by a full bluish
black shade and excellent fastness. Since they are
4.8.8. Dyeing with Coupling and
easily reserved, they are still used occasionally
Diazotization Dyes [211, pp. 547 – 548],
for printing grounds. For individual processes,
[214, p. 286]
see [215].
Direct dyes (see Section 4.2) that contain aro-
matic amino groups can be diazotized on the fiber
4.8.7. Dyeing with Phthalogen Dyes after dyeing and then coupled with a ‘‘develop-
er’’ – a phenol, naphthol, or aromatic amine.
As with oxidation dyes, the actual dye in the Wetfastness, in particular, is improved by en-
phthalogen process (Bayer) – the insoluble largement of the molecule and, naturally, the
phthalocyanine pigment – is formed in the fiber shade changes as well (! Azo Dyes, 3. Direct
itself (! Phthalocyanines, Section 8.2.). Precur- (Substantive) Dyes, Chap. 2.).
sors are involved in dyeing. A distinction is made Conversely, water-soluble, substantive azo
between two processes: dyes, which carry amino or hydroxyl groups
capable of coupling, can also be used followed
Low Molecular Phthalogen Developer. by aftertreatment with a diazonium compound
Aminoiminoindolenine or its derivatives are ap- (usually diazotized 4-nitroaniline as a stabilized
plied together with heavy-metal donors (prefer- diazonium salt). The resulting polyazo dye shows
entially Cu or Ni) by padding. The pigment is excellent wetfastness (see Section 4.6).
262 Textile Dyeing Vol. 36
4.9. Other Plant Fibers (! Cellulose, range, carboxyl groups are present largely in the
Section 2.2., ! Cellulose, Section 2.3., undissociated state.
! Cellulose, Section 2.4., ! Cellulose, The number of ionic groups in the fiber de-
pends on the pH of the medium. Keratin is most
Section 2.5., ! Cellulose, Section 2.6.)
stable when the number of negative and positive
ions is identical. This isoionic region differs
Hard and bast fibers, not, like cotton, isolated
somewhat from the isoelectric region of charge
from seed hairs but from parts of stems and
neutrality. This means that charges of adsorbed
leaves, can also be colored with direct or reactive
ions add to the ion charges of the fiber. According
dyes. The noncellulosic portion of these fibers is
to EL€oD, the isoelectric point of wool is pH 4.9 at
frequently so large that even simple acid and
room temperature [218].
metal-complex dyes attach. Basic dyes can also
The morphological structure of the fiber de-
be used to produce colors that are brilliant but
termines the pathway that dyes take during dye-
have poor fastness [214, pp. 433 – 434], [217,
ing and is of decisive importance for the rate and
p. 534]. Hard fibers, such as jute and coir (the
extent of dye uptake. In the past, the dye was
fibrous outer layer of coconut), have a strong self-
assumed to have to penetrate the scaly layer on
color that is not lightfast. For this reason, they
the fiber surface. The epicuticle and the exocu-
affect the quality of all types of dyeing. Bleach-
ticle were regarded as barriers because of their
ing does not help because the fibers become
hydrophobic character. This idea was supported
yellow again when exposed to light.
by the fact that oxidative or chlorinating degra-
dation of epicuticle and exocuticle considerably
facilitates dye uptake. Oxidative or chlorinating
5. Dyeing of Wool and Silk degradation is still used in the preparation of
wool materials to be printed.
5.1. Dyeing of Wool In contrast, LEEDER [219], [220] and LEAVER
[221] showed that the penetration of dyes into the
The dyeing properties of wool (! Wool) vary fiber proceeds through the intercellular regions.
depending on the origin, breed, age, food, season, The cell membrane complex is regarded as a
and habitat of the sheep. Even fleece from a ‘‘solvent’’ for hydrophobic textile chemicals
single sheep reveals pronounced differences in [222]. The strong swelling capacity of the inter-
quality. In fact, differences are also found within cellular cement is important for the dyeing
a single fiber due to biological and environmental process [223–225]. Only subsequently are the
factors (tippy dyeing). By means of the special- sulfur-rich keratins also penetrated by the dye
ized sorting of wool provenances and fleece molecules thus, determining the position of
components, batches are put together that largely the dyeing equilibrium.
correspond with each other with regard to fine-
ness and to processing and application properties.
Apart from shorn wool, certain amounts of Bonding Forces between Dye and Fiber
hide and slipe wool from slaughtered animals are Ionic Bonds. Dye anions can participate in
available on the market. While hide wool is equal ionic interactions with fibers that possess cationic
to shorn wool, slipe wool exhibits alkali damage. groups. However, the formation of ionic bonds is
not sufficient to explain dye binding because
compounds that can dissociate are cleaved in the
5.1.1. Principles (see also, ! Dyes, General presence of water.
Survey, Section 1.4.1.)
Secondary Bonds (dispersion and polar
Wool fiber is composed of protein filaments and bonds, hydrogen bridges) are additionally formed
consists mainly of keratin with a very complex between dye and fiber. Close proximity between
structure. The amino groups of keratin are very the two is a prerequisite for bond formation.
important for the dyeing process. The number of However, this is counteracted by the hydration
basic groups titratable with acid is 850 mmol per spheres of the dye and of wool keratin. On ap-
gram of wool fiber. In the acidic and neutral proach, these spheres are disturbed, especially at
Vol. 36 Textile Dyeing 263
higher temperature, and common hydration Dyes with similar absorptive behavior should
spheres are formed (‘‘iceberg structures’’) [226]. be selected for combined application. The com-
The entropy of the water molecules involved is bination values for acid dyes established origi-
increased in this process (hydrophobic bonding). nally for polyamide were later transferred to
Dye binding can be regarded as an ion ex- wool [228–230].
change in which the ionic bond is supported by In dyeing, salt additives exhibit a retarding
secondary bonds between the dye and the poly- and leveling effect. Higher concentrations of
mer [227]. ZOLLINGER termed it an ‘‘Einweisungs- sulfate ions are assumed to compete with dye
funktion’’ that is based on the far-reaching po- anions for ammonium groups of the fiber. Weak-
tential of ionic groups (‘‘pilot ions’’). ening of the electrostatic attraction between dye
Coordinate and covalent bonds can be super- and fiber due to coulombic forces is more likely;
posed on secondary and ionic bonds. This aspect this effect decreases with increasing pH. Instead,
is discussed in connection with chrome, metal- salt additives exert an aggregating effect on dye
complex, and reactive dyes. molecules, and increased attachment can occur
[231].
5.1.2. Dye Classes and Dyeing Processes Dyeing Processes. Dyeing instructions for
different types of acid wool dyes vary, espe-
5.1.2.1. Acid Dyes cially with regard to the pH range used (see
Table 7). The greater the affinity for the fiber,
Acid dyes consist of simple chromophoric sys- the more strongly must the ionic binding
tems (! Azo Dyes, 2. Anionic Dyes, Chap. 2., component be repressed [i.e., the pH value at
! Anthraquinone Dyes and Intermediates, Sec- the beginning of dyeing must be higher (see
tion 3.2.), which are made water soluble by the Table 7)].
introduction of sulfonic acid groups. Dissociation The starting temperature is 60 C for leveling
gives rise to dye anions that interact with the dyes, 50 C for milling dyes, and 30 C for
ammonium groups of the fiber. These groups are super-milling dyes. Usually, the acid is allowed
formed from amino groups in the presence of acid, to react with the fiber for 10 min; then salt is
which explains the name of this class of dyes. added followed, after another 10 min, by the
From a coloristic standpoint, acid dyes are dissolved dye. After another 10 min, the system
subdivided according to their affinity. Affinity is heated for 30 – 45 min until a final tempera-
increases from leveling dyes and weakly acidic ture of 95 C is reached and then further dyed at
absorbing (moderately leveling) milling dyes to 95 C for 45 – 90 min. Addition of acid toward
neutral absorbing (poorly leveling) super-milling the end of the dyeing process completes bath
dyes (! Azo Dyes, 2. Anionic Dyes, Chap. 2.). exhaustion. Warm and cold rinsing follows. With
This sequence approximates the increase in size selected dyes dyeing can be performed at 80 C.
of the dye molecule. The presence of aliphatic Milling dyes require the addition of a leveling
groups in the dye molecule contributes to a agent (! Textile Auxiliaries, 5. Dyeing Auxili-
substantial increase in binding to wool, convert- aries, Chap. 6.).
ing leveling dyes to types that are fast to fulling. Trichromic dyeing can be conducted with
The sulfonic acid groups determine not only the leveling dyes. In the case of milling dyes, the
number of possible ionic bonds to the fiber, but desired shade is better achieved by selection of a
also hydration, which counteracts binding. dye with similar hue and shading.
Improvement in Fastness. The wetfastnesses contributes to fiber protection [238]. In the past,
of chlorinated wool that has been finished with the amount of dichromate required was 50 %,
synthetic resin (polyamide – epichlorohydrin or based on the dye used, but no less than 0.25 % or
polyurethane) (superwash wool) can be in- more than 2.5 %, based on the fiber. According
creased by means of methylol amide compounds. to Ciba – Geigy, the amount of potassium di-
Both fastness and antifelting finish can be im- chromate used is a standard 0.2 þ 0.15 the
proved through the application of a polyquatern- amount of dye in percent. In the meantime,
ary compound (i.e., a compound with several considerable reductions of potassium dichro-
quaternary groups) [232] [Basolan F (BASF), mate content have been found to be possible
Sandofix L (Sandoz)]. Anionic condensation [239], [240]. Individual chrome factors are
products can form a barriere at the surface of given in pattern cards.
the fiber and thus dimish the bleeding of anionic Auxiliary agents cause the disaggregation of
dyes (see Section 6.4.2) [Mesitol HWS (Bayer)]. chrome dyes and form adducts with them. These
adducts break down only at boiling temperature.
5.1.2.2. Chrome Dyes In this way, the number of free amino groups
available for complex formation is decreased and
Chrome dyes (! Azo Dyes, 2. Anionic Dyes, less acid is required. The dyeing becomes more
Chap. 2.) refer to selected acid dyes that form level, and ‘‘tippy dyeing’’ is reduced. Ethoxy-
complexes with chromium ions. During complex lated fatty alcohols, alkylphenols, and fatty
formation a strong bathochromic shift of shade amines are suitable auxiliaries.
occurs. As a result of the superposition of several
excited states, a marked dulling of the hue is Application
observed.
Complex formation occurs during the dyeing Afterchroming Method (Chrome-Developing
process in a strongly acidic medium under the Dyes). For dyeing the liquor is prepared with
participation of electron donors (ligands) from 1 – 2 g/L of formic acid (50 %) (pH 3.5 – 3.8),
the chromophore and the fiber [233], [234]. 0 – 2 g/L of calcined sodium sulfate, and 1 –
Chromium, the central atom of the complex, acts 2 g/L of wool protectant. The process is started at
as a link between dye and fiber. This results in a 40 C, and dissolved dye is added after 10 min.
very strong bond, which is reflected in the excel- The system is heated within 30 min, and dyeing
lent fastnesses obtained. The binding of chromi- is performed at 90 C for 30 – 45 min. If the
um occurs by substitution of the H in COOH or exhaustion of the bath is too low, 0.5 – 1.0 g/L of
OH groups and via lone electron pairs from formic acid is added and dyeing is continued for
>CO, NH2 or N¼N groups (dative bonds). 15 min.
Thus, the dyes must contain suitable functional For subsequent chroming the bath is cooled to
groups: 70 C, followed by the addition of potassium
dichromate and heating. Temperature is main-
1. Monofunctional: salicylic acid or alizarin tained at 90 – 100 C for 30 – 45 min. After
type 15 min, 5 – 10 g/L of sodium sulfate is added
2. Bifunctional: o,o0 -dihydroxyazo groups to detach the saltlike bound chromate from the
wool and make it accessible to complex forma-
Chromium(III) with the coordination num- tion (Bayer). Other variants use reducing and
ber 6 acts as the central atom. It is formed from complexing agents to support the chemical reac-
dichromate, which is reduced by the fiber. tions [241]. Finally, neutralization is carried out
Strong acids have an activating effect on this with ammonia (pH 8).
process [235]; the reducing effect of wool can
also be enhanced by organic acids (tartaric, One-Bath Chroming Method (Metachrome
lactic, or formic acid) [236]. Thiosulfate also Process). Complex formation must be preceded
acts as a reducing agent, increasing the rate and by dye diffusion. For this reason, the release of Cr
degree of conversion in chroming [237] and (VI) must be delayed.
decreasing fiber damage [236]. Lowering the The dye liquor is prepared with 3 – 8 % of
temperature from boiling temperature to 90 C metachrome mordant (a mixture of sodium
Vol. 36 Textile Dyeing 265
chromate and ammonium sulfate) and 2.5 – 5 g/ can be added to the last rinsing bath. A lowering
L of crystalline sodium sulfate. After a prerun of of the temperature to 80 C is possible in the
10 min at 40 – 50 C, the system is heated slow- presence of an ethoxylated fatty amine (pH
ly and dyed at boiling temperature for 45 – 1.9 – 2.2).
90 min. Shortly before dyeing is completed, the Dye Ranges. Chromolan (Ostacolor), Ino-
bath is exhausted by the addition of 1 – 2 g/L of chrom (Zeneca), Neolan (Ciba – Geigy), Palati-
30 % acetic acid. necht (BASF).
The boiling time is shortest in the afterchrom- Auxiliaries. Albegal NF, Albegal Plus
ing method, and the most level and fast colors are (Ciba – Geigy); Avolan S, SCN (Bayer); Lyogen
produced. Poor shading possibilities represent a WD (Sandoz); Syntegal V7 (Ostacolor); Uniper-
disadvantage. The one-bath chroming method is ol O and SE (BASF).
most important.
The following auxiliaries are used: Albegal W 5.1.2.4. 1 : 2 Metal-Complex Dyes (! Metal-
(Ciba – Geigy), Avolan AV (Bayer), Lyogen omplex Dyes, ! Metal-omplex Dyes, Section
MS, WD, Lyocol CR (Sandoz), Syntegal V7 5.1.1.)
(Ostacolor),Uniperol O (BASF).
Metal complexes are formed in a molar ratio of
5.1.2.3. 1 : 1 Metal-Complex Dyes (! Metal- 1 : 2 in the weakly acidic pH range [i.e., two
omplex Dyes, Section 5.1.1.) chromophores are coordinated to one central
atom (Cr or Co)] [244]. This atom is located
Metal-complex dyes are chemically very similar between the two chromophores, which are usu-
to chrome dyes. The risk of fiber damage is ally arranged perpendicular to each other
reduced because the complex is formed in dye (Drew – Pfitzner complexes, ! Metal-omplex
production. Dyes, Section 2.2.). The high affinity for the fiber
Dyeing is conducted in a strong sulfuric acid is based on the large size of the dye molecules;
medium at pH 1.9 – 2.2. Amino groups in the their compact, often almost spherical shape; and
fiber are converted to the ammonium form, and their negative charge [245].
ionic bonds to the dye anion are formed. Under To achieve sufficient evenness (levelness), the
these conditions, amino groups are not available incorporation of sulfonic acid groups into the dye
as ligands. Only with increasing pH during rins- molecules was initially avoided so additional
ing can they be included in the complex in ionic interactions between fiber and dye could be
exchange for aquo ligands [242]. The addition excluded. Instead, water solubility was achieved
of auxiliaries (alkanolethoxylates) allows a de- by incorporation of methylsulfone (SO2CH3)
crease in the amount of acid added (pH 2.5 – 3) [246] or sulfonamide (SO2NH2) groups.
because they form addition compounds with the Only after 1960 did dyes containing sulfonic
dye and thus repress complex formation. The acid groups also find application. They have the
dyeing process is slowed down and made uni- advantages of inexpensive production, higher
form. With synergistic amphoteric mixtures of yield, and cold solubility. In general, the wetfast-
auxiliary agents, dyeing can be performed at even ness is somewhat higher than that of dyes con-
higher pH (3.5 – 4) [243]. taining methylsulfone and sulfonamide groups.
Unfortunately, dyes containing two sulfonic acid
Dyeing Process. Depending on the liquor groups, in particular, are susceptible to nonlevel
ratio, the bath is adjusted with 2 – 6 g/L of dyeing. To avoid tippy dyeing, auxiliary agents,
sulfuric acid (96 %) to pH 1.9 – 2.2 (pH 2.5 in especially ethoxylated fatty amines, are added
the presence of 1 – 2 g/L of auxiliary agents). [247], which form adducts with the dye. These
After addition of 5 – 10 g/L of calcined sodium adducts break down at higher temperature. The
sulfate, the material is treated with the liquor for leveling effect is increased by addition of
10 min at 40 – 50 C; then the dissolved dye is Glauber’s salt.
added. Ten minutes later, the system is heated Since the 1 : 2 dye complexes are formed in a
up in 30 – 45 min and dyeing is carried out at weakly acidic medium, they can be applied to
boiling temperature for 90 min; 1 – 2 mL/L of wool under the same conditions. This enables a
ammonia (25 %) or 2 – 3 g/L of sodium acetate gentle mode of dyeing, which implies neither an
266 Textile Dyeing Vol. 36
oxidative attack by Cr(VI) nor a hydrolytic attack sulfone) have the advantage that their functional
by sulfuric acid. groups are masked at the start of the process;
consequently, no premature reaction occurs be-
Dyeing Process. Ammonium sulfate (1 – low boiling temperature [251]. At the same time,
2 g/L) or ammonium acetate (2 – 4 g/L) (pH level dyeing is made possible by the increased
5.5) is added to the liquor. After a prerun of solubility. Drimalan and Lanasol dyes are bi-
10 min at 30 – 50 C, dissolved dye is added. functional and can have a cross-linking effect on
The system is heated in 30 – 60 min and dyed for wool [226], [252].
30 – 60 min at boiling temperature.
In the presence of auxiliaries (1 – 2 g/L) dye- Influence of pH. In the acidic range, ionic
ing is performed with the addition of 1 – 3 g/L of bonds are formed between dye and fiber, with the
acetic acid (30 %) (pH 4.5 – 5) and 1 – 2 g/L of dye still being capable of migration. At pH 5,
calcined sodium sulfate. Acid dosing using con- covalent binding to the fiber predominates.
trol and monitoring systems is also possible
[248], [249]. After rinsing, 1 – 2 g/L of formic Dyeing Process. Auxiliary agent (1 – 2 g/
acid is used for acidification to improve the feel L) is added to the liquor, and the pH adjusted to
and wetfastness. 3 – 4 with formic acid or 1 – 3 g/L of acetic
Auxiliary Agents. Albegal A, SET, SW acid. The process is started at 40 C, and dis-
(Ciba – Geigy);Avolan IL, IS, IWN, UL75 solved dye is added after 10 min. After 20 –
(Bayer); Eganal SZ (Hoechst); Lyogen FN, MS 30 min, the pH is adjusted to 5 – 6 with sodium
(Sandoz); Remol U (Hoechst); Uniperol SE, W dihydrogenphosphate. Dyeing is conducted at
(BASF);Unisol WL (Zeneca); Wofalansalz EM boiling temperature for 1 h.
(Wolfen). To eliminate hydrolyzed dye, an aftertreat-
ment is performed for 15 min at 80 C with the
5.1.2.5. Reactive Dyes (! Reactive Dyes) addition of 1.5 g/L of ammonia (pH 8.5 – 9.0).
The last rinsing bath is weakly acidified.
Reactive dyes for wool produce brilliant colors Auxiliary Agents. Albegal B (Ciba – Ge-
with good fastness. They are not identical to igy), Avolan REN (Bayer), Eganal GES
reactive dyes for cellulose fibers because the (Hoechst), Lyogen FN (Sandoz).
reactivity of the amino groups in the wool is
considerably higher than that of the hydroxyl 5.1.2.6. Vat Dyes, Leuco Esters of Vat Dyes
groups in cellulose. To achieve level dyeing on
wool, the reactivity of the dye must be reduced In the past, vat dyes played an important role in
and an auxiliary agent added. dyeing wool. Indigo (! Indigo and Indigo Col-
orants) was considered to be ‘‘king of dyes’’
Reactive anchor groups Dye ranges
because of its unsurpassed fastness on wool.
N-Methyltaurine ethylsulfone- Hostalan E, Procilan E Until the mid-1950s, navy cloth was dyed with
b-Sulfatoethylsulfone- Remalan indigo. The application was problematic with
Acrylamide-, chloroacetyl- Procilan regard to the negative effect of reducing agents
a-Bromoacrylamide- Lanasol, selected Lanaset
2,4-Difluoro-5- chloropyrimidyl- Drimalan F
and alkali on wool. Today, indigo, thioindigo,
and their derivatives have been replaced by
classes of dyes that are easier to handle.
Wool contains many reactive groups – amino,
imino, and hydroxyl groups being the most im-
portant [250]. Reactions occur in a weakly acidic 5.1.3. Technology of Dyeing (see Chap. 2)
medium (pH 3 – 5) and include nucleophilic
substitution of leaving groups (usually Cl, F, and Wool is dyed in equal amounts in the form of
rarely, sulfonate or ammonium groups) or addi- flock and slubbing. There is a trend toward piece
tion reactions to polarized aliphatic double bonds and yarn dyeing [253]. The overflow can take the
(see Section 4.1). place of winch and beam dyeing machine, and
The first two anchor groups mentioned (N- jigger if the material has previously been made
methyltaurine ethylsulfone and b-sulfatoethyl- shrink proof [254]. High-quality, cool wool
Vol. 36 Textile Dyeing 267
articles that are woven from fine yarns require not only on the required level of fastness, but also
especially gentle treatment. on the necessary brilliance. Brilliant shades are
Wool dyeing is usually conducted near boil- produced by acid and reactive dyes, whereas
ing temperature. The fiber suffers clear degrada- chrome dyes dominate in the case of black.
tion at this temperature. In some cases, the tem- Among the chrome and metal-complex dyes,
perature can be lowered to 80 – 90 C. An in- 1 : 2 metal-complex dyes are easiest to use, and
crease in dyeing temperature has proved neces- corrections of shade (shading) are possible. Super-
sary when poorly leveling dyes are applied. wash articles require a high levelof fastness,which
However, 108 C is generally accepted as the can be achieved with reactive dyes. The fastness of
upper temperature limit. A further increase in dyeings with various classes of wool dyes at 1/1
temperature can be required only in dyeing poly- standard depth of shade is given in Table 8.
ester – wool mixtures by the high-temperature Excellent fastness to milling and potting is
process (see Section 11.2). In this case, the upper achieved with chrome and metal-complex dyes.
limit is 120 C. Formaldehyde is added to the Damage of the wool during dyeing is due to
liquor, which leads to formation of methylene action of acid, oxidizing agent (chromate), water,
bridges in the fiber and stabilizes the keratin to heat, and mechanical stress. Exposure to boiling
hydrolytic degradation [255], [256]. water for a longer period results in cleavage of
The fields of application of various classes of cystine cross-links. New bridges are formed,
wool dyes are based on the absorptive and level- such as lysinoalanine, which can contribute to
ing capacity [257]: crease fixation. Thus, woolen fabrics should be
setted before dyeing. Hydrolytic degradation
<1/1 standard depth disulfonic acid dyes
increases with increasing distance from the iso-
1/1 – 3/1 standard depth monosulfonic acid dyes electric point [259]. The sodium sulfate present
>3/1 standard depth 1 : 2 metal- complex dyes increases hydrolysis, which is closely connected
to a deterioration of mechanical properties [260].
The 1 : 2 metal-complex dyes are considered
Continuous processes are frequently used to
most favorable with respect to maintenance of
dye slubbing. Here, a thickening agent based on
feel, elasticity, and strength.
etherified guar or locust bean gum, a special
Chlorinated wool exhibits a different coloris-
auxiliary agent, and an acid or acid donor are
tic behavior. Elimination of the scaly layer facil-
added to the pad liquor. Chromium trifluoride is
itates both dye uptake and release. The wetfast-
generally used as the chroming agent. The mate-
ness is much lower, so reactive dyes should be
rial is steamed for 15 – 60 min after padding.
used. In contrast, antifelting treatments with
synthetic resin seldom lead to changes in color-
5.1.4. Properties of Dyeings istic behavior.
Class of dye Washfastness (40 C) Fastness to perspiration (acidic) Fastness to perspiration (alkaline) Lightfastness
Acid dyes 4 – 5 2 – 4 2 – 4 3 – 6
Milling dyes 4 – 5 4 – 5 4 – 5 5 – 6
Super-milling dyes 4 – 5 4 – 5 2 – 5 4 – 6
Chrome dyes 4 – 5* 4 – 5 4 – 5 6 – 8
1 : 1 Metal-complex dyes 4 – 5* 4 – 5 4 – 5 5 – 7
1 : 2 Metal-complex dyes 4 – 5* 4 – 5 4 – 5 6 – 7
Reactive dyes 4 – 5* 4 – 5 3 – 5 4 – 6
*
At 60 C.
268 Textile Dyeing Vol. 36
fibers. Stretch fabrics made of wool weft and PA The isoionic point of silk is at pH 5.0. The
textured yarn warp have gained importance as ski stability of silk is considerably lower than that
tricot. Both types of fiber are, in principle, dye- of wool because silk has no cystine cross-links.
able with the same classes of dyes. However, PA Even under mild conditions, e.g., at pH 4.0 and
is more accessible to the dye and is, consequent- 85 C, hydrolytic degradation is observed.
ly, dyed more deeply than wool in the case of Therefore, acid must be added continuously
light colors. Only when the limited ionic binding during the dyeing process and not at once. For
capacity of the NHþ 3 groups in PA is exhausted this reason, dyeing is frequently conducted at
does the higher binding capacity of wool become 70 – 80 C, but no higher than 90 C. In this
noticeable so that, for deep shades, the wool way, damage to the surface structure and
component is darker. For light shades, the differ- wrinkle and crease formation are minimized
ent affinity can be adjusted by using fiber- [262].
affinitive retarding agents, such as aromatic As a result of its fineness, light is strongly
sulfonates, which partly reserve the PA compo- reflected from the surface of silk. Thus, consid-
nent. The level of auxiliary agents depends on the erably more dye is required to achieve the
depth of color and is 0.5 – 4 %. Monosulfonated required shade than with other materials.
acid dyes are the most suitable.
For the pretreatment of silk (steeping, soupling, Modified Types of Polyamide (! Fibers,
degumming, hardening), see [267], [270]. 4. Polyamide Fibers. Chap. 4.) contain a varying
The dyeing of yarn hanks is frequently con- number of amino groups [272]. The dyeing char-
ducted on spray or package dyeing machines. acteristics of PA fibers as a function of the
The winch, beam and overflow are preferred for content of amino groups (mmol per gram of
fabrics (see Section 2.2.3). polymer) are given below
270 Textile Dyeing Vol. 36
Additional dye uptake beyond the ionic bind- As a result of the level dyeing of even struc-
ing capacity is possible only in the form of purely turally nonuniform material, disperse dyes are
secondary adsorption (‘‘overdyeing’’). Dissocia- applied especially in dyeing lighter shades. Wet-
tion and hydration counteract this effect. The fastness deteriorates with increasing depth of
dyeings obtained by overdyeing have poor wet- color.
fastness. The amount of these weakly bound dyes
can be determined under conditions in which Dyeing Process. A dispersing agent
ionization of the amino groups does not occur (0.25 – 2 g/L) is added to the liquor, and the pH
(‘‘neutral absorptive capacity’’ according to is adjusted to 5 with acetic acid. The process is
HOFFMANN). started with the material at 40 C and followed
The simultaneous action of ionic bonds and by addition of dye after 5 min. After another
secondary bonds determines the degree of dye 5 min, the system is heated up within 30 min, and
uptake in equilibrium. This is frequently re- dyeing is conducted in 60 min near boiling
flected in a superposition of the Langmuir and temperature.
Nernst isotherms [284], [285]. Dye Ranges. Artisil (Sandoz), Cibacet
The amount of dye bound at equilibrium (Ciba – Geigy), Dispersol (Zeneca), Celliton
decreases with increasing number of sulfonic (BASF), Ostacet (Ostacolor), Resolin P (Bayer),
acid groups in the dye molecule due to increasing Samaron (Hoechst).
hydration. For this reason, mono- and polysulfo- Auxiliary Agents. Eganal SZ (Hoechst), Le-
nated acid dyes should not be used together in vegal HTN (Bayer), Uniperol EL (BASF), Uni-
combination dyeing. vadin DP (Ciba Geigy).
direct dyes – the rotatability of the linked parts is 2. Acid donors release acid during the dyeing
maintained. So the affinity to the fiber is in- process. Substances used are ammonium
creased without changing the color. In larger sulfate, which liberates NH3 during dye-
molecules a similar effect is achieved by a steric ing; sodium pyrophosphate (Na4P2O7),
hindrance of coplanarity within the chromophore which is converted to the acidic disodium
system (benzidine dyes with sulfonic acid groups hydrogenphosphate [293]; esters of organic
in o,o0 -position). acids; and heterocyclic compounds, which
The secondary binding of dye to PA is coun- slowly release organic acids when exposed
teracted by hydratable sulfonic acid groups, to heat.
which explains the large spectrum of dyeing
properties. A classification according to techni- In the case of low-affinity acid dyes, addition
cal application is given below: of acid toward the end of dyeing is recommended
for full exhaustion of the dyebath.
1. Monosulfonated Acid Dyes. Leveling dyes The classical temperature control is more
and neutral absorbing dyes. These grades can favorable than pH control for regulation of the
easily be combined with each other. dyeing process [293]. In the case of pH control,
2. Disulfonated Acid Dyes. These dyes produce absorption of ca. 60 % of the dye is quick and
dyeings with good wetfastness. They are used nonlevel, and only the last 50 – 20 % is absorbed
as self- colorants but are not recommended for in a controlled manner.
trichrome dyeing [287]. In the acidic range, electrolytes retard liquor
exhaustion [294]. The competition of sulfate
The dyeing behavior of acid dyes can be anions with the dye for dye-affinitive positions
described with the help of the combination values is responsible for this effect (see Section 5.1.2.1).
K (see Chap. 12), which are derived from com-
bination dyeings at 70, 80, and 90 C [288], Auxiliary Agents improve leveling. In the
[289]. In the case of matching shades from case of fiber-affinitive agents, the sum of the dye
dyeing and subsequent dyeing in the same bath anions and auxiliary agent anions should not
the combination values of the dyes involved are exceed the binding capacity of the fiber to avoid
equated. Monosulfonated acid dyes lie in the blocking effects [295].
range K ¼ 1 – 5, and polysulfonated acid dyes
have still higher values. The higher this number, Aftertreatment. The wetfastness of dye-
the greater are the contrasts. The combination ings produced with acid dyes is often unsatisfac-
values of dyes from different dye manufacturers tory. In contrast to wool where the hydrophobic
cannot be compared [287], [290], [291]. scaly layer hinders the escape of dye molecules
The pH of the liquor is important for level from the fiber during washing, PA does not have a
dyeing, for exhaustion of the bath, for wastewater barrier of this kind. However, a barrier can be
contamination, and for the effort involved in produced by aftertreatment.
rewashing after dyeing. With increasing dye In older processes, tannic acid (polygalloyl-
affinity, the ionic interaction in the initial phase glucose) and potassium antimony(III) oxide tar-
must be repressed to achieve uniform absorption, trate (tartar emetic) are used that form a 1 : 1
i.e., the liquor must be neutral at the start of the adduct on the material via hydrogen bridges
dyeing process. Only in the course of dyeing is [296]. This finishing process is expensive and
the liquor slowly acidified by one of the follow- said to be carcinogenic.
ing methods [292]:
Synthanes. The synthetic tanning agents
1. Acid is added at the beginning of dyeing (synthanes) represent a more favorable alterna-
or continuously, preferably by using pH- tive. They are high molecular mass condensation
controlling instruments: Telon ST process products of aromatic sulfonic acids with formal-
(Bayer), Dosacid process (Ciba – Geigy). dehyde [297], [298] or condensation products of
Special care is required in the neutral range phenol, cresol, catechol, and naphthol with form-
because small amounts of acid give large aldehyde, which are made water soluble by re-
shifts in pH value. action with bisulfite.
Vol. 36 Textile Dyeing 273
These products deposit on the fiber surface 1 – 2 % (per weight of fiber) of synthane is added.
and, because of an accumulation of negatively Aftertreatment is started at 40 C, the bath is
charged sulfonate anions, form an electrostatic heated to 70 – 80 C, and the material is treated
barrier that counteracts the release of dye anions for 20 – 30 min; the material is then rinsed.
from the fiber. In accord with this is the observa- Auxiliary Agents for pH Control. Eulysin
tion that a highly negative electrokinetic (zeta) WP (BASF), Sandacid V, VS (Sandoz).
potential is formed [299]. Synthanes. Cibatex PA (Ciba – Geigy), Me-
This treatment mainly increases the contact sitol NBS (Bayer), Matexil FA-SN (Zeneca),
fastness (e.g., to water, perspiration, and seawa- Nylofixan P (Sandoz).
ter) of acid and metal- complex dyes and, to a
lesser extent, their washfastness. The fastness to
chlorinated water in swimming pools is hardly 6.4.3. 1 : 2 Metal-Complex Dyes
improved. Synthanes also have a stain-repelling
effect on floor coverings [299]. The classical 1 : 2 metal- complex dyes (!
Aftertreatment with synthanes has a number Metal-Complex Dyes) are acid dyes that are
of disadvantages. Synthanes can reduce the ad- coordinately bonded to transition metals, espe-
hesive strength of coatings or laminates [300]. In cially chromium and cobalt, in the molar ratio of
addition, they are poorly resistant to dry heat, 1 : 2. These dyes are negatively charged and can
afterfixing, and steam; treatment with synthanes enter into ionic bonding with the fiber. The amino
results in slight changes in shade, reduced light- groups of the fiber are not included in the com-
fastness, and a hardening of the feel. In the plex. In contrast to acid dyes, the water solubility
presence of cationic softeners, the fastness to of classical 1 : 2 metal- complex dyes is not based
rubbing is decreased. Synthanes are frequently on the presence of sulfonic acid groups. Rather, it
applied despite their disadvantages. is due to sulfonamide and methylsulfone groups.
The product Fadex CL (Sandoz) was devel- Only after 1960 were dyes containing sulfonic
oped specially to improve the fastness of bathing groups put on the market (see Section 5.1.2.4).
suits to chlorinated water. However, it cannot be Their high affinity for the fiber is caused by
used for printed articles with a white ground or secondary bonds with the large molecules that
bleached material because of its brown self- color. are frequently almost spherical. As a result of
their low water solubility, the traditional 1 : 2
metal- complex dyes are not as suitable for dye-
Dyeing Processes. ing PA as for wool. Dyes containing sulfonic acid
Dyeing with Temperature Control. The pH groups behave more favorably and, at the same
of the dyebath is adjusted to about 4.5 – 7, and time, produce better wetfastness. Their high fast-
0.2 – 2 g/L of dyeing auxiliary is added. The ness level makes them suitable for articles that
process is started cold with the material and are exposed to special use, such as floor cover-
allowed to prerun for 20 min. Dissolved dye is ings and car seat covers. The tendency of these
added; the system is heated up in 30 – 45 min dyes to mark structural differences in the material
and dyeing is continued for 20 min near boiling is a disadvantage. For this reason, they are re-
temperature. commended only for dark shades. The disulfo-
nated acid dyes give good light- and wetfastness
Dyeing with pH Control. Dye is dissolved in on PA and are frequently used in PA dyeing
the liquor, the pH is adjusted to 8.5 – 10 with despite the poorer build-up properties. The high
ammonia, and the auxiliary agent is added as affinity of 1 : 2 metal- complex dyes makes the
described above. The material is placed in the addition of amphoteric or nonionogenic leveling
boiling liquor, and acid is added slowly. The final agents necessary.
pH of 4.5 is attained after 45 – 60 min. (Alter- The absorption of dyes by PA increases with
natively, 0.25 – 1 g/L of a pH regulator can be decreasing pH. This tendency is especially pro-
added.) nounced in the case of disulfonic acid dyes. They
are dyed in the presence of acetic acid. Dyeing
Aftertreatment. The exhausted bath or fresh with dyes free of sulfonic acid groups depends
liquor is adjusted to pH 4.5 with formic acid, and less on the charge of the fiber and more on the
274 Textile Dyeing Vol. 36
extent of formation of free complex acid, which of dye taken up being given as the fiber sum
absorbs more easily than the anion [301]. number in SF units (1 SF ¼ 25 mmol/kg) [291].
The values lie between 1 and 3. The exhausted
Dyeing Process. Dye and 0.5 – 1 g/L of bath can be used again, e.g., for a blue color by
auxiliary agent are added to the liquor. It is then addition of a yellow dye and the shade compared
made weakly acidic by the addition of 0.5 – 2 g/L with a chart [302].
of ammonium sulfate and 0.5 – 1 g/L of acetic
acid (60 %), if necessary. High-affinity dyes can Pretreatment (Washing, Prefixing). Be-
be used in a neutral or weakly alkaline medium. fore dyeing, fabrics generally must be prefixed
The process is started at 30 – 40 C, followed by to compensate for material-related differences in
heating up within 30 – 60 min, and dyeing at affinity and to reduce the sensitivity to creasing
boiling temperature for 30 – 60 min. A prerun during the dyeing process. Prefixing can be per-
with auxiliary agent at boiling temperature formed as thermofixing on the frame [15 – 20 s
reduces the stripiness of the color. at 190 C (PA 6) or 200 – 230 C (PA 66)] or as
hot-water fixing (45 min at 130 C).
Class of dye Washfastness (40 C) Fastness to perspiration (acidic) Fastness to perspiration (alkaline) Lightfastness
Year Total Staple fiber Filament Total fiber production Synthetic fiber production
Since the fundamental work of MEYER and At constant temperature, the distribution coeffi-
KARTASCHOFF in 1925 [313] and the studies of cient K [i.e., the ratio of the concentration of dye
VICKERSTAFF [314] in the beginning of the 1950s, dissolved in the fiber (CF) and in the liquor (CL) at
a large number of studies have been published on equilibrium] is constant.
the kinetics and thermodynamics of dyeing cel- At normal dyeing temperatures the rate of
lulose acetate and synthetic fibers with disperse dissolution of dispersed dyes in the dye liquor
dyes in aqueous dyebaths. For a survey, see [315, is assumed to be high, so that CL is constant as
pp. 67, pp. 147]. Disperse dyes as well as acid long as undissolved dye is present. Although not
and basic dyes must be molecularly dispersed in always valid in practice, the motion of the liquor
the dyebath; i.e., the dye must be dissolved in the is also assumed to be high enough so that mo-
aqueous bath before it can adsorb to the fiber lecularly dissolved dye is always transported to
surface and then diffuse into the fiber. the fiber surface in sufficient amounts and the
Thus, the form in which the disperse dye is adsorption of dye proceeds rapidly. Then, diffu-
present in the dye liquor is decisive for the dyeing sion in the fiber is the step that determines the rate
process. The water solubility and rate of dissolu- of dyeing. The amount of dye g that diffuses in a
tion are influenced by many factors including certain time follows Fick’s first law:
[316–318]:
D
g¼ ðCL CF Þ
h
1. Temperature
2. Particle size
3. Crystal modification The diffusion coefficient D is 1010 to 1012
4. Crystal growth cm2/s and can be increased only by an increase in
Vol. 36 Textile Dyeing 277
temperature. The diffusion path h is predeter- For this reason, the practical dyeing process
mined by fiber geometry; the concentration gra- cannot (yet) be described by simple theoretical
dient CL CF, by CL. models. Despite many careful studies of model
Many experiments were carried out to devel- systems and individual processes, which permit a
op an equation for the kinetics of dyeing. How- semiquantitative interpretation of individual
ever, only approximations result because of the steps under standardized conditions, dyeing re-
complexity of the fiber state and of the processes sults still cannot be mathematically predicted
occurring in the dye liquor. The following phe- unambiguously. Thus, a dyeing process must be
nomena are of special interest: elaborated from dyeing experiments. Recipes are
drawn up on the basis of trial dyeings with the
1. The polyester fiber contains varying propor- help of color measurements.
tions of crystalline and amorphous regions, When elaborating a dyeing process in prac-
depending on the degree of drawing and the tice, it is important to realize that, with regard to
fixing state. Only regions that are amorphous the rate of absorption, the system consisting of
above the glass transition temperature are hydrophobic fiber and disperse dye occupies an
accessible to dye diffusion. During dyeing, intermediate position compared to other classes
the amorphous portion can change as a func- of dyes. The rate of diffusion of disperse dyes
tion of stress and shrinkage. In addition, the into hydrophobic fibers is moderately tempera-
dyeing medium (water) and the dye already ture dependent. Absorption can be easily regu-
diffused into the fiber change the fiber struc- lated by controlling the temperature. Further-
ture and, thus, the dyeability. more, this intermediate position between fast
2. In the dyebath, the dye goes through a large and slowly diffusing dyes is characterized by
number of stages, from solid particle to a adequate migration capacity of the dyes, espe-
single molecule, which interact with each cially at high temperature. Thus, unlevel dye-
other. These include: ings can be leveled out within manageable
Dissolving in the liquor periods of time. Both methods (temperature
Possibly melting control during exhaustion and high temperature
Adsorption of dispersing agent leveling) are basically available for dyeing with
Association to dispersing agent disperse dyes:As a result of rapid absorption of
Incorporation into dispersing agent micelles the dyes, the dyeing at the end of the exhaust
Diffusion through the laminar liquor layer phase is uneven and becomes level through
on the fiber surface subsequent adequate migration at high temper-
Adsorption to the fiber ature. The dyeing at the end of the exhaust phase
Agglomeration, aggregation, crystal growth is largely level due to controlled absorption with
Mutual influencing of dyes, isomorphism of a bath exhaustion rate that is below a previously
different dyes (formation of mixed determined limit. The subsequent high-temper-
crystals with different solution behav- ature phase serves only to ensure good
ior than pure components) penetration.
Chemical changes (e.g., reductive destruction)
Irrespective of the method selected, a series of
3. The levelness of dyeing – the basic require-
basic rules with regard to the time requirement,
ment of coloring – is endangered by differ-
safety, and quality can be deduced from knowl-
ences in temperature and concentration. In
edge of the optimization of the absorption phase
practice, such differences are unavoidable
(method b). These are:
because of irregularities in the velocity and
direction of the liquor flow at various posi-
1. In one formulation, dyes should be combined
tions in the dyeing aggregate and gradual
that, in the amounts applied, have exhaustion
depletion of dye in the liquor during passage
characteristics that are as similar as possible.
through the dyebath. Hence, a constant supply
2. While the dyeing apparatus is being heated,
of dye at the fiber surface is not guaranteed,
the main exhaust range of the dyes, which
and diffusion no longer determines the rate of
covers about 30 C, should be passed through
dyeing.
sufficiently slowly.
278 Textile Dyeing Vol. 36
3. The heating rate in the critical temperature temperature increase of 10 C doubles the rate.
range should be adjusted to the type and For this reason, at ca. 200 C fast colored fibers
design of the textile and to liquor circulation can be obtained with disperse dyes within sec-
or the circulation rate of the material [320], onds. Especially for PES – cellulose mixtures,
[321]. this property is used to dye PES fibers continu-
ously in a pad-fix process, which was introduced
To follow the first of these rules, information by Du Pont as the thermosol process [315,
about the combinability of dyes is obtained from pp. 191 – 202], [325, pp. 141 – 142] (see Sec-
dye suppliers. The fact that the temperature range tion 11.1). Application of the dye from an aque-
in which the main amount of dye exhausts de- ous dispersion is followed by drying and fixing.
pends on the amount of dye must also be taken During drying, the padded dye liquor on the
into account. Moreover, dye producers offer fiber surface can migrate to positions with a
premixed disperse dyes whose components are higher rate of drying. This danger is counteracted
selected in such a manner that the mixture ab- with an antimigration aid (! Textile Auxili-
sorbs evenly at relatively low temperature and, aries, 5. Dyeing Auxiliaries, Chap. 9.) [326]. To
consequently, makes fewer demands on the dis- obtain a dye distribution on the fiber surface that
persion stability (e.g., [322]). At the same time, is as homogeneous as possible, a uniform liquor
the melting behavior of mixtures (usually melt- film must be produced on the fiber. For this
ing point depression) should not be overlooked purpose, additives are used that wet the fiber
[323]. When using mixed dyes, differences in the and, at the same time, have a dissolving effect
fastness of the components must be accepted. on dyes (e.g., ethoxylated fatty alcohols or fatty
Trade names of combination dyes include Foron acids).
RD (Sandoz), Resolin K (Bayer), Dianix UN-SA After drying, the dye is present on the fiber
(Mitsubishi-Hoechst), and Sumikaron RPD surface embedded in a film of dyeing aids and
(Sumitomo). dispersing agents. In the case of PES – cellulose
For the second and third rules, empirical fiber blends, the dye is also present on the surface
values are used to elaborate apparatus-specific of the cellulose fibers. At fixing temperatures of
control programs that guarantee optimization of 210 C, most disperse dyes have melted or are
the dyeing process with regard to the time course dissolved in the liquid film of auxiliary agents.
and dyeing levelness. Balancing the critical dye- Three processes overlap in actual dye fixation:
ing rate of the apparatus system (VCRIT) with the (1) heating, (2) dissolving of the dye in the fiber
significant dyeing rate of the formulation (VSIG) surface layer, and (3) diffusion. Disperse dyes
(see Section 2.1) is helpful. Programs of this type diffuse into the fiber only in the molecular form.
are marketed as fast dyeing processes [324]. Sorption on the fiber proceeds rapidly. Buildup of
The dyeing process can be also controlled a high dye concentration on the fiber surface
with dyeing accelerants (carriers) (see Section layer and diffusion are competing steps that
7.2). Carriers are aromatic compounds that exert depend on the prevailing temperature and deter-
a swelling effect on PES fibers and a dissolving mine the rate of dyeing.
effect on disperse dyes. In the presence of car- In heat fixation of disperse dyes, suitable heat
riers, as in the case of special leveling agents transfer media are hot air, superheated steam,
developed for PES dyeing, theoretical elucida- contact heat, and radiant heat. Hot air and contact
tion of the dyeing process becomes even more heat are used most commonly. Steam has a
complicated. Only models are available at swelling effect on the fiber. If superheated steam
present. is used for fixation, the temperature can be
lowered in comparison with hot air, the fixing
times being the same. This is an advantage
7.1.2. Thermosol Process especially with articles made of textured fibers.
In the case of PES – cellulose fiber blends, the
In dyeing PES fibers, the dyeing time can be largest part of the liquor is absorbed by the
shortened significantly by increasing dyeing tem- cellulose fiber during drying, because of its high-
perature. The rate of dyeing increases exponen- er absorption capacity. Nevertheless, in the sub-
tially above the glass transition temperature; a sequent thermofixing step, disperse dyes are
Vol. 36 Textile Dyeing 279
almost completely fixed to the PES fiber. Trans- obtained from liquid products in various dyeing
fer from the cellulose to the PES fiber occurs both processes can deviate from those given by pow-
by migration via direct fiber contact points and ders. The advantage of liquid products is that they
through the gas phase. The type of transfer are easier to handle in the preparation of large
apparently depends on the sublimation behavior amounts of dye liquor.
of the dyes. Dyes that are resistant to sublimation Among the number of trade names available,
migrate by direct contact of the fibers, whereas the dyer selects dyes in accordance with the
those that are not prefer the gas phase. Transfer required properties and with their suitability for
through the gas phase can lead to more level certain dyeing techniques. A strict standard is
dyeing, but with easily subliming dyes a risk applied to the lightfastness of articles for car seat
exists of contaminating dyeing equipment and covers, furnishings, etc., and to the wetfastness of
incurring dye losses [327]. textiles that are washed in commercial laundries.
Fastness to thermofixing is important for all
articles that are heat-set, pleated, or resin finished
7.2. Dyeing Processes for Polyester after dyeing. Thermal stability plays an impor-
Fibers tant role in the selection of suitable products for
thermosol dyeing. Easily subliming dyes con-
PES fibers are almost exclusively colored with taminate the fixing aggregate. Many dye produ-
disperse dyes. For some time, diazotization dyes cers divide their dyes into groups according to
were used for dark shades. They are coupled to the thermal stability (e.g., ICI in Class A to D and
fiber with suitable components (e.g., 2-hydroxy- Sandoz in Class S, SE, and E). Choosing the
naphthoic acid). Although fast colors are ob- proper dye for a certain dyeing process is not
tained, the dyeing process is time consuming and easy. For this reason, dyes are also classified into
susceptible to failure, and dyeing reproducibility groups according to their rate of dyeing and the
is poor. Vat dyes are also occasionally used for main temperature range in which they exhaust
PES dyeing. Small molecular thioindigo deriva- [328]. A combination of dyes with similar ab-
tives, in particular, diffuse into PES fibers if they sorption characteristics quickly leads to level
are applied according to the thermosol process. dyeing. To determine combinability, the Ameri-
can Association of Textile Chemists and Color-
ists (AATCC) recommends an easy-to-perform
7.2.1. Requirements to Be Met by Dyes and immersion test [329].
Auxiliaries Another classification is based on covering up
material differences in textured PES fibers. Dyes
A large variety of disperse dyes are available for that have a low fastness to thermofixing often
coloring PES fibers. For the trade names of dyes hardly mark differences in texture; they dye at
recommended for PES fibers, see ! Disperse relatively low temperature and are suited to
Dyes, Chap. 7.. The Colour Index provides in- carrier dyeing processes. Dyes that are very fast
formation on dyes made by various producers to thermofixing diffuse slowly into the fiber and
that correspond chemically with each other. In must be dyed at high temperature. With a carrier,
the case of disperse dyes, however, chemically the color yield of these dyes is unsatisfactory at
identical dyes can exhibit marked differences not boiling temperature; texture and fixing differ-
only in coloring strength and shade, but also in ences in the fiber are frequently marked.
their preparation and finish. Especially in modern According to the recommendation of the So-
dyeing processes, exacting standards are set for ciety of Dyers and Colourists, four tests are used
fine dispersion and dispersion stability. Disperse to characterize the dyeing properties of disperse
dyes are supplied as powder and liquid products. dyes [330]:
Powdered dyes contain a high percentage of
dispersing agent, which is required to maintain 1. Migration test for leveling capacity
a very fine dispersion when drying a dye that has 2. Building up capacity to deep shades
been ground and dispersed in an aqueous slurry. 3. Exhaustion test to determine the temperature
Liquid products contain much less dispersing range in which the main amount of dye
agent. Depending on concentration, the yields attaches
280 Textile Dyeing Vol. 36
4. Diffusion test (BASF Combi Test [331]) for and ecologically harmful. For this reason, the
rate of diffusion in the fiber carrier dyeing technique is recommended only
when dyeing temperatures of 130 C are impos-
Many dyeworks illustrate the coloring behav- sible (e.g., with PES – wool blends).
ior of dyes by absorption curves (e.g., [332]).
For dyeing aids and carriers especially suited Dyeing below 100 C. The highest possible
to dyeing PES fibers, ! Textile Auxiliaries, 5. dyeing temperature is of advantage for coloring
Dyeing Auxiliaries, Chap. 4., ! Textile Aux- PES fibers. However, if no pressure-stable dye-
iliaries, 5. Dyeing Auxiliaries, Chap. 5., ! Tex- ing aggregates are available, dyeing can be car-
tile Auxiliaries, 5. Dyeing Auxiliaries, Chap. 6., ried out at atmospheric pressure with the addition
! Textile Auxiliaries, 5. Dyeing Auxiliaries, of dyeing accelerants. In addition, all conditions
Chap. 7. must allow the theoretically attainable boiling
temperature to be approached as closely as pos-
sible under local conditions (i.e., by using closed
7.2.2. Dyeing from Aqueous Dye Baths or at least covered dyeing equipment). At the
same time, this also prevents inhalation problems
Articles made of pure PES fibers are dyed almost due to the carriers, which are generally steam
exclusively in exhaustion processes. Disperse volatile and can be ecologically harmful (!
dyes are most stable at a pH of 4 – 5, acetic acid Textile Auxiliaries, 5. Dyeing Auxiliaries, Chap.
being used preferentially for pH adjustment. A 7.). Carriers must be accurately dosed; too much
dispersing agent is also added to the dyebath or too little can result in decreased yield. Since
(! Textile Auxiliaries, 5. Dyeing Auxiliaries, they can also affect fastness, especially lightfast-
Chap. 4.). Dyes sensitive to heavy metals (e.g., ness, carriers must be removed after dyeing by
anthraquinoid red products) are dyed in the pres- hot rinsing and washing or by drying at high
ence of a complexing agent [ethylenediaminete- temperature or heat setting.
traacetic acid (EDTA) type].
dyeing process, considerable amounts of water MPa are used. Short dyeing times, good level-
are required e.g., for pretreatment and afterclean- ness, and low disposal costs are expected. The
ing. For continuous foam application, see Section CO2 is recovered. The equipment is naturally
7.2.4. very complex.
Air as Transport Medium. A clear eco- Dyeing via the Gas Phase. Dyeing with dye
nomic advantage is observed when air is used vapor in the vacuum or in a gas stream as the
as the transport medium for the textile material medium, has also been investigated. Although
(Then Air Jet, see Section 2.2.4.5). Here, efforts advantageous from an energy standpoint, the
are made to prevent foam formation. The small problems encountered on a practical scale have
amount of aqueous dye liquor present serves as not yet been solved [338].
the medium for dyes and auxiliaries.
sensitive to alkali. A padding auxiliary, e.g., a would be required. In the pad roll process, rapidly
polyacrylate or an alginate thickener (! Textile diffusing dyes must be used at any rate.
Auxiliaries, 5. Dyeing Auxiliaries, Chap. 9.), is
used to prevent migration of dye liquor on the Continuous Dye Application in Foam.
fiber surface during drying. Migration can cause Dyeing from foam (Section 7.2.3) has also been
two-sidedness of the material, as well as darker- studied for continuous dyeing [339]. Since a
or lighter- colored fiber ends (frosting). Further- slightly inhomogeneous application of the foam
more, dye migration is counteracted by low becomes visible immediately in a color differ-
liquor application (concentrated pad liquor, high ence, the consistency, pore size, and disintegra-
squeezing pressure in the padder), low drying tion time of the foam must be kept as constant as
temperature, and low air circulation. Drying is possible and the articles must be carefully pre-
carried out contact free up to a residual moisture cleaned [340]. Equipment for foam formation
of 20 – 30 % and then on any equipment and for continuous application has been devel-
available. oped. The continuous foam dyeing technique
The fixing time and temperature depend on the offers advantages for dyeing floor coverings by
aggregate, the dyes used, and the depth of shade greatly reducing liquor application. However, it
(see Table 11 for guide values). For equipment is not an attractive method for dyeing PES piece
requirements, see Section 2.3.1. goods.
In one formulation, dyes with similar rates of
diffusion should be used as much as possible. Continuous Dye Fixation with Micro-
Very quickly diffusing dyes sublime easily, con- waves. The moist fabric padded with dye liquor
taminate the fixing aggregate, and produce dye- is irradiated with microwaves in the presence of
ings that have a low fastness to thermofixation. vapor. The addition of urea or carrier is recom-
The color yield of very slowly diffusing dyes is mended for rapid diffusion of the dyes
sensitive to temperature variations. [341–343].
After the dyes are fixed, dyes and auxiliaries
that adhere superficially must be washed out, if
necessary by an alkaline reductive treatment. In 7.2.5. Dyeing of Microfibers
the case of PES – cellulose fiber blends, this
washing can be combined conveniently with Fibers with a fineness of less than 1 dtex are
afterdyeing of the cellulose component, e.g., called microfibers. Articles made of microfibers
simply by overdyeing with vat dyes (see Section are characterized by a low weight, soft feel,
11.1). For exact instructions for use of the ther- weather resistance, and good breathing activity.
mosol process, see [332, pp. 122 – 131]. The large fiber surface leads to rapid dye absorp-
tion and, thus, to the risk of unevenness. For
Pad Roll Process (Section 2.3.2). Disperse physical reasons, the colors also appear to be
dyes are fixed only incompletely to PES fibers lighter than on normal fibers. Therefore, greater
under the conditions of the pad roll process amounts of dye are required to achieve a required
(padding, retention in saturated vapor atmo- shade. The large fiber surface and the great
sphere). Only light colors can be produced eco- amounts of dye used also lead to lower light-
nomically with adequate fastness. Carrier addi- and wetfastness. Preliminary tests are useful
tions are not useful because very large amounts [244], [345].
Temperature*, C
Dyeing aggregate Dyes with average rate of diffusion Dyes with low rate of diffusion Time, s
PES fibers that have been subjected to a classes of dyes that differ in their affinity to the
surface peeling process with alkali behave simi- fiber components).
larly to microfibers [346].
7.3. Aftertreatment
7.2.6. Dyeing of Modified Polyester Fibers
In the case of light and medium PES dyeings, as
Since disperse dyes diffuse very slowly into PES in the coloring of other fibers, the material need
fibers, efforts are made to increase the rate of dye only be rinsed thoroughly or soaped after dyeing.
strike by chemical or physical alteration of the In the case of dark shades, nonfixed dye compo-
fiber. The fiber is also modified to reduce the nents are held firmly on the fiber surface and
pilling tendency, to increase shrinkage and elas- decrease fastness. Oligoesters (oligomers) leav-
ticity, and to reduce flammability (! Fibers, 5. ing the fiber can also interfere with spinning or
Polyester Fibers, Chap. 2.). Such modified fibers winding because they deposit on yarn guiding
exhibit improved dye receptivity. Fibers with devices. Therefore, loose material and yarn, in
improved dyeability can be dyed with disperse particular, must frequently be subjected to reduc-
dyes at boiling temperature without a carrier or tive alkaline clearing after dyeing. For this pur-
with basic dyes when they are modified with pose, ‘‘hydrosulfite’’ (sodium dithionite) is used
acidic components (5-sulfoisophthalic acid). Fi- in the presence of an emulsifying washing agent.
bers of this type are used if dyeing cannot be In the case of loose stock, reductive after-
carried out easily above 100 C (e.g., in the case treatment also improves spinnability because the
of floor coverings, articles made of PES – wool fiber becomes smoother. Good spinnability is
blends, stretch materials, and cord). Strongly especially pronounced when organic reducing
crimped PES bicomponent fibers are produced agents are used for aftertreatment (Cyclanon,
for special purposes. These fibers are normally BASF, ! Textile Auxiliaries, 5. Dyeing Aux-
also dyeable at the boil and without a carrier iliaries, Chap. 10.).
[347–351]. To improve the lightfastness of dyes used to
Modified PES fibers are usually more sensi- color car fittings, benzophenone or triazole com-
tive to hydrolysis than normal fibers. This must pounds (e.g., Cibafast, Ciba) are often employed
be taken into account in finishing. The lightfast- in the dyebath or as aftertreatment [352].
ness of the dyeings is often lower than on normal For partial and complete stripping of faulty
fibers. Thus, dyes for coloring carpeting, uphol- dyeings, ! Textile Auxiliaries, 5. Dyeing Aux-
stery, and drapery must be carefully selected. iliaries, Chap. 13.
When dyeing, one should take into account the
fact that dyes start exhausting at low tempera-
tures (ca. 60 C) and the dyebath is exhausted 8. Dyeing of Cellulose Acetate
after a short time, so problems with levelness
may arise. For properties of cellulose acetate fibers, see
! Fibers, 1. Survey, Chap. 8.; for chemistry and
Anionically Modified PES Fibers not only production, see ! Cellulose Esters, Section 2.1.,
exhibit affinity for cationic dyes but also are ! Cellulose Esters, Section 2.3. Cellulose 2.5-
more easily dyeable with disperse dyes than acetate (CA) and cellulose triacetate (CT) are
normal fibers. They are dyed with basic dyes up preferentially processed as filaments. Because of
to 115 C in the presence of Glauber’s salt to their silklike feel, dull gloss, and pleasant wear-
protect the fibers from hydrolysis. If the dyeing ing quality, they are especially popular for dress
aggregates available do not allow dyeing tem- and blouse materials, scarves, and linings. In the
peratures of 110 C, a carrier is employed to textile sector, the importance of cellulose acetate
give deep shades on anionically modified is decreasing: world consumption in 1970 was
fibers. 354 000 t, in 1980 338 000 t, and in 1992
The joint use of anionically modified and 232 000 t. Cellulose acetates are being increas-
normal PES types can be exploited for differen- ingly replaced by synthetic polyamide and poly-
tial dye effects (joint application of different ester fibers. In contrast to the other regenerated
284 Textile Dyeing Vol. 36
cellulose fibers, CA and CT are hydrophobic. Piece goods made of CA are usually dyed in a
Therefore, they have little in common with vis- jigger, less often in a star frame or winch beck
cose or cuprammonium rayon from the view- with gentle material guidance. The piece beam
point of dyeing. As hydrophobic fibers, they can is suitable for warp materials. Yarn was previ-
be dyed with disperse dyes (! Disperse Dyes). ously dyed in hanks. Since suitable winding
The dyeability of CA and CT with disperse dyes machines are available, CA can also be dyed
is very similar to that of PES and other synthetic on cylindrical cheeses. Woven CA fabrics are
fibers. The rules described for dyeing PES fibers occasionally dyed semicontinuously in a pad
with disperse dyes (see Chap. 7) basically apply roll system (Artos) at 80 – 90 C (see Sec-
to CA and CT as well. Tests have been drawn up tion 2.2.3). Dyeing auxiliaries are subsequently
by the Society of Dyers and Colourists for the washed out.
selection of suitable dyes [353]. Trade names of A dyeing process with developing dyes,
disperse dyes available for CA and CT are, e.g., which was used in the past for various shades,
Artisil (Sandoz), Celliton (BASF), Cibacet is still being employed for black. Although this
(Ciba – Geigy), Dispersol (ICI), Dianix (Mitsu- process produces dyeings that are especially fast
bishi – Hoechst), and Serisol (Yorkshire). to wet treatments, it is more tedious than dyeing
In addition, the ranges of disperse dyes in- with direct disperse dyes. The process starts with
tended for PES fibers contain numerous products the application of an amino-group- containing
that are very well suited to CT in particular. diazotizable disperse dye [e.g., Cellitazol
The choice of dye depends, on the one hand, (BASF), Cibacet-Diazo (Ciba – Geigy)], which
on the desired use and production fastness and, is diazotized on the fiber and then coupled with a
on the other hand, on the suitability for certain naphthol [e.g., 2-hydroxynaphthoic acid (Devel-
dyeing techniques. Dyes that produce especially oper ON)]. Thus, a large-molecular, insoluble,
washfast dyeings require higher dyeing tem- wetfast dye is formed in the fiber.
peratures for level absorption. An important
criterion for the selection of dyes for CA can
be fastness to exhaust gases (see Section 8.3). 8.2. Dyeing Processes for Cellulose
Articles made of CT are subjected to thermal Triacetate [355]
treatment in the course of finishing. The fastness
to thermofixing or pleating of the disperse dyes In terms of dyeing and finishing, CT is more
recommended for CT is usually at least as good similar to purely synthetic fibers than CA. It can
as on PES fibers. be permanently pleated. For stress relaxation,
articles made of CT, like those made of PES,
are heat set (thermofixed) after dyeing [356,
8.1. Dyeing Processes for Cellulose pp. 92 – 100]. Triacetate, like PES, can be dyed
Acetate [354], [355] according to the thermosol process (see
Section 7.1.2).
Theoretical aspects of dyeing CA and CT are The absorption of disperse dyes from a long
described in [356, pp. 74 – 92]. Cellulose ace- liquor by CT fibers is slower than CA and some-
tate is dyed by the exhaustion method with what faster than PES fibers. With a few disperse
disperse dyes in the presence of a nonionic or dyes, acceptable dyeings are obtained on CT
anionic dispersing and leveling agent in a weakly even at boiling temperature. As a rule, however,
acidic bath (pH 5 – 6). A series of less wetfast dyeing is conducted at 120 C, especially to
disperse dyes are taken up by acetate at tempera- obtain dyeings with adequate fastness properties.
tures as low as 50 – 60 C. For this reason, the If this is not possible, a dyeing accelerant (based
process must be started at a correspondingly low on butyl benzoate or butyl salicylate) is used. As
temperature to obtain level dyeings. Dyeing is in the case of CA, CT is dyed in a weakly acidic
normally done at 80 – 85 C. Dyes that are fast liquor (pH 5 – 6) in the presence of a leveling
to wet treatments require temperatures up to dispersing agent. The lower the dyeing tempera-
90 C. If CA is dyed at boiling temperature, the ture, the more must leveling be supported with a
fibers may become delustered. suitable auxiliary agent.
Vol. 36 Textile Dyeing 285
suitable comonomers, gave fibers with a high process. Because of their considerably higher
glass transition temperature Tg and with insuffi- affinity, dye cations displace an equivalent
cient dye-binding possibilities. Fibers of this type amount of cations (Hþ, Naþ) that were previous-
could be dyed only in light shades with disperse ly present at the anionic groups in the fiber (ion
dyes or with acid dyes according to the compli- exchange). This process determines the dye dis-
cated copper ion process [358]. Today, anionic tribution in the dyeing equilibrum [364–367] and
comonomers are used, and anionic groups are can be described by the Donnan theory [368],
incorporated into the chain ends of the fiber [369].
molecules. In this way, Tg is lowered and anionic In acrylic dyeing, the dyeing (or absorption)
groups are available that can act as dye sites for rate v is especially important. Because of the
cationic dyes. Thus, acrylic fibers are reliably and high affinity of cationic dye for the fiber, their
economically dyeable. migration capacity is poor. Thus, dyeing must
be sufficiently level from the start; this requires
the control of v, which can be reliably achieved
9.2.1. Disperse Dyes only if the effects of relevant parameters are
known. Since v is determined by the diffusion of
Disperse dyes (! Disperse Dyes) can be used to dye in the fiber, the following relation is valid
produce light to medium deep shades. The dyeing according to the laws of diffusion [370] (see
mechanism and process correspond to those used Section 2.1.3)
on polyester fibers (see Chap. 7). However, dye-
v DCD ð9:1Þ
ing can be performed at < 100 C. Addition of
carriers is not required. The good migration where DC is the concentration gradient and D is
properties of disperse dyes result in problem-free the average, apparent diffusion coefficient of
level dyeing. dye cations in the fiber. The parameter DC
depends on the dye concentration on the fiber
surface Cs. The amount of dye CF (t) that has pffi
9.2.2. Cationic Dyes diffused into the fiber after time t follows a t
law [371]:
Cationic dyes (! Cationic Dyes) are used pre- pffiffiffiffiffiffi
dominantly for acrylic fibers [359] because vir- CF ðtÞ Cs D t ð9:2Þ
tually any depth of color can be obtained and they
are dyeable with high brilliancy and good fast- Except when only a small number of dye cations
ness. In choosing the dyeing conditions, the are available (for production of very light dye-
dyeing mechanism and relevant properties of the ings), the fiber surface is almost saturated during
dyes and fibers should be taken into account. This dyeing, i.e., Cs is approximately constant until
is relatively easy because despite the great vari- most of the dye is exhausted. At constant dyeing
ety of fibers and dyes, uniform and – in compari- temperature, D can also be regarded as approxi-
son with other dyeing processes – simple laws are mately constant. Thus
valid for dyeing with cationic dyes. A detailed pffi
CF ðtÞ t ð9:2aÞ
description is presented in [360], and a discussion
with a literature survey of the more recent devel-
opments in certain areas (e.g., pore and surface To a good approximation, this is valid until ca.
structure, fiber modifications, thermal yellowing, 70 % of the dye supplied is absorbed (bath ex-
effect of carriers and solvents during dyeing, and haustion BE ¼ 70 %). Thus, some rules exist
transfer print) in [361]. The physical chemistry of concerning the dependence of dyeing time and
dyeing in general is presented in [362], [363]. rate of dyeing on the concentration p of supplied
The dyeing process with cationic dyes can be dye [372]. For a given temperature or tempera-
described by the following model. The dye rap- ture program:
idly absorbs to the surface of the fiber from the
aqueous solution in the dyebath until saturation 1. The dyeing time required increases with p2 ( p
occurs. Above Tg, dye diffuses into the fiber. This is normally given in percent based on fiber
diffusion is usually rate determining for the entire mass).
Vol. 36 Textile Dyeing 287
2. The relative (based on p) rate of dyeing vrel conditions and the rate of dyeing V of the fiber
dp/dt (percentage of dye per minute) is in- have been introduced for this purpose [372].
versely proportional to p2. The degree of occupation by dye cations of
3. The absolute rate of dyeing vabs ¼ dCF/dt anionic dye sites present in the fiber is decisive
(milligrams per minute) is independent of p. for the dyeing equilibrium, in practice the final
exhaustion of the dyebath. At constant temper-
Thus, the lighter the color, the faster is the ature (maximum dyeing temperature), dye dis-
absorption and the greater the danger of nonle- tribution follows a Langmuir isotherm [376],
velness if absorption is not controlled by a suit- [377].
able temperature program or retarders. Further-
sCL
more, Equation (9.2) denotes the following. Un- CF ¼ ð9:3Þ
s=aþCL
even surface charging with dye cations leads to
differences in CF (i.e., nonlevelness). Surface where CL is the dye concentration in the dye-
charging occurs rapidly and can hardly be influ- bath, s is a saturation concentration, and a is
enced by temperature guidance. In the case of essentially the affinity of the dye. The value s
light colors, when the number of dye cations denotes the maximal possible dye uptake by the
provided is insufficient to saturate the surface, fiber for very high p. In this case, all dye sites are
retarders (! Textile Auxiliaries, 5. Dyeing Aux- occupied, the number of dye cations ncat on the
iliaries, Chap. 6.) must be applied to achieve this fiber equals the number of anionic dye sites of
purpose; only then can uniform surface charging the fiber ns. [Virtually all of the anionic dye sites
be expected. of the fiber are accessible to dye cations under
The temperature dependence of v is especially dyeing conditions (i.e., above Tg)]. If ncat < ns,
pronounced in acrylic dyeing [364], [372], [373]. the supplied dye is exhausted almost completely
Depending on the type of fiber, Tg is in the range because of the normally high affinity; if ncat >
of 70 – 80 C; above Tg is the absorption range. ns, the excess remains in the bath. This relation-
In the absorption range, D and, according to ship is stoichiometrically valid and usually in-
Equation (9.2), v increase steeply with T in ac- dependent of dyeing conditions. Thus, the posi-
cordance with the Williams – Landel – Ferry tion of the dyeing equilibrium can be calculated
(WLF) equation derived from the theory of chain for each individual dyeing process. For this
segment motion [373–375]. The Arrhenius equa- purpose, fiber- and dye-specific values derived
tion is also valid to a usable approximation and is from molar quantities are used. The following
more practical because it contains only one con- have proved useful [372], [378]:
stant, the activation energy E [362]. The values of
E for v are 250 – 300 kJ/mol [364], [372], the 1. The fiber saturation value SF, a measure of the
lower values being for wet spun fibers. This concentration N (in millimoles per kilogram
corresponds to a doubling of v for a temperature of fiber) of anionic dye sites in the fiber:
increase of only 2.5 – 3 C. (In the case of
SF ¼ N=25 ð9:4Þ
disperse dyes on PES or acid dyes on PA a
doubling of v is observed at a temperature in-
crease of ca. 5 and 10 C, respectively.) These 2. The saturation factor f of a cationic dye
values are practically independent of the choice having a molecular mass Mr and a net dye
of dye, depth of color, and mode of dyeing [372]. content e (grams of pure dye per gram of
The steep increase of D and v with temperature is commercial dye):
predominantly caused by changes in the fiber.
f ¼ 400e=Mr ð9:5Þ
Apart from T and the amount of dye applied
(in the case of vrel), v also depends on the
properties of individual dyes and the type of
fiber. To take this into account, in practice, The saturation concentration ps (percent dye,
especially in systematic dyeing processes, these based on the mass of textile material) of an
effects are separated and described in terms of individual dye (with ncat ¼ ns) is
dye- and fiber-specific characteristic values. For
ps ¼ SF =f ð9:6Þ
instance, the dyeing times of dyes under standard
288 Textile Dyeing Vol. 36
A combination of several dyes (1, 2, 3, . . .) the fiber surface. Cs (dye) and the concentration
exhausts almost completely if gradient of the dye become smaller and remain
constant longer in the course of dyeing [383]. For
ðpf Þ1 þðpf Þ2 þðpf Þ3 þ . . . < SF ð9:7Þ
this reason, at constant temperature T, the rate of
In the case of PAC types with strongly anionic dyeing is lowered by the retarders. However, this
(acidic) dye sites, SF increases slightly with effect does not justify the use of retarders because
increasing pH (by ca. 10 % from pH 4 to 6.5). it would be obtainable at a lower cost by dyeing at
In the case of PAC types with weakly anionic dye lower temperature.
sites (carboxyl groups), the increase is consider-
ably greater [377]. Cationic Softeners. Depending on their af-
Another important quantity is the relative finity and penetrating ability, some cationic soft-
saturation of the fiber in the dyeing equilibrium eners – when used in the dyebath – act like cat-
[372] ionic retarders and contribute to Srel. Thus, less
X cationic retarder is required. However, their soft-
Srel ¼ ðpf Þ=SF ð9:8Þ ening effect is lower than when applied in after-
The higher the Srel (other parameters being treatment at temperatures below Tg.
equal), the better is the levelness of dyeing during
absorption. If Srel is about equal in different Migration Aids. Colorless cationic auxiliary
dyeings and certain other conditions are met agents having a considerably lower affinity for
(compatibility, use of retarder, proper tempera- the fiber than dyes are available as migrators
ture guidance), a similar course of the dyeing (migration aids) (! Textile Auxiliaries, 5. Dye-
process with regard to the rate of dyeing, bath ing Auxiliaries, Chap. 6.). They can be used in
exhaustion, and levelness can be expected. larger molar amounts than cationic retarders
without danger of blocking. They influence Srel
and levelness during absorption only slightly, but
Retarders and Auxiliaries. they promote migration and help compensate for
Cationic Retarders. With light and moder- unevenness in the fiber [384].
ately deep shades, the amount of dye applied is
often not enough for an adequate Srel. Sometimes Electrolytes. The addition of electrolytes has
even saturating the fiber surface is not sufficient. a similar effect [380]. In accordance with their
To meet the danger of nonlevelness in such cases, much lower affinity compared to migration aids,
cationic retarders are used (! Textile Auxili- this effect is weaker, based on the number of
aries, 5. Dyeing Auxiliaries, Chap. 6.) [379], cations used. However, since this number is
[380]. These are colorless cationic compounds generally much higher than in the case of mi-
that absorb like dyes and compete with dyes for grators comparable effects are obtained.
acidic groups in the fiber and on the fiber surface.
They are usually quaternary amines with an Polycationic Retarders [i.e., compounds
aromatic substituent and an aliphatic chain. The (usually polymeric) with numerous cationic
longer this chain, the greater is the affinity for the groups] have been recommended as leveling
fiber [381], [382]. agents [385]. They occupy the fiber surface
These compounds are used mainly to increase without penetrating into the fiber and counteract
Srel, thereby improving levelness. The increase dye adsorption, thereby reducing the rate of
can be calculated in accordance with Equations dyeing [386], [387]. Depending on their adsorp-
(9.5) – (9.8), the retarder being assigned a satu- tion characteristics, they also decrease the mi-
ration factor according to Equation (9.5) and gration capacity and the bath exhaustion in the
treated formally like a dye [372]. This calculation dyeing equilibrium. However, a favorable effect
is important to guarantee the desired effect and on leveling has not been found. (The rate of
prevent Srel from becoming too large (close to 1 dyeing can be influenced better through a suitable
or higher). Dye absorption would then be incom- temperature program.)
plete (blocking of anionic groups).
Depending on the affinity and amount applied, Anionic Retarders. In some cases, anionic
cationic retarders partially displace the dye from auxiliaries are also used as retarders (! Textile
Vol. 36 Textile Dyeing 289
Auxiliaries, 5. Dyeing Auxiliaries, Chap. 6.) level dyeing. In combinations with different K,
[388]. These contain two or more anionic groups dyes with a lower K absorb before those with a
(sulfonic acid groups) per molecule, forming a higher K. Cationic retarders can also be assigned
1 : 1 addition compound with the cationic dye; K values [360], [391]. The K values change with
that is soluble in the dye liquor. To ensure this the use of anionic retarders.
solubility, at least two anionic groups must be
available from the start for each dye cation. The
minimum amount of anionic retarder required 9.3. Exhaustion Process
can be calculated via f values according to Equa-
tion (9.5) [360]. In the course of dyeing a grow- Normal PAC textile material is dyed as cable or
ing excess of auxiliary anions is formed, and the stock in package dyeing, as yarn in hanks or
concentration of free dye cations in the liquor packages (cross wound, cylindrical, or conical)
falls below that required for saturation of the fiber (320 – 350 g/L, direction of liquor inside – out-
surface. Dyeing rate and bath exhaustion at dye- side), as pieces on beam, overflow, paddel (knit-
ing equilibrium are decreased. wear), or drums (socks) (see Section 2.2). High-
Anionic retarders promote the migration of bulk (HB) yarns are applied as muffs (cylindrical
cationic dyes. They reduce the danger of pre- bobbins without tubes, without intermediate
cipitations when anionic dyes are used in addi- plates) [392]. Strongly soiled textile material is
tion to cationic dyes (for fiber blends). They prewashed, preferably in a weakly alkaline wash.
influence the compatibility of dyes (see below). The principles of recipe and process operation
The higher the affinity of the cationic dyes, the are described in [383]. Because of the poor
greater is their effect. The main disadvantages migration properties, dye absorption must be as
are the lower bath exhaustion and poorer level as possible from the start. Correspondingly,
reproducibility. attention should be paid to uniform packaging,
package density, flow or movement of textile
Compatibility of Cationic Dyes. Cationic material, and controlled machine conditions. As
dyes influence each other during absorption far as possible, dyes with the same K are selected
[268], [367]. If several dyes exhaust tone-in-tone (the largest choice of dyes and most suitable
from one bath (i.e., the depth of color, but not the retarders are available at K ¼ 3). In cases where
shade, changes in the course of absorption), the sufficient levelness during absorption is critical,
dyes are referred to as compatible. In the case of dyes with a relatively low affinity (with high K )
cationic dyes on PAC, the property of being are recommended. These dyes migrate somewhat
compatible is dye specific and also applies to better than normal dyes [393]. The dyeing for-
dyeing under other conditions and in other mula is drawn up with the assistance of a color
shades. It depends on the product D A (A ¼ dye measuring system (see Chap. 12) or according to
affinity) and can be described by the compatibil- available documentation, and the amount of re-
ity value K (see Chap. 12) [372], [389], [390]. tarder is adjusted to give a favorable Srel. The
In acrylic dyeing, combinations of dyes with dyebath is charged with the dissolved dye and all
the same K exhibit considerable advantages in the other additives (see Table 12) at 60 – 70 C,
Table 13. Temperature range of controlled heating (general method) 4. The dwelling time at the maximum (final)
(Tstart – Tend) and residence time (tmax) at maximum temperature Tmax
dyeing temperature required for penetration
Srel
In following this method, the rules mentioned
Low Medium High in Section 9.2.2, the properties (characteristic
Tstart, C 75 80 85 values) of the fibers and the dyes, and the con-
Tend, C 95 98 – 100 98 – 100 ditions of the dyeing machine and the article are
tmax, min systematically taken into account. This optimi-
(at Tmax ¼ 98 C) 20 40 60
(at Tmax ¼ 102 C) 15 30 40 zation can be performed with the help of tables
[397] or with a computer [398].
Substantial advantages are obtained by:
and the textile material is added. After a mixing 1. Appropriate amounts of auxiliary agents
time of ca. 5 min, dyeing is conducted by con- applied
trolling the temperature, as shown in Tables 13 2. Shorter dyeing times
and 14. This is followed by cooling (ca. 0.3 C/ 3. More protection against nonlevelness
min to 60 C), rinsing, and aftertreatment. 4. Better programmability
The details given in Tables 12, 13 take into 5. Better reproducibility
account in a general way (same conditions for 6. Saving of laboratory work
larger groups of dyeings) the principles ex- 7. Help in searching for errors
plained in Section 9.2.2 – especially the need to
achieve sufficiently level dyeing from the start 9.4. Dyeing of Special Fiber Types
and to have the shortest possible dyeing time. According to the Exhaustion Process
The liquor movement or circulating speed of the
material can be taken into account [394–396]. High-Bulk Material. The bulking of high-
As a rule, satisfactory results are obtained in this bulk material proceeds either as a pretreatment
manner. (continuous for yarn, batchwise and usually with
Dyeing can be performed more economically steam for yarn and knitwear) or in the dyebath
and reliably according to systematic methods for before dye absorption at ca. 80 C for 5 – 10 min
the optimization of formulations and dyeing without liquor movement [392]. To avoid non-
conditions [372], [383], [397]. Here, dyes with levelness in this process, retarders are employed
the same K are selected and the following are (high Srel) to ensure that very little dye absorbs
determined for each dyeing: during the bulking time. The formulas given in
Section 9.2.2 or systematic dyeing processes
1. The amount of retarder that leads to the most (Section 9.3) are used. With HB bicomponent
favorable relative saturation Srel fibers, a high Srel can interfere with the reversible
2. The temperatures at which exhaustion starts shrinkage. For this reason, anionic retarders and
or ends (the critical temperature range outside dyes with K 4 are preferred [393].
which rapid heating will not cause unlevel-
ness, see Section 2.2.1) Pore Fibers. For the surface and pore struc-
3. The most favorable rate of heating in this ture of PAC fibers, see [361]. As a result of their
temperature range greater light scattering, pore fibers (type Dunova,
Heating rate, C/min
a
Temperature range Stock, top Yarn (pack.) Hank, piece
light fibers with high water absorption capacity) Cooling to < 60 C should not proceed more
require up to three times more dye than normal than twice as fast as heating.
fibers to achieve a given shade [399]. This rela-
tion depends on the angle of observation. Navy Modacrylic Fibers (! Fibers, 8. Polyacry-
and black shades are hardly dyeable; for dyeing lonitrile Fibers). Modacrylic fibers containing
other deep hues, an ammoniacal reductive after- more than 20 % of vinyl chloride or vinylidene
cleaning step is required. The diffusion of dyes chloride as comonomer are used because of their
proceeds mainly in the pores of the fiber [400], reduced flammability. Depending on the como-
[401], changing the K values of the dyes. With the nomers, various types of modacrylic fibers exist
exception of a higher softener requirement, the that differ especially in the range of dyeing tem-
rules of normal PAC dyeing apply. peratures. In all cases, the critical temperature
range is greater (25 – 50 C) than with normal
Microfibers. PAC microfibers (single titer fibers (15 C), and absorption starts in most cases
below 1 dtex) behave differently in some respects at lower temperature. Modacrylic fibers generally
from normal acrylic fibers [402]. First, more dye exhibit increased plasticity and a strong tendency
is required for the desired shade in each case to shrink at higher dyeing temperature. The fiber
because of the greater light scattering of the fiber. types and their dyeing properties change frequent-
This requirement increases more than twofold ly. The lightfastness on these fibers is consider-
with increasing depth of color (similar to pore ably poorer than on normal PAC fiber, making a
fibers). For this reason, the fiber saturation SF is corresponding dye selection necessary [403],
usually adjusted to a higher value by the fiber [404]. Dyeing is performed at pH 4.5 with acetic
producer. The characteristic dyeing rate V of the acid, 0.5 wt % of sodium acetate, and 1 – 2 wt %
fiber is also higher. Corresponding to these in- of nonionogenic dispersing agent. Depending on
creased values, more cationic retarder is required the type of fiber, carriers or cationic retarders and
and the starting temperatures are lower. Above different temperatures are recommended. Exam-
Srel 0.75, the rub- and wetfastness can be ples of fiber types are given in Table 15. The
lower; reductive aftercleaning is sometimes nec- relustering required in the past after dyeing is
essary. Some dyes exhibit increased sensitivity to usually no longer necessary.
boiling down (lower dyebath stability) when the Modacrylic fibers can also be dyed with dis-
pH clearly deviates from 4.5. For this reason, dye perse dyes (similar to normal PAC fibers, but the
producers recommend a special selection of dyes fastness to sublimation is poor).
for microfibers. In the dyeing of stock, top, or
yarn, one should take into account the fact that
the liquor flow is lower and its uniformness is 9.5. Continuous Processes
more problematic than in the case of normal
acrylic fibers. For this reason, packaging and Stock, cable, and top can be dyed on special
winding must be especially even and the rate of machines according to the pad steam process (see
heating should be slower if possible. In piece Section 2.3.2) [405–407], preferably with pres-
dyeing, longitudinal tension should be kept as surized steam of clearly more than 100 C to
low as possible and creasing must be avoided. obtain short fixing times. To avoid drying and
Table 15. Dyeing properties and recommended range of dyeing temperature for different types of modacrylic fiber
Type of fiber (producer) S Fa V b
Auxiliary Temperature range, C
c
Dynel (Union Carbide) 0.9 1.0 carrier 40 – 98
Kanekalon S (Kanegafuchi) 2.2 1.2 migrator carrier (deep hues) 60 – 98
Teklan (Courtaulds) 4.3 2.4 cationic retarder 60 – 98
Velicren FRS (Snia) 4.1 2.5 cationic retarder 80 – 98
Verel (Eastman) 0.8 1.0 carrier 30 – 70
a
SF ¼ Fiber saturation value (see Section 9.2.2).
b
V ¼ Characteristic value for the rate of dyeing of a fiber (see Section 9.2.2).
c
Several types with partially different properties.
292 Textile Dyeing Vol. 36
condensed water spots, the steam should not be their flame retardance. For this reason, they are
either superheated or wet. A typical pad liquor used, e.g., for airplane seat covers, quilt fillings,
contains acetic acid (pH 4.5) and dye solvent in and purely technical purposes.
addition to especially steam-resistant, readily PVC fibers are dyed preferably with disperse
water-soluble cationic dyes (usually liquid dyes (! Disperse Dyes) [416, p. 404], [417, pp.
brands) [406], [408]. Space dyeing can be re- 611]. As with modacrylic fibers, excessively high
garded as a variant of this mode of dyeing. A new temperatures must not be used because of shrink-
suggestion involves simultaneous bulking and age of the PVC fiber. Hence, some fibers are dyed
dyeing in a continuous process [409]. at 60 – 65 C with dyeing accelerants. Other
The pad steam process with fixing by saturat- PVC fibers can be dyed at 100 C without a
ed steam at 100 – 102 C is used for piece goods, carrier and a few even at 110 C. Dyes must be
especially upholstery material (velour). This re- selected with regard to the lightfastness desired.
quires longer fixing times (10 – 20 min). Rapid- Cationic dyes in combination with an anionic
ly diffusing cationic dyes and dye solvents, auxiliary can also be used to achieve average
which also exhibit a carrier effect (! Textile depths of shade. Here, good lightfastness is
Auxiliaries, Section 5.6.5.) [361], [410], [411], achieved with selected dyes.
are required. If substantive dyes are used simul- Similar to certain modacrylic fibers, some
taneously (for cotton backs), the dye solvent PVC fibers, such as Leavil, also lose their luster
should also have a good dispersing action. on dyeing. It can be recovered by relustering (dry
Dry heat fixing (thermosol process, see Sec- heat at 110 – 130 C).
tion 2.3.2) is unimportant for PAC dyeing because
the fiber tends to yellow and harden in this process
and cationic dyes are fixed slowly and incom- 10.2. Elastomeric Fibers
pletely [361], [406]. Transfer printing is also not
suitable without either elaborate pretreatment or Elastomeric fibers made of polyurethane (! Fi-
special swelling agents or solvents [361]. Dis- bers, 6. Polyurethane Fibers) are contained in
perse dyes produce only very light shades. most stretch articles and also in fashion materials
Dyeing wet spun PAC fibers during the pro- and knitted fabrics [418]. Mixtures with polyam-
duction process in the gel state is especially ide are used for corsetry, orthopedic support
economical. This occurs after the solvent has stockings, panty hoses, and swim or sports wear.
been washed out and before the usual follow-up Articles made of cotton – elastomeric fibers and
processes, especially stretching and drying PES – cotton – elastometric fibers are also very
[412–415]. The gel absorbs cationic dyes very common. The companion fiber is often spun
rapidly (within seconds or a few minutes). There around the elastomeric thread, which makes
is almost no difference from normal PAC dyeing separate dyeing of the polyurethane fiber unnec-
with regard to saturation, shade, and fastness. The essary. This is substantiated by the usually mod-
dyes are required in large amounts. Thus, liquid erate fastness of most dyes on polyurethane
brands, which are miscible without the occur- fibers.
rence of precipitation, are preferably used. Mix- Polyurethane fibers can be dyed with acid
tures, even diluted, must be stable in storage dyes (! Anthraquinone Dyes and Intermedi-
(premixability). ates, Section 3.2.1.; ! Azo Dyes, 2. Anionic
The mass dyeing of PAC is important only for Dyes, Chap. 2.), metal- complex dyes (! Azo
highly weather-resistant, special articles (awn- Dyes, 2. Anionic Dyes, Chap. 2.; ! Metal-
ings and tents). Complex Dyes), chrome dyes (! Azo Dyes,
2. Anionic Dyes, Chap. 2., and disperse dyes
(! Disperse Dyes). In general, higher dyeing
10. Dyeing of Other Synthetic Fibers temperatures, especially below pH 4 and above
pH 9, are not permissible because the fibers are
10.1. Poly(Vinyl Chloride) Fibers degraded (i.e., they lose their elasticity and
strength). Efforts are made to circumvent the
Poly(vinyl chloride) (PVC) fibers (! Fibers, 9. difficulties arising due to the inadequate dye
Polyvinyl Fibers) are characterized especially by receptivity of polyurethane fibers with the help
Vol. 36 Textile Dyeing 293
of fiber-affinitive cationic dyeing aids in combi- scale method of choice for coloring unmodified
nation with ethoxylated fatty alcohols or fatty polypropylene fibers (! Fibers, 7. Polyolefin
amines [417, pp. 572 – 574]. Fibers, Section 1.2.) [421].
Light shades can be made tone-on-tone on For wide application, fibers should be dyeable
polyamide – polyurethane mixtures with dis- in processes commonly used in textile dyeing.
perse dyes at 95 – 98 C and pH 6 – 7. However, For this reason, numerous attempts have been
the wetfastness of these dyeings on polyurethanes made to modify polypropylene to make it dye-
is lower than on polyamide. The mode of dyeing able from aqueous liquor. For surveys, see
with acid and metal- complex dyes corresponds to [422–424], [425, pp. 671 – 675], [426].
that of polyamide dyeing at boiling temperature In all dyeing processes, the low melting point
and pH 5 – 6 (see Sections 6.4.2, 6.4.3) [419]. If of the polypropylene fiber must be taken into
polyamide – polyurethane mixtures are dyed account. The fiber becomes plastic at 130 C, and
with chrome dyes, the polyurethane fibers lose treatment temperatures must be kept below
elasticity and the articles acquire a brittle feel. 120 C because of shrinkage.
Because of the temperature sensitivity of
polyurethane fibers, mixtures of elastomeric and Modified Polypropylene Fibers. Polypro-
polyester fibers must be dyed with small molec- pylene, which contains nickel compounds for
ular, rapidly diffusing disperse dyes in 30 min at light stabilization, can be dyed with dyes that
120 C according to the HT process [420]. Mod- are capable of forming nickel complexes. Non-
ified PES fibers that are dyeable at 100 C with- fading, wetfast dyeings are produced in mostly
out a carrier are often used in mixtures with dull shades with water-insoluble, chelating dyes
elastomeric fibers. [e.g., Altcolene (Althouse)].
Fiber blends that contain cotton in addition to The polypropylene fibers that were on the
elastomeric fibers can be dyed with vat dyes, market for some time were modified by basic
sulfur dyes, combinations of reactive and dis- components and could be dyed with the acid dyes
perse dyes, and combinations of substantive and commonly used for wool and polyamide fibers.
acid dyes [416, pp. 342 – 349]. To obtain acceptable lightfastness, pretreatment
In all dyeing processes for elastomeric fibers, with an acid or an alkylsulfonate was required
dyeing equipment that permits low-strain guid- before dyeing.
ance of the material and the lowest possible In a third method, the polypropylene structure
thermal stress are important. is loosened by a polyether or a polyamide, mak-
ing the fiber accessible to disperse dyes. The
depth of shade and fastness properties of these
10.3. Polypropylene Fibers dyes are sufficient for many textile purposes
including floor coverings.
Polypropylene is an inexpensive raw material Preliminary tests are required in any case. The
that produces fibers with a series of desirable type of modification can be determined easily by
properties such as dimensional stability, low two test dyeings. If an acid dye is absorbed by the
weight, low water absorption, resistance to che- fiber, the modification must be basic. A test with a
micals, and rotproofness (! Fibers, 7. Polyole- disperse dye capable of complex formation
fin Fibers). shows if nickel is present in the fiber. Polypro-
Consisting of pure aliphatic hydrocarbons, pylene fibers that contain nickel are dyed brown
these fibers have no groups with a special dye with C.I. Disperse Red 91, and differently modi-
affinity that can specifically interact with dyes fied fibers are dyed pink.
normally used for textile dyeing. Lipophilic dyes,
which are employed for dyeing mineral oil, have
sufficient affinity for polypropylene so that they 10.4. Poly(Vinyl Alcohol) (PVA)
were occasionally recommended for dyeing car- Fibers
pet backing materials. However, they produce
dyeings of such poor fastness that they are not The importance of PVA fibers for the textile
useable for textile purposes. Hence, mass dyeing industry is decreasing greatly. The cotton-like
with pigment formulations is the commercial- feel, high strength, low moisture absorption,
294 Textile Dyeing Vol. 36
From time immemorial the properties of tex- fiber improves tear and abrasion resistance, in-
tiles have been varied by mixing fiber types. creases dimensional stability, and makes wash-
Blends that are rather unimportant today (e.g., ing and care easier.
half linen, a mixture of cotton and linen, and half
wool, a mixture of wool and cellulose fibers)
were widely employed in the past. For the dyeing 11.1.1. General Finishing Information
of these blends, see [427]. Of the worldwide
consumption of PES fibers, 55 – 60 % is used For detailed information on the dyeing and fin-
in blends with cellulose fibers or wool. About ishing of PES – cellulose blends, see [428,
40 % of polyamide is used in blends, and for pp. 209 – 289], [429, pp. 453 – 457], [430, pp.
polyacrylonitrile fibers, 50 % is used especially 592 – 600].
in blends with wool for knitwear. Thus, the As in the case of cellulose articles, the dye-
introduction of man-made fibers has resulted in ability of PES – cellulose mixtures is influenced
rapid expansion of the mixed processing of vari- greatly by the methods used for pretreatment, the
ous types of fibers. Of the large number of such boiling and bleaching of the cellulose compo-
blends, some have proved very worthwhile, es- nent, and the heat setting of the PES component.
pecially PES – cellulose blends. Pretreatment methods depend especially on the
Since efforts are made to place the dyeing step type of cellulose fiber employed. In addition to
as close as possible to the end of the finishing the shades to be dyed and the scheduled dyeing
process, the problem of coloring fiber blends method, tests must also be conducted to deter-
arises frequently. In the joint dyeing of two mine the required degrees of whiteness and
components, a compromise often must be made hydrophilicity (! Textile Auxiliaries, 4. Pre-
with regard to the dyeing process, tone-on-tone treatment Auxiliaries, Chap. 2.).
dyeing or fastness of the finished product. In dyeing PES – cellulose mixtures, disperse
For this reason, not every fiber blend is ad- dyes are used for the PES component. The cellu-
vantageous from the point of view of finishing, lose portion can be dyed with practically all
and satisfactory dyeing methods still have to be classes of dyes suited to cellulose (see Chap. 4).
found for some blends (e.g., PES – cellulose The selection of suitable dyes depends not only
acetate). on the equipment available, the desired shade,
and the batch size, but also on economic factors,
with the required fastness taken into account.
11.1. Polyester – Cellulose Blends Thus, reactive dyes are used preferentially for
all types of clothing textiles, but vat dyes are
The most important fiber blend consists of poly- employed where extreme demands are made on
ester and cellulose fibers. A large part of the washfastness or weatherproofness.
entire production of PES, ca. 45 %, is used to Dyeing with mixed dyes that were first put on
make this mixture. Polyester – cellulose blends the market by BASF is especially easy. Examples
are used for all types of clothing textiles and for of suitable mixtures of disperse and vat dyes are
bed linen. A considerable amount is consumed by Cottestren (BASF) and Teracoton (Ciba – Ge-
the knitwear sector. The cellulose component is igy). The mixed dyes can be applied in a single
usually cotton, but viscose staple fibers, modal bath via the exhaustion or continuous process.
fibers (! Cellulose), and occasionally linen are The mixed dyes are formulated in such a way that
also used. Modal fibers are often employed in the same shade is obtained on both fibers, which
knitwear because of their luster. The preferred facilitates shade matching [431].
mixing ratio is PES : cellulose 67 : 33 and, for In dyeing PES and cellulose components with
textiles worn close to the skin, 50 : 50 to 20 : 80. two dye classes, the staining of one fiber by the
Articles produced from a mixture of cellulose dye used for the other fiber should be taken into
and PES have more versatile application than account. Disperse dyes stain cellulose fibers only
those made of either cellulose or PES fibers slightly. The soiling can be removed easily by
alone. Cellulose with its hydrophilicity, its ability washing or, in stubborn cases, by alkaline reduc-
to transport moisture, and its low electrical charg- tive treatment, which is required anyway in vat
ing contributes to wearing comfort. The PES dyeing. Most of the dyes used for cellulose stain
296 Textile Dyeing Vol. 36
PES only slightly or not at all. Dyes such as passed fastness to washing (e.g., for work
selected vat dyes that are fixed to PES by a special clothes) and thermofixing (e.g., for colored
application process (see Section 7.2) and sulfur weaving yarn). Mixed dyes are usually prepared
dyes, which often dye PES deeply, exhibit good in such a way that PES – cellulose blends mix-
fastness in use and produce a shade that corre- tures of ca. 80 : 20 to 50 : 50 can be dyed in the
sponds with the tint on cellulose. same shade. The PES component is dyed at ca.
In the case of light shades, a slight staining of 130 C without a carrier since carriers can hold
the partner fiber can give an attractive appearance back vat dyes in the dyebath (for mode of dyeing,
to the entire article. Therefore, for pastel shades, see Section 7.2.2). During the HT step, the
depending on the article and its design, only one cellulose portion is uniformly covered with vat
component may be dyed, provided that the stain- dye. After the PES component is dyed, the bath is
ing on the other is fast enough. Leuco esters of vat cooled to 80 C and made alkaline, the vat dye is
dyes are also suitable for the simultaneous fast vatted with hydrosulfite, and dyeing is completed
dyeing of PES and cellulose in pastel shades. The according to the rules for vat dyeing (see Section
mode of dyeing is simple (see Section 4.8.1). To 4.3.6). The disperse dye attached to the cellulose
obtain good fastness on the PES component, portion is removed by means of the vat so that a
drying should be carried out at 170 – 180 C. reductive clearing step to improve fastness be-
Pigment dyeing is also commonly used for light comes unnecessary. The mode of operation in
shades (see Section 4.7). individual dyeing aggregates is described in Sec-
For matching off the two fibers, the compo- tion 2.2.
nents often must be inspected separately. Fiber
blends often look better being dyed tone-on-tone Continuous Dyeing Process. For PES – cel-
if the glossy fiber, PES in this case, is kept lulose blends, continuous dyeing with disperse
somewhat darker. To inspect the dyeing of the and vat dyes is especially safe, easy, and repro-
components, the cellulose in PES – cellulose ducible and produces very fast dyeings. Migra-
blends can be dissolved out by treatment with tion of the dye pigment during drying is a fre-
sulfuric acid (72 %, 45 min at room temperature quent source of faults. In PES – cellulose blends,
or 5 min at 70 C) or orthophosphoric acid the cellulose fiber is the absorptive component
(85 %, 3 – 5 min at 80 – 90 C), which is facili- and counteracts uninhibited migration. In addi-
tated by ultrasonic treatment. Furthermore, small tion, active migration inhibitors (e.g., polyacry-
samples of the individual components in a pre- lates), which can be washed out easily later, are
sentation similar to the material to be dyed can be available. In continuous dyeing, the materials
dyed for inspection together with the fiber must be carefully pretreated to guarantee rapid
mixture. wetting and uniform absorption of liquor (!
Textile Auxiliaries, 4. Pretreatment Auxiliaries,
Chap. 2.).
11.1.2. Dyeing Processes After dye application, the fabric is uniformly
and gently dried and the disperse dye is fixed to
Since safe and efficient continuous dyeing meth- the PES component by the thermosol process (see
ods are well known and large yardages are often Section 7.2.3). Subsequently, the vat dye on the
dyed in the same color, PES – cellulose mixtures cellulose fiber portion is developed either con-
are frequently dyed in continuous processes. tinuously according to the pad steam process or
Nevertheless, the batch dyeing is of major im- batchwise in a jigger (see Section 4.3.6). Jigger
portance for dyeing yarn as well as piece goods, development is performed according to the pad
especially in the knitwear sector. jig process for vat dyes and is advantageous with
respect to penetration into nap containing or
11.1.2.1. Dyeing with Disperse and Vat Dyes densely woven materials. The most elegant
or Appropriate Mixed Dyes method is pad steam development, which fre-
quently follows the thermosol process in one
Batch Dyeing Process. In batchwise dyeing, pass. In pad steam development, the fabric is
a single bath is used in two stages. A suitable padded with reducing agent and alkali, and the
choice of dyes produces dyeings with unsur- vat dye is fixed by steaming in saturated steam
Vol. 36 Textile Dyeing 297
(103 – 105 C dry thermometer). Finely dis- Of little importance is a thermosol exhaus-
persed vat dyes must be used in this process tion process in which the PES component is
because of the short vatting time. The mode of predyed by the thermosol method and the cellu-
operation with individual dyeing aggregates is lose portion is then topped in a bath dyeing
described in Section 2.3.2. process. Also of little significance is a pad batch
HT process in which disperse dye, reactive dye,
11.1.2.2. Dyeing with Disperse and Reactive and chemicals are applied together in the pad-
Dyes der. The reactive dye is then fixed in a pad batch
process, and the disperse dye is fixed in an HT
Reactive dyes are often used to dye the cellulose step. Here, too, alkali-stable disperse dyes are
portion of PES – cellulose blends because the required.
coloring possibilities of reactive dyes are espe-
cially diverse and a large number of relatively Continuous Processes. The most important
easy application processes produce dyeings that continuous dyeing methods are the thermosol
are sufficiently fast for the clothing sector and, pad steam process and the thermosol pad batch
frequently, for household textiles. process. In all continuous processes, the substan-
tivity of the reactive dyes should be taken into
Batch Processes. Since the worldwide ten- account (i.e., the reactive dye can exhaust from
dency is toward smaller batch sizes, PES – cel- the pad liquor or accumulate to a higher or lesser
lulose blends are dyed mainly batchwise by the extent even at room temperature as a function of
exhaustion method. the pH value and salt content).
The two-bath method is a safe mode of dyeing In the thermosol pad batch process, a semi-
that results in reproducible dyeings. The PES continuous process, alkali-sensitive disperse
component is usually predyed with disperse dyes, dyes can be used if the alkali is applied after the
and the cellulose portion is topped with reactive thermosol process. Conversely, if the thermosol
dyes after reductive intermediate clearing, if process is carried out after the pad batch step, the
necessary. pH must be lowered before the thermosol process
In a one-bath two-stage process, the bath so that the disperse dye is not destroyed.
contains all the dyes from the start. After the The thermosol pad steam process is especially
PES component is dyed at 130 C, the bath is important. Disperse and reactive dyes are padded
cooled to ca. 80 C, and alkali is added, resulting together, and alkali and salt are padded after the
in the fixation of the reactive dyes to the cellulose thermosol passage. If a steamer is not available,
component. A careful selection of dyes is re- the reactive dye can be fixed continuously by
quired because the reactive dyes must be stable at means of ‘‘alkali shock’’ in a roller vat with a
pH 4 – 5 and 130 C. relatively high alkali concentration.
In a reverse process, the cellulose component Although the thermosol thermofixing process
is first predyed at alkaline pH, the pH is then is especially easy and economical, it is less
lowered, and the PES component is dyed at easily reproducible and, therefore, of little im-
130 C. In this case, alkali-stable disperse dyes portance. In this process, disperse and reactive
must be chosen if the disperse dye is added at the dyes are padded together with alkali and fixed by
start. In addition, large amounts of salt in the bath dry heat at ca. 210 C. This is followed by
can interfere with dispersion stability. Hence, washing in an open-width washing machine and
especially fast exhausting disperse dyes are used. soaping. Disperse dyes used for this process
Alkali dosing processes with controlled addi- must be alkalistable, and the dispersing agent
tion of alkali are of great importance for dyeing contained in the dye must not react with the
the cellulose component, particularly when vi- reactive dye. Especially suitable reactive dyes
nylsulfone anchor dyes are used. The control are hot dyers that are stable and poorly substan-
program can also allow a progressive increase tive in the pad liquor.
in pH. Thus, the rate of absorption, which is However, none of the one-step processes with
responsible for leveling, and the rate of fixation disperse and reactive dyes achieves the safety of
are optimized. Occasionally, the pH is controlled operation of the thermosol pad steam process
by cleavable alkali-releasing chemicals. with disperse and vat or sulfur dyes.
298 Textile Dyeing Vol. 36
11.1.2.3. Dyeing of the Cellulose Component outerwear sector. They offer the advantages of
with other Dyes dimensional stability, easy care, and fashionable
design possibilities. PES is generally used as
Sulfur Dyes. The thermosol pad steam pro- staple fiber and frequently as a low-pilling type
cess is the primary method for application of [432]. The ratio PES : wool 55 : 45 is widely
disperse and sulfur dyes. However, the sulfur employed.
dyes that are used preferentially in the ready-for- In methods used for pretreating and dyeing
dyeing soluble form, e.g., Cassulfon (Hoechst) PES – wool blends, the relatively high sensitivi-
and Sodyesul (Southern Dyestuff), and are spe- ty of wool must be taken into account. Difficul-
cially inexpensive for muted shades, must be ties are circumvented by dyeing the components
applied after the thermosol step because of their separately as loose stock or slubbing (see
incompatibility with disperse dyes. Chaps. 5 and 7). Especially fast dyeings are
obtained in this manner. However, quick changes
Leuco Esters of Vat Dyes. If a thermosol in fashion and short-term planning frequently do
passage is provided under conditions that cleave not permit separate dyeing.
the ester and the vat acid can diffuse into the PES
fiber, leuco esters of vat dyes can produce up to
medium shades with a high fastness level without 11.2.1. Dyes
the additional use of disperse dyes (ATE process,
Hoechst). In dyeing PES – wool mixtures, disperse dyes
are used for the PES component and acid or
Small Molecular Vat Dyes. Only one class of
metal- complex dyes for the wool. Disperse dyes
dyes is needed when small molecular vat dyes are
can soil wool to a great extent. Since they pro-
used. Fast dyeings are obtained in lighter shades.
duce poorly fast dyeings on wool, the dyes
Padding and the thermosol process are, if neces-
selected must stain wool as slightly as possible
sary, followed by vatting and normal aftertreat-
or must be easily removable by a washing step,
ment to improve fastness on the cellulose
which may be reductive if necessary. Frequently
component.
used dyes are C.I. Disperse Yellow 23, 54, 64, C.
Direct Dyes. If no great fastness demands I. Disperse Orange 30, 33, C.I. Disperse Red 50,
are made on the dyed article, PES – cellulose 60, 73, 91, 167, 179, and C.I. Disperse Blue 56,
blends can be dyed in a one-bath, one-step or two- 73, 87. Premixed dyes consisting of disperse and
step process with disperse and direct dyes. The wool dyes are occasionally available, e.g., For-
direct dyes selected here must be stable under HT osyn (Sandoz).
dyeing conditions. Dyes whose wetfastness can Wool is stained less at high temperatures and
be improved by aftertreatment are of advantage. longer dyeing times because the disperse dye that
The subsequent resin finishing must also be taken was initially on the wool component migrates to
into account in dye selection. the PES fiber. Carrier-free dyeable PES fibers
In a two-bath, two-step dyeing process, other should preferably be employed; these fibers are
dyes suited to cellulose fibers may also be used easily dyeable even at boiling temperature (see
for PES – cellulose blends. For instance, in spite Section 7.2.6). The nature of the wool also plays a
of its tediousness, Naphtol AS dyeing is still role, fine wool and reclaimed wool being more
employed, especially for wetfast red shades (see strongly soiled.
Section 4.6), and the phthalogen process is used
for turquoise (see Section 4.8.7). Pigment dyeing
is also applied to PES – cellulose blends (see 11.2.2. Dyeing Processes
Section 4.7).
For practical information about the dyeing of
PES – wool mixtures, see [428, pp. 291 –
11.2. Polyester – Wool Blends 328], [433]. Wool cannot be dyed at the high
temperatures normal in the HT dyeing of PES
Mixtures of PES fibers and wool are used widely, fibers or PES – cellulose blends. The dyeing
especially as woven goods and knitwear in the time should also be as short as possible so that
Vol. 36 Textile Dyeing 299
the wool is not damaged. The following dyeing A leveling agent is required primarily if tippy-
processes are usually employed: dyeing grades of wool are present.
In the selection of a carrier, technical as well
1. At boiling temperature with a carrier as ecological factors must be considered (!
2. At 103 – 106 C with little carrier Textile Auxiliaries, 5. Dyeing Auxiliaries, Chap.
3. At 110 – 115 C with the addition of formal- 5.). As in the dyeing of pure PES fibers, the
dehyde as a wool protectant and without a amount of carrier to be applied is determined by
carrier (HT dyeing) the type of carrier, the dyes, the type of fiber, the
dyeing temperature, the depth of shade, the liquor
The significance of HT dyeing has increased ratio, and the dyeing aggregate.
in more recent times. If possible, yarn is dyed at 106 C or still
The dyeing of PES – wool blends is carried higher temperatures because, in this way, the
out in one or two baths. In the one-bath process production fastness (e.g., fastness to setting)
preferred in practice, PES and wool are dyed required for further processing is easier to guar-
simultaneously at pH 4 – 5, which is favorable antee. This is possible because thermally stable
for wool. Reductive aftertreatment is possible disperse dyes that exhaust only at higher tem-
only if the wool dyes used can withstand it. peratures are used.
The two-bath process is applied for deep To separately inspect the PES component of
shades and for stringent fastness requirements. PES – wool mixtures, the wool can be dissolved
Disperse dyes, which soil wool to a somewhat out with sodium hydroxide (5 % solution, boil for
greater extent, can also be used in this case. The 5 min) or a chlorine bleach (50 g/L active chlo-
first step involves the use of disperse dyes for rine, 5 min at 50 C).
predyeing the PES part, followed by reductive
intermediate clearing and wool dyeing. Howev- Aftertreatment. After dyeing, an afterwash
er, while dyeing the wool component, dye must is always indicated to remove the disperse dye
always be expected to detach from PES and retint attached to the wool. The materials are treated
the wool. with an ethoxylated fatty amine in a weakly
Prebleached wool becomes somewhat yellow acidic liquor at 60 C. Reductive aftertreatment
on dyeing. To obtain clear pastel shades bleach is possible only in the case of appropriately stable
and dye are used preferably in the same bath. wool dyes.
Mildly bleaching reducing agents (especially
stabilized bisulfite or hydroxylamine salts) can
be employed because they do not affect the dyes 11.3. Polyamide – Cellulose Blends
used.
Continuous or semicontinuous dyeing pro- Polyamide (PA) fibers are included in articles
cesses are uncommon because dry heat treatment made of cellulose fibers to improve dimensional
(thermosol) hardens wool. Besides, application stability, ease of care, and durability. Examples
of the wool dye requires dyeing in aqueous liquor of articles include sportswear and knitwear, cor-
or dye fixation by steaming. duroy fabrics, or plush articles in which a PA pile
is often anchored to a cellulose fabric base.
Different dyeing methods are described in
11.2.3. Auxiliaries [429, pp. 433 – 437], [430, p. 570].
must be made and the dyeing process adapted yield on the cellulose component. Finally, the
appropriately. liquor is made alkaline for reaction with the
If dyeing is carried out in the presence of 1 % cellulose fiber. Dyes (e.g., with monochlorotria-
sodium dihydrogenphosphate without salt at zine anchor) that dye PA from a neutral liquor in
boiling temperature, solid shades from light to the presence of salt are applied in a two-step
moderate can be obtained with high-leveling process, as in the case of cellulose. In the reversal
direct dyes (e.g., C.I. Direct Yellow 44, Direct of this dyeing process, the cellulose component is
Red 81, and Direct Black 51). The choice of dyed first at alkaline pH, followed by neutraliza-
suitable dyes is greater if dyeing is performed in a tion with acid, and the PA component is then
single bath with direct and disperse dyes at pH 8 covered at elevated temperature.
in the presence of a leveling agent and a resist for Dyeing processes with reactive dyes are de-
the PA fiber (! Textile Auxiliaries, 5. Dyeing scribed in Section 4.1.
Auxiliaries, Chap. 6.) to prevent the direct dyes to
exhaust mainly on the PA component.
If, instead of disperse dyes, wetfast acid or 11.4. Polyacrylonitrile – Cellulose
metal- complex dyes are used for the PA compo- Blends
nent, union shades having good lightfastness and
moderate wetfastness can be obtained. Dyeing is Polyacrylonitrile (PAC) – cellulose blends are
carried out at pH 5 – 8, depending on the depth of used for household textiles and imitation fur. In
shade and the type of acid dye used. The dyeing these plush and fur materials, the pile consists of
temperature is raised to boiling to guarantee good PAC fibers while the back is made of cotton or
leveling and firm fixation of the wetfast acid dyes cellulose regenerated fibers. The wool-like char-
in the PA fiber. acter, favorable price, and easy care of PAC
Dyeings of the highest wetfastness are ob- fibers combine with the high water-absorbing
tained on PA – cellulose blends with vat dyes. capacity of cellulose fibers. Furthermore, PAC –
The coloring strength on the PA component cellulose mixtures are used for leisure wear, sport
depends on the type of PA fiber and on dyeing stockings, drapery, and table linen. The percent-
conditions (the depth of shade on PA 6 is deeper age of PAC in the mixtures varies between 30 and
than on PA 66). The lightfastness of some vat 80 %. For a survey of dyeing methods, see [429,
dyes can be lower on PA than on cellulose fibers. pp. 474 – 476] and [430, pp. 608 – 610].
The advantage of using vat dyes is that in a single Continuous dyeing of PAC – cotton plush
bath with selected products, dyeings of the same with cationic and direct dyes according to the
shade are obtained on both components. For pad steam process plays an important role. The
instance, C.I. Vat. O. 26, V.B. 4 and 14, V. Br. choice of dyes must take into account liquor
55, V. Bl. 9 and 25 are widely applicable (in the stability, reservation of PAC or cellulose fiber,
exhaust and pad steam process). The dye yield on and solubility. Precipitation of cationic and an-
the PA component increases with increasing ionic dyes present in the pad liquor at relatively
temperature. With a dyeing time of 60 min, the high concentrations cannot be avoided solely by
most favorable temperature for the dyes men- dye selection. Suitable auxiliary systems have
tioned above is 80 – 90 C. The additives to the been developed. Differently charged dyes are
dyebath and the dyeing processes are the same as kept in solution separated from each other in two
those used for dyeing cellulose fibers with vat phases by the combination of anionic and non-
dyes (see Section 4.3). ionogenic surfactants. With the help of fixing
Clear shades with very good fastness are accelerators, good penetration of PAC fibers can
obtained on PA – cellulose blends with reactive be achieved in 10 – 15 min with saturated steam
dyes. Like vat dyes, the depth of shade of reactive at 98 – 100 C.
dyes depends relatively strongly on the type of With cationic and vat dyes, dyeing can be
PA and structural differences. Dyeing is carried conducted batchwise according to the pigment
out in a three-step process with appropriately process in one bath and two steps. Here, the PAC
selected products. First, the reactive dyes in a component is dyed with cationic dyes and the
weakly acidic liquor are allowed to absorb to the cellulose portion is simultaneously pigmented.
PA component. Salt is then added to improve the After being cooled to 70 C (maximum) and
Vol. 36 Textile Dyeing 301
vatted, the Indanthren dye is fixed (see also mutual precipitation. Precipitation can be pre-
Section 4.3). Another possibility is to complete vented by dispersing auxiliaries and precise dye
the dyeing of the PAC component first with selection. Very deep shades (e.g., black) are
cationic dyes and then add the vat dye to the normally dyed in a one-bath, two-step process.
same bath after cooling. Although only cationic dyes may be used for
PAC – cellulose mixtures can also be dyed in dyeing the PAC component, metal- complex
a one-bath, two-step process with reactive and dyes, chrome dyes, or reactive dyes can be used
cationic dyes. Here, too, the PAC component is for wool.
predyed at pH 5 with cationic dyes, and after the In the case of 1 : 1 metal- complex dyes, al-
pH is raised, the cellulose component is covered most no danger of precipitations exists because
with reactive dyes. Process safety is obviously of intramolecular compensation of the negative
increased when a two-bath process is employed. charge by the positively charged metal atom. The
For the dyeing of yarn, see [434]. pH is adjusted to 2.5 – 3 (see also Section 5.1.4).
Most cationic dyes can be applied at this low pH
value. Only the auxiliaries and the acid are added
11.5. Polyacrylonitrile – Wool Blends while the dyebath is being heated. After the initial
dyeing temperature (ca. 70 C) is reached, the
No other synthetic fiber achieves the wool-like cationic dyes are added first. After balancing
character of PAC fibers. For this reason, PAC concentration differences (ca. 5 to 10 min), the
fibers are especially suited to the production of anionic dyes are then added. A pH of 4.5 – 5.5 is
blends with wool for applications in which the maintained for acid, chrome, reactive, and 1 : 2
woolly character is indispensable. The high wa- metal- complex dyes.
ter-absorbing capacity of wool and the high In the choice of dyes, attention must be paid
strength of PAC fibers complement each other not only to the prevention of precipitation but
and confer good wearability on articles made of also to the reserve of PAC fibers and wool.
this mixture. Woven and knitted fabrics possess a Cationic dyes attach first to wool, producing
greater dimensional stability and mechanical colors of very poor fastness, and then boil over
stressability than corresponding wool textiles. onto the PAC fiber. Even if well-reserving dyes
The very low water-absorbing capacity of the are selected, dyeing must be conducted for a
PAC fiber does not have such an unpleasant sufficiently long time (60 – 90 min) until the
effect as in textiles made of PAC alone, and the boilover is complete, in order to obtain the
felting tendency is lower than that of wool. The absolutely essential good wool reserve.
blending ratio of PAC to wool varies from about Apart from chemical problems (precipitation,
20 : 80 to 80 : 20. The blends are preferred for reserve), the mechanical properties of the mate-
outer clothing, especially knitwear (e.g., pull- rials must also be taken into account. Knitwear
overs and socks), and for household textiles. made of PAC – wool must not be exposed to
excessively high tensile stress during dyeing.
Dyeing Processes. In principle, three possi-
bilities exist for dyeing PAC – wool mixtures
[429, pp. 473 – 474], [430, p. 610]: 11.6. Blends of Synthetic Fibers
1. The two-bath method, i.e., dyeing of wool and No fiber exists that has not at least on a trial basis
PAC in succession in two baths been combined with every other fiber to attain
2. The one-bath, two-step method, i.e., dyeing of new fashionable or technical effects (see survey
wool and PAC in succession in the same bath in [429, pp. 420 – 421]). From a dyers’ stand-
3. The one-bath, one-step method, i.e., dyeing of point, these mixtures do not always make sense.
wool and PAC simultaneously Practically all synthetic fibers can be dyed with
disperse dyes. Thus, the affinities of these dyes
The one-bath, one-step method is preferred for the fiber components and their fastness prop-
for economic reasons. However, problems arise erties should always be taken into account in
due to the simultaneous presence of cationic and dyeing blends of synthetic fibers [435]. In the
anionic dyes in the dyebath, with the danger of selection of a dyeing process, the individual
302 Textile Dyeing Vol. 36
components must be considered. With blends of or 1 : 2 metal- complex dyes for the PA compo-
PA and PES fibers, for example, one should note nent. Disperse dyes can naturally be used as well.
that although disperse dyes have a higher affinity However, a lower wetfastness level must be
for PES than for PA fibers, the rate of dyeing on expected, and a distinct amount will absorb to
PES at boiling temperature in the absence of the PAC component [429, pp. 471 – 473]. For
dyeing accelerants is so low that the PA compo- the dyeing of mixtures containing elastomeric
nent is usually dyed to a deeper and, frequently, fibers, see Section 10.2.
in a different shade. If the same shades are to be
produced on a blend of this type, a small selection
of disperse dyes is used at the highest possible 12. Characterization of Textile Dyes
temperature under exactly stipulated dyeing con-
ditions. To obtain better fastness on the PA This chapter gives a description of those proper-
component, the disperse dye can then be reduc- ties that are of general importance for dyes or
tively eliminated to a large extent and the mate- groups of dyes. Such a description is based on
rial redyed with acid or metal- complex dyes experimentally determined quality data.
[428, pp. 359 – 363].
A frequently processed mixture (e.g., for out- Color Strength, Hue, Chroma (! Dyes,
erwear or furnishing fabrics), consists of PES and General Survey, Section 3.2., ! Dyes, General
PAC fibers. No basic difficulties are involved in Survey, Section 3.3., ! Dyes, General Survey,
dyeing, both union shades (tone-on-tone dyeing) ! Dyes, General Survey, Section 3.5., ! Dyes,
and bicolor dyeing being possible. Selected dis- General Survey, Section 3.6.). The dominating
perse and cationic dyes are used for dyeing. characteristics of a dye are its coloring properties.
Although disperse dyes color PAC more weakly These are assessed by preparing a dyed test
than PES, the shade produced is the same. In the sample whose color is evaluated. This must, in
case of bicolor dyeing, the PAC component must principle, always be done by the human eye
always be kept darker. A dyeing temperature of because color perception, being a subjective
106 C should not be exceeded because of the sense impression, is not accessible to direct
PAC component. Thus, carriers must be used as a measurement. However, with the aid of colorim-
rule. In one-bath dyeing, attention must be paid to etry, which can be regarded as a simulation of the
the compatibility of the various dyebath additives visual perception of color, this visual perception
with each other. Cationic retarders are not used in can be represented by measurable quantities.
one-bath dyeing [428, pp. 346 – 355], [430, Since colorimetry is an objective method and is
pp. 601 – 602]. therefore more accurate and reproducible than
Problems with the compatibility of the dyes subjective visual assessment, it is very widely
used can also arise in dyeing mixtures of PA and used today. Color is a three-dimensional quantity
PAC fibers. Mixtures of this type are occasionally and must therefore be expressed by a set of three
produced for skiing articles and for wool – PA numbers (color coordinates). In practice, these
imitations. The cationic dyes used for the PAC are typically the values of color strength, hue, and
component do not dye normal PA fibers. Acid chroma (! Dyes, General Survey) [436].
and metal- complex dyes leave PAC fibers prac- Color can be described with any accuracy only
tically white. Sulfo group containing 1 : 1 metal- in a comparative way (i.e., in terms of deviations
complex dyes possess a zwitterionic character from a standard). Although the three-dimension-
and, therefore, can be applied in low concentra- al color coordinates can be determined by color-
tion in the same bath with cationic dyes, without imetry (as absolute values), this is in practice not
the occurrence of precipitation. In this manner, sufficient to provide an exact specification. In the
one-bath dyeing can be carried out. The stability case of a dye, the reference is a standard dye
of the bath can be improved by addition of a sample provided by the producer against which
nonionic auxiliary (e.g., an ethoxylated fatty all further supplies are controlled and standard-
alcohol). Cationic retarders should be excluded ized. To be used as a basis for assessment the
in all cases. Dyeing is accomplished most safely standard sample must be extremely stable.
in two steps: first with cationic dyes, because they To test a dye, dyed test specimen are prepared
exhaust almost quantitatively, and then with 1 : 1 from both the sample dye and the standard under
Vol. 36 Textile Dyeing 303
conditions that are as identical as possible and the dye is dissolved under defined conditions of
then assessed visually or colorimetrically. In temperature, time, and concentration, and is
practice, color strength is calculated from various filtered after a storage time or after addition
color strength values agreed upon by the produc- of electrolytes. The filter should then be free of
er and the customer. A widely used method is a residues. To give consistent and comparable
determination based on the weighted sum of the results, the values of various parameters (tem-
K/S values (K is the coefficient of absorption, S perature, etc.) should be kept constant and
the coefficient of scatter), which is used in stan- should be specified in standards. For example,
dard specifications [437] (! Dyes, General Sur- the temperatures for hot and cold solubility are
vey, Section 3.6.). The relative color strength is set at 90 C and 25 C, respectively (ISO/DIS
calculated as the ratio of the color strength values 105-Z07, ISO/DIS 105-Z08, and ISO/DIS 105-
for the sample dye and the standard expressed as Z09) [440].
a percentage. For disperse dyes, the dispersion properties
Dyers can in practice compensate for differ- are of similar importance, but they are not easy to
ences in color strength by adjusting the concen- describe because of the complex processes and
tration. Therefore, the hue and chroma of a unstable dispersion states. Therefore, a large
dyeing are always judged against a standard number of test methods exist, the results of which
dyeing of equivalent color strength. This is car- are usually limited in their application. A critical
ried out by visual assessment in which the color- review can be found in [441].
ist estimates the remaining differences in hue and
chroma for a strength- corrected dyeing. In a Dust. The dust produced from dyes is of
colorimetric evaluation, the residual color differ- great importance for many reasons, including
ence is determined by a mathematical correction possible health hazards and intense coloration,
to give equivalence in color strength. The result is leading to severe soiling, that can be caused by
expressed in CIELAB color difference units very small amounts of dust particles. The content
(DIN 6174) and is usually separated into com- of fine dust (1 – 10 mm) must be reduced by
ponents for hue (DH*) and chroma (DC*) [437], adhesive bonding or prevented by the use of
[438] (! Dyes, General Survey, Section 3.5.). special formulations (granulation) of the dye.
In practice, color strength is often determined Fine dust is especially troublesome because of
by the simpler and more easily reproducible the stability of its suspensions in air, and it can
measurement of the extinction of the dye solu- constitute a health hazard when inhaled.
tion. However, this does not in all cases agree The amount of dust depends not only on the
with the values determined by dyeing because the dust behavior of the dye, but also on the nature
dye is not always absorbed quantitatively by the and intensity of handling operations that generate
fiber [439]. dust [442]. Therefore, the dusting behavior of a
product is significant only for comparison with
Solution and Dispersion Behavior. For the other products and cannot be used to predict dust
dyeing process in aqueous liquor, the dye must exposure. In a widely used test method, the dust
have adequate solubility or dispersibility. In produced when a defined amount of dye is al-
general, good solubility is necessary for good lowed to fall is determined quantitatively or
application properties. If the solubility is poor qualitatively [443]. The dust is first collected on
(i.e., if any of the dye is present in the dye liquor a filter, and assessment occurs by visual compar-
in the form of undissolved particles), local col- ison of the dust-laden filter with a gray scale
oration (specks), spots, uneven effects, and poor divided into five levels (ISO 105-A03) or by
fastness can be produced, leading to serious quantitative gravimetric or photometric determi-
defects and costly complaints. nation of the quantity of dust.
In addition to solubility properties, the sta-
bility of the liquor during preparation and use Compatibility of Basic Dyes for Acrylic
(i.e., the solution stability) is important. For Fibers. Basic dyes usually have limited migra-
reactive dyes applied to cellulose, the solution tion ability. Therefore, with combination (tri-
stability in the presence of electrolytes is im- chromic) dyeing processes, the dyes are chosen
portant (electrolyte stability). To test for this, so that they are absorbed at as uniform a rate as
304 Textile Dyeing Vol. 36
possible to prevent local color differences that The latest, very important development is
would otherwise occur readily. the edition of European Standards (EN), which
To characterize combination behavior, dyes are published in English, French, and German.
are divided into five groups numbered 1 to 5 For testing colorfastness, these European stan-
(compatibility values). Higher numbers corre- dards correspond completely with ISO 105,
spond to a lower bath exhaustion rate. The com- which became EN 20 105 with the same code
patibility of a dye is determined by producing numbers (i.e., ISO 105-B02 becomes EN
samples of dyed materials in which the test dye is 20 105-B02). Since the editorial work takes
combined with five standard dyes whose com- considerable time, publishing the European
patibility values are known (AATCC Test Meth- standards will take several years. At the mo-
od 141 – 1987; ISO/DIS 105-Z03) [444]. ment, very few EN denominations exist. When
the European standards are published the na-
tional standards (e.g., DIN standards) are
13. Testing of Colorfastness [445] withdrawn.
ISO 105-A02: Grey Scale for Assessing brightened) textiles, the fastness is assessed by
Change in Colour (¼ DIN 54 001-A02: comparing the change of whiteness with that of
Herstellung und Handhabung des Graumaßstabes the references used. Five different methods are
zur Bewertung der €anderung der Farbe) describes described.
the gray scale for determining changes in the
color of textiles in colorfastness tests, and its use. ISO 105-B03: Colour Fastness to Weather-
A precise colorimetric specification of the scale ing: Outdoor Exposure (¼ DIN 54 070-B03:
is given. Bestimmung der Wetterechtheit von F€arbungen
und Drucken in freier Atmosph€are). Specimens
ISO 105-A03: Grey scale for Assessing of the textile are exposed under specified condi-
Staining (¼ DIN 54 002-A03: Herstellung und tions in the open air without any protection from
Handhabung des Graumaßstabes zur Bewertung weathering. At the same time and place, eight
des Anblutens) describes the gray scale for de- dyed wool references are exposed to daylight, but
termining staining of adjacent fabrics in color- they are protected from rain, snow, etc., by a
fastness tests, and its use. A precise colorimetric sheet of glass. Fastness is assessed by comparing
specification of the scale is given. the change in color of the specimen with that of
the references. Two different methods are
ISO 105-A04: Method for the Instrumental described.
Assessment of the Degree of Staining of Adja- The wide variations in conditions under which
cent Fabrics (DIN standard in preparation). outdoor exposures are usually carried out make
This part of ISO 105 specifies an instrumental replicate exposures at different times of the year
method for assessing the degree of staining of desirable. The most reliable indication of weath-
adjacent fabrics in any fastness test, as an alter- ering fastness is obtained by taking the mean of
native to the visual method. the assessment of several exposures.
ISO 105-B02: Colour Fastness to Artificial ISO 105-B05: Detection and Assessment of
Light: Xenon Arc Fading Lamp Test (¼ DIN Photochromism (¼ DIN 54 069-B05: Verfah-
54 004-B02: Bestimmung der Lichtechtheit von ren zur Erkennung und Bestimmung der Photo-
F€arbungen und Drucken mit Xenonbogenlicht). chromie von F€arbungen und Drucken). A speci-
A specimen of the textile is exposed to artificial men of the textile is exposed to light of high
light under prescribed conditions, along with intensity for a time much shorter than that nec-
blue wool references. Two different sets of blue essary to cause a permanent change. The change
wool references exist, which are not interchange- in color of the specimen is assessed immediately
able. Colorfastness is assessed by comparing the after exposure, by using the gray scale. The
change in color of the specimen with that of the specimen is then stored in the dark and assessed
references used. For white (bleached or optically again.
306 Textile Dyeing Vol. 36
ISO Designation Test no. Corresponding DIN/EN designation Time, min Temperature, C
echtheit von F€arbungen und Drucken). A speci- textile, while it is still wet and after drying, are
men of the textile in contact with one or two assessed with the gray scale.
specified adjacent fabrics is immersed in water,
drained, and placed between two plates under a ISO 105-E06: Colour Fastness to Spotting:
specified pressure in a test device for 4 h at Alkali (¼ DIN 54 030-E06: Bestimmung der
37 C. The specimen and the adjacent fabric(s) Alkaliechtheit von F€arbungen und Drucken).
are dried separately. The change in color of the Drops of a solution of sodium carbonate are
specimen and the staining of the adjacent fabric placed on the specimen, whose surface is rubbed
(s) are assessed with the gray scales. gently with a glass rod to ensure penetration. The
change in color of the textile is assessed with the
ISO 105-E02: Colour Fastness to Sea gray scale.
Water (¼ DIN 54 007-E02: Bestimmung der
ISO 105-E07: Colour Fastness to Spotting:
Meerwasserechtheit von F€arbungen und Druck-
Water (¼ DIN 54 008-E07: Bestimmung der
en). This test is performed in the same manner as
colorfastness to water but a 30-g/L aqueous Wassertropfenechtheit von F€arbungen und
Drucken). Drops of water are worked into the
sodium chloride solution is used instead of water.
specimen with a glass rod, so that a spot approxi-
ISO 105-E03: Colour Fastness to Chlori- mately 20 mm in diameter is formed. The change
nated Water (Swimming-Bath Water) (¼ of color of the textile is assessed with the gray
DIN 54 019-E03: Bestimmung der Farbechtheit scale after 2 min and after drying.
von F€arbungen und Drucken gegenüber ge- ISO 105-E08: Colour Fastness to Water:
chlortem Wasser). A specimen of the textile is Hot Water (¼ DIN 54 047-E08: Bestimmung
treated with a weak aqueous chlorine solution of der Heißwasserechtheit von F€arbungen und
a given concentration and dried. The change in Drucken). A specimen of the textile in contact
color of the specimen is assessed with the gray with adjacent fabrics is rolled around a glass rod,
scale. treated with slightly acidified hot water (pH 6 at
Three alternative test conditions are specified: 70 C), and dried. The change in color of the
Active chlorine concentrations of 50 mg/L and specimen and the staining of the adjacent fabrics
100 mg/L are intended for swimwear. An active are assessed with the gray scales. The method is
chlorine concentration of 20 mg/L is intended for applicable mainly to wool and to textiles contain-
accessories such as beach robes and towels. ing wool.
ISO 105-E04: Colour Fastness to Perspira- ISO 105-E09: Colour Fastness to Potting
tion (¼ DIN 54 020-E04: Bestimmung der (¼ DIN 54 048-E09: Bestimmung der Pottin-
Schweißechtheit von F€arbungen und Drucken). gechtheit von F€arbungen und Drucken). A speci-
Specimens of the textile in contact with adjacent men of the textile between adjacent fabrics is
fabrics are treated in two different solutions rolled around a glass rod and treated with boiling
containing histidine, drained, and placed be- water. The specimen and adjacent fabrics are
tween two plates under a specified pressure in dried separately. The change in color of the
a test device for 4 h at 37 C. The specimens and specimen and the staining of the adjacent fabrics
the adjacent fabrics are dried separately. The are assessed with the gray scales.
change in color of each specimen and the staining
of the adjacent fabrics are assessed with the gray ISO 105-E10: Colour Fastness to Decatiz-
scales. ing (¼ DIN 54 054-E10: Bestimmung der De-
katurechtheit von F€arbungen und Drucken). A
ISO 105-E05: Colour Fastness to Spotting: specimen of the textile is wrapped around a
Acid (¼ DIN 54 028-E05: Bestimmung der perforated cylinder, and steam is passed through
S€aureechtheit von F€arbungen und Drucken). it for 15 min. The change in color of the dried
Drops of a solution of acid (acetic acid, sulfuric specimen is assessed with the gray scale. Correct
acid, tartaric acid) are placed on the specimen, handling of the method is controlled by use of a
whose surface is rubbed gently with a glass rod to test- control specimen tested under identical con-
ensure penetration. The changes in color of the ditions. Two tests, mild and severe, are given.
308 Textile Dyeing Vol. 36
ISO 105-E11: Colour Fastness to Steam- Specimens of textiles are exposed to nitrogen
ing (¼ DIN 54 058-E11: Bestimmung der oxides in a closed container until either one (dyes
D€ampfechtheit unter atmosph€arischem Druck with poor color fastness to nitrogen) or three
von F€arbungen und Drucken). A specimen of (dyes with good color fastness to nitrogen) test-
the textile in contact with specified adjacent control specimens exposed simultaneously with
fabrics is rolled into a cylinder and placed for the test specimens have changed color to a pre-
30 min in the neck of a flask containing boiling determined extent. The change in color of the
water. The staining of the adjacent fabrics is textile is assessed with the gray scale.
assessed with the gray scale.
ISO 105-G02: Colour Fastness to Burnt
ISO 105-E12: Colour Fastness to Milling: Gas Fumes (no DIN standard issued up to
Alkaline Milling [¼ DIN 54 041-E12: Bestim- now). A specimen of the textile and the test-
mung der alkalischen Walkechtheit (schwere control fabric are exposed simultaneously to
Beanspruchung)]. A specimen of the textile in oxides of nitrogen from burnt gas fumes until
contact with one or two specified adjacent fabrics the test- control shows a change in color corre-
is milled at 40 C in a jar containing 50 steel balls sponding to that of the standard of fading. The
and a solution of soap and sodium carbonate. The change in color of the specimen is assessed with
severity of action is controlled by means of a test- the gray scale. If no color change is observed in
control dyeing milled separately in the same way. the specimen after one exposure period or cycle,
After rinsing and drying, the change in color and exposure may be continued either for a specified
the staining of the adjacent fabrics are assessed number of periods or for the number of periods
with the gray scale. required to produce a specified amount of color
change in the specimen.
ISO 105-E13: Colour Fastness to Acid-
Felting: Severe [DIN 54 043-E13: Bestim- ISO 105-G03: Colour Fastness to Ozone in
mung der sauren Walkechtheit von F€arbungen the Atmosphere (no DIN standard issued up to
und Drucken (schwere Beanspruchung)]. A spec- now). A specimen and a swatch of test- control
imen of the textile in contact with adjacent sample are exposed simultaneously to ozone in
fabrics is milled in solutions of acetic or sulfuric an atmosphere at ambient temperature and rela-
acid as used under severe conditions in the acid- tive humidities not exceeding 65 %, until the
felting process, rinsed, and dried. The change in control sample shows a color change correspond-
color of the specimen and the staining of the ing to that of a standard of fading. This exposure
adjacent fabrics are assessed with the gray scales. period constitutes one cycle. The cycles are
repeated either until the specimen shows a defi-
ISO 105-E14: Colour Fastness to Acid- nite color change or for a prescribed number of
Felting: Mild [¼ DIN 54 042-E14: Bestim- cycles.
mung der sauren Walkechtheit (leichte Bean-
spruchung)]. A specimen of the textile in contact
with adjacent fabrics is milled in mineral acid 13.2.7. Group J: Measurement of Colour
solutions at 60 C, as used under mild felting and Colour Differences
conditions in the hatmaking and felt industries,
rinsed, and dried. The change in color of the ISO 105-J01: Measurement of Colour and
specimen and the staining of the adjacent fabrics Colour Differences (no DIN standard). This
are assessed with the gray scales. part of ISO 105 selects from several options
published by the CIE those best suited to the
needs of the textile industry whenever the differ-
13.2.6. Group G: Colour Fastness to ence in color between two specimens has to be
Atmospheric Contaminants quantified.
ISO 105-G01: Colour Fastness to Nitrogen ISO 105-J02: Method for the Instrumental
Oxides (¼ DIN 54 025-G01: Bestimmung der Assessment of Whiteness (no DIN standard).
Stickoxidechtheit von F€arbungen und Drucken). This part of ISO 105 specifies a method intended
Vol. 36 Textile Dyeing 309
for quantifying the whiteness of textiles, includ- ISO 105-N05: Colour Fastness to Stoving
ing fluorescent materials. (¼ DIN 54 038-N05: Bestimmung der Schwef-
elechtheit von F€arbungen und Drucken). A spec-
imen of the textile, containing its own mass of
13.2.8. Group N: Colour Fastness to soap solution, and a test- control specimen are
Bleaching Agencies exposed in an atmosphere containing sulfur di-
oxide. The change in color of the specimen and
ISO 105-N01: Colour Fastness to Bleach- the staining of the adjacent fabrics are assessed
ing: Hypochlorite [¼ DIN 54 035-N01: Bes- with the gray scales.
timmung der Hypchlorit-Bleichechtheit (schwere
Beanspruchung)]. A specimen of the textile is
agitated in a solution of 2 g/L sodium hypochlo- 13.2.9. Group P: Colour Fastness to Heat
rite or lithium hypochlorite, rinsed in water, Treatments
agitated in a hydrogen peroxide solution or sodi-
um hydrogensulfite solution, rinsed, and dried. ISO 105-P01: Colour Fastness to Dry Heat
The change in color of the specimen is assessed (Excluding Pressing) (¼ DIN 54 060-P01:
with the gray scale. Bestimmung der Trockenhitzefixier- und Trock-
enhitzeplissierechtheit von F€arbungen und
ISO 105-N02: Colour Fastness to Bleach- Drucken). A specimen of the textile in contact
ing: Peroxide (¼ DIN 54 033-N02: Bestim- with specified adjacent fabrics is heated by close
mung der Peroxid-Bleichechtheit von F€arbungen contact with a medium that is brought to the
und Drucken). A specimen of the textile in required temperature (30 s at 150, 180, or
contact with adjacent fabrics is immersed in the 210 C). The change in color of the specimen
bleaching solution, containing sodium peroxide and the staining of the adjacent fabrics are as-
in concentrations commonly used in textile sessed with the gray scales.
bleaching processes, rinsed, and dried. Four dif-
ferent bleaching baths are described. The change ISO 105-P02: Colour Fastness to Pleating:
in color and the staining are assessed with the Steam Pleating (¼ DIN 54 059-P02: Bestim-
gray scales. mung der D€ampfechtheit mit überdruck von
F€arbungen und Drucken). A specimen of the
ISO 105-N03: Colour Fastness to Bleach- textile in contact with specified adjacent fabrics
ing: Sodium Chlorite: Mild [¼ DIN 54 036- is steamed under pressure (135, 170, 270 kPa, for
N03: Bestimmung der Chlorit-Bleichechtheit 5, 10, or 20 min) and dried. The change in color
von F€arbungen und Drucken (leichte Beanspru- and the staining of the adjacent fabrics are as-
chung)]. A specimen of the textile in contact with sessed with the gray scales.
specified adjacent fabrics is treated in a sodium
chlorite solution (1 g/L, pH 3.5 at 80 C for 1 h),
rinsed, and dried. The change in color and the 13.2.10. Group S: Colour Fastness to
staining of the adjacent fabrics are assessed with Vulcanization
the gray scales.
ISO 105-S01: Colour Fastness to Vulcani-
ISO 105-N04: Colour Fastness to Bleach- zation: Hot Air (¼ DIN 54 065-S01: Bestim-
ing: Sodium Chlorite: Severe [¼ DIN mung der Heißluftvulkanisierechtheit von
54 037-N04: Bestimmung der Chlorit- F€arbungen und Drucken). A specimen of the
Bleichechtheit von F€arbungen und Drucken textile in air is in direct contact with an (initially)
(schwere Beanspruchung)]. A specimen of the unvulcanized rubber compound. The change in
textile in contact with specified adjacent fabrics color of the specimen is assessed with the gray
is treated in a sodium chlorite solution (2.5 g/L, scale.
pH 3.5 at 80 C for 1 h), rinsed, and dried. The
change in color of the specimen and the staining ISO 105-S02: Colour Fastness to Vulcani-
of the adjacent fabrics are assessed with the gray zation: Sulfur Monochloride (¼ DIN 54 064-
scales. S02: Bestimmung der Kaltvulkanisierechtheit
310 Textile Dyeing Vol. 36
von F€arbungen und Drucken). A specimen of the ISO 105-X04: Colour Fastness to Mercer-
textile is exposed to sulfur monochloride vapor izing (¼ DIN 54 039-X04: Bestimmung der
under conditions usually occurring during the Mercerisierechtheit von F€arbungen und Druck-
cold vulcanization of rubber. The change in color en). A specimen of the textile in contact with a
of the specimen is assessed with the gray scale specified cotton adjacent fabric is treated with a
before and after neutralizing with aqueous 300 g/L sodium hydroxide solution (5 min at
ammonia. 20 C), rinsed with 70 C water and subsequent-
ly with cold water, acidified, rinsed again, and
ISO 105-S03: Colour Fastness to Vulcani- dried. The change in color of the specimen and
zation: Open Steam (¼ DIN 54 066-S03: Bes- the staining of the cotton adjacent fabric are
timmung der Heißdampfvulkanisierechtheit von assessed with the gray scales. Completely resis-
F€arbungen und Drucken). A specimen of the tant specimens may show an apparent increase in
textile is heated in live steam in direct contact depth of color. In such cases an assessment of 5
with an (initially) unvulcanized rubber com- cannot be given; the fastness number is marked
pound – the textile material being wrapped in by an asterisk, which must be explained in a
either footnote.
1. Sheeting impermeable to steam and water ISO 105-X05: Colour Fastness to Organic
(Method A) or Solvents (¼ DIN 54 023-X05: Bestimmung
2. Undyed bleached cotton cloth, but ensuring der L€osemittelechtheit von F€arbungen und
that live steam is not prevented from infiltra- Drucken). A specimen of the textile in contact
tion into the specimen (Method B) with adjacent fabrics is agitated in the solvent and
dried. The change in color of the specimen and
The change in color of the specimen and the the staining of the adjacent fabrics are assessed
staining of the adjacent fabric are assessed with with the gray scales.
the gray scale.
ISO 105-X06: Colour Fastness to Soda
Boiling (¼ DIN 54 031-X06: Bestimmung der
13.2.11. Group X: Colour Fastness to Sodakochechtheit von F€arbungen und Drucken).
Miscellaneous Agencies A specimen of textile between specified undyed
cloths is rolled around a glass rod and treated with
ISO 105-X01: Colour Fastness to Carbon- boiling sodium carbonate solution for 1 h with
izing: Aluminium Chloride (¼ DIN 54 044- and without the addition of a reduction inhibitor.
X01: Bestimmung der Karbonisierechtheit von The composite specimen is rinsed and dried. The
F€arbungen und Drucken mit Aluminiumchlorid). change in color and the staining of the undyed
A specimen impregnated with aluminum chlo- cloths are assessed with the gray scales.
ride solution is dried, baked (15 min at 115 C),
rinsed, and neutralized. The method is applicable ISO 105-X07: Colour Fastness to Cross-
mainly to wool and textiles containing wool. The Dyeing: Wool (¼ DIN 54 049-X07: Bestim-
changes in color after rinsing, neutralizing, and mung der Überf€arbeechtheit von F€arbungen und
drying are assessed with the gray scale. Drucken). Specimens of the textile in contact
with adjacent fabrics are treated in different types
ISO 105-X02: Colour Fastness to Carbon- of wool dyebaths, but without any dye. The
izing: Sulphuric Acid (¼ DIN 54 045-X02: change in color of the specimen and the staining
Bestimmung der Karbonisierechtheit von of the adjacent fabrics are assessed with the gray
F€arbungen und Drucken mit Schwefels€aure). A scales.
specimen impregnated with sulfuric acid solu-
tion is dried, baked (15 min at 105 C), rinsed, ISO 105-X08: Colour Fastness to Degum-
and neutralized. The method is applicable mainly ming (¼ DIN 54 055-X08: Bestimmung der
to wool and textiles containing wool. The Entbastungsechtheit von F€arbungen und Druck-
changes in color after rinsing, neutralizing, and en). A specimen of the textile in contact with
drying are assessed with the gray scale. adjacent fabrics is treated with a soap solution,
Vol. 36 Textile Dyeing 311
similar to those used in degumming raw silk, then Reibechtheit von F€arbungen und Drucken).
rinsed, and dried. The change in color of the Specimens of the textile are rubbed with a dry
specimen and the staining of the adjacent fabrics rubbing cloth and with a wet rubbing cloth in a
are assessed with the gray scales. suitable testing device. Two alternative sizes
of rubbing finger are specified. The staining of
ISO-105-X09: Colour Fastness to Formal- the rubbing cloths is assessed with the gray
dehyde (¼ DIN 54 061-X09: Bestimmung der scale.
Formaldehydechtheit). A specimen of the textile
is exposed in a closed container to the action of ISO 105-X13: Colour Fastness of Wool
gaseous formaldehyde (24 h at 20 C). The Dyes to Processes using Chemical Means for
change in color of the specimen is assessed with Creasing, Pleating, and Setting (no DIN
the gray scale. standard). A specimen of the textile, treated
with the chemical solution, is placed in contact
ISO 105-X10: Assessment of Migration with specified adjacent fabrics and subjected to
of Textile Colours into Polyvinyl Chloride steam pressing. A comparison specimen, not
Coatings (¼ DIN 54 072-X10: Bestimmung treated with the chemical solution, is steam
der Echtheit von F€arbungen und Drucken pressed simultaneously. The specimens are
gegenüber PVC-Weichmachern). A specimen dried, and any differences between the colors
of a textile impregnated with plasticizer is of the two specimens and the staining of the
brought into contact with a white-pigmented adjacent fabrics are assessed with the gray
poly(vinyl chloride) film and kept under pres- scales.
sure for 3.5 h at 80 C. Then the specimen and
excess plasticizer are removed from the film, ISO 105-X14: Colour Fastness to Acid
and the staining of the film is assessed with the Chlorination of Wool: Sodium Dichloroiso-
gray scale. cyanurate (no DIN standard). A specimen of
the textile is treated in a formic acid buffer
ISO 105-X11: Colour Fastness to Hot solution to which solutions of sodium dichlor-
Pressing (¼ DIN 54 022-X11: Bestimmung oisocyanurate and sodium hydrogensulfite are
der Bügelechtheit von F€arbungen und Drucken). added successively, and is then rinsed and dried.
Three methods are described; in each method, hot The change in color of the specimen is assessed
pressing is performed for 15 s at 110, 150, or with the gray scale.
200 C:
a b
Parameter 38. VwV from 1984 Appendix 38, generally Appendix 38, state of the
accepted technological art c
conventions
establish and enforce quality standards for waters selection of Japanese wastewater standards for
[456], [457]. direct discharge is given below [458]:
A compilation of the requirements to be met Table 21. Typical wastewater of a cotton finisher [446]
for the discharge of some important substances
Parameter Average Minimum Maximum
into public-owned treatment plants in various
countries is given in Table 20 [457], [459]. pH 8.5 10.3
Conductivity, mS/m 650 420 1400
Temperature, C 27 25 38
COD, mg/L 650 420 1400
14.3. Components of Textile BOD5, mg/L 180 80 500
Wastewater Phosphate (as P), mg/L 50 26 80
Sulfate, mg/L 810 750 1050
Ammonium (as N), mg/L 0.7 0.6 1.0
The composition of textile wastewater depends Hydrocarbons, mg/L 5 3 15
to a large extent on the dyed substrates, dyes, Chloride, mg/L 800 400 1500
textile auxiliaries, and chemicals used, which AOX, mg/L 0.8 0.5 1.2
Settleable substances, mg/L 10 1 150
makes the statement of average values impossi- Copper, mg/L < 0.1 < 0.1 0.6
ble. As a rule, untreated textile wastewater has Chromium, mg/L < 0.01 0.015 0.034
an alkaline pH, a higher temperature, high con-
ductivity, and a poorer BOD5 : COD ratio (i.e.,
lower degradability) compared to domestic per gram and is due partially to the catalysts used
wastewater. Typical BOD5 : COD values lie in production [459].
between 1 : 2.5 and 1 : 5 [455]. The organic load Depending on the coloristic class, dyes are
of the wastewater originates largely from pre- fixed in various quantities (see below) [447]:
treatment of the materials – BOD5 values of up
to 140 kg O2 per tonne of material being ob- Direct dyes 70 – 95 %
tained for desizing and 210 kg/t in the case of Vat dyes 80 – 95 %
Sulfur dyes 60 – 70 %
alkaline boiling out of polyester – cotton blend Reactive dyes 50 – 95 %
fabrics [461], [462]. Wastewater from dye- Disperse dyes 80 – 92 %
houses, which work primarily with sulfur or vat Acid dyes 80 – 93 %
dyes, have high COD values because of the Afterchroming dyes 98 – 99 %
Cationic (basic) dyes 97 – 98 %
organic or inorganic reducing agents (glucose,
hydroxyacetone, sodium dithionite) used. An
analysis of the wastewater from a cotton finisher Nevertheless, their share (ca. 1 – 2 %) of the
is shown in Table 21. organic wastewater load is very low [466].
The contaminants, which are controlled on
discharge into the public sewage system or into 14.4. Reduction of Wastewater Load
surface water, can have many different sources by Special Preventive Measures
(Table 22) [459], [461], [463–465]. Apart from
metal complexes, the heavy-metal content in If certain requirements are not fulfilled, the
dyes is usually in the range of a few micrograms wastewater must be treated or the discharge of
Vol. 36 Textile Dyeing 315
Table 22. Important sources of contaminants in wastewater from grams [469]. In the case of copper- containing
dyehouses
metal- complex dyes, these methods result in the
Parameter, contaminant Source lowering of an increased copper concentration.
The complete avoidance of metal complexes,
Alkaline pH value dyeing with reactive, vat, and
sulfur dyes; mercerization, which are employed for some violet, blue, navy
boiling-off, bleaching blue, and black shades in direct and reactive
Acidic pH value dyeing with basic, acidic, and dyes, results in marked losses in lightfastness.
disperse dyes; easy care finish Turquoise and brilliant green shades can be
Color reactive and sulfur dyes
Heavy metals produced only with copper or nickel phthalocy-
Chromium metal-complex dyes, oxidant anine complex dyes.
Cobalt metal-complex dyes In padding processes, a general problem is the
Copper metal-complex dyes, pig- unused dye liquor in the pad-trough, piping, and
ments, improvers of
lightfastness dissolving tank. Better utilization of dye liqour
Nickel metal-complex dyes can be achieved by using padders with a smaller
Zinc cationic dyes, resist and content [470] or by reusing the remaining liquor
reducing agents, biocides, in other dyeing processes, which requires colori-
catalysts, water piping
Antimony flame retardant metric determination of the correct formulation
Tin biocides in the laboratory [471]. With reactive dyes,
Halogenated hydrocarbons detergents, degreasers, however, reuse is limited because the liquors are
carrier, chlorine bleaching not stable for long in the presence of fixing alkali.
AOX dyes, carrier, chlorine
bleaching, preservatives, In the wastewater from wool dyeworks, in-
mothproofers, wool creased chromium concentrations are frequently
chlorination encountered. They are caused by chromium met-
Mineral oils yarn preparations, spinning al- complex dyes and/or by the chroming of
oils, defoamers, dedusting
agents, print thickening chrome dyes. To lower chromium concentration,
Phosphorus, phosphates buffers, sequestrants, flame optimized chroming methods have been devel-
retardants oped. In fact, chromium concentrations in resid-
Sulfide sulfur dyes ual liquors have been reduced from 20 –
Neutral salts reactive and substantive
dyeing 150 mg/L in the case of traditional dyeing to
1 – 6 mg/L. Thus, the concentrations lie below
those obtained on black dyeing with 1 : 2 metal-
complex dyes, which can have up to 13 mg/L of
chromium [472], [473]. Optimized chroming
the contaminants in question must be lowered or methods include the International Wool Secre-
completely eliminated. As a rule, preventive tariat (IWS) low-temperature chrome dyeing
measures are more economical than subsequent method at 90 C with the addition of thiosulfate,
contaminant elimination. The discharge of a the Bayer Glauber’s salt technique with dye-
number of the contaminants listed in Table 22 specific chrome factors, and the Sandoz method
can be reduced or eliminated by process changes with minimum chrome factors and a special
or exchange of products. Residual color from auxiliary agent.
reactive dyes can be reduced by using dyes with a The bleaching of cotton with hypochlorite is
higher fixing yield (i.e., with more affinitive, an important source of absorbable organic halo-
bifunctional, or bireactive dyes [467]). Higher gen (AOX). In laboratory experiments with raw
yields are also achieved by a shorter liquor ratio cotton, the AOX detected in the bleaching liquor
or by using continuous or semicontinuous pro- was up to 30 mg/L and, in the case of desized
cesses instead of exhaustion processes [468]. materials, up to 80 mg/L. In addition, up to
Another possibility is the use of higher salt 11 mg/L of chloroform can be formed by a halo-
concentrations, which, however, stand in the way form reaction during hypochlorite bleaching un-
of the demand for lower electrolyte concentra- der standard conditions. In contrast, bleaching
tions in wastewater. From an economic view- with sodium chlorite or hydrogen peroxide gives
point, optimization of the formulation can be ca. 10 or less than 0.5 mg/L AOX, respectively
achieved by means of suitable computer pro- [474], [475]. The transition to bleaching with
316 Textile Dyeing Vol. 36
hydrogen peroxide can reduce both AOX content dyeing of cotton velvet with direct dyes. Polyam-
and free chlorine in the wastewater. ide can be dyed with acid dyes, acrylic fibers with
Phosphorus enters wastewater largely via cationic dyes, and polyester with disperse dyes in
buffer substances or sequestering agents. Al- a standing bath [466], [477]. Multiple use of the
though some countries have already installed residual liquors from finishing processes should
stages for phosphate elimination in sewage treat- also be aimed at. However, the possible staining
ment plants, a reduction is desirable because of of the padding liquors with dyes, the correct
the possibility of eutrophication of surface analysis of present composition, and the storage
waters. Apart from the use of phosphorus-free stability can cause problems [478]. The advan-
substances, an alternative to phosphorus com- tages of reuse are reduced organic load of the
pounds as buffers is dosing with acids or bases via wastewater and savings of water, heating energy,
automatic dosing equipment. As sequestering and, in part, auxiliary agents and chemicals.
agents and peroxide stabilizers in peroxide Water consumption can also be decreased by
bleaching, polyhydroxy carbonates, aminocar- using dyeing equipment with shorter liquor ratios
boxylates [e.g., ethylenediaminetetraacetate [479] (see Section 14.1), optimized process oper-
(EDTA) or nitrilotriacetate (NTA)], phospho- ation (e.g., washing in reactive dyeing [480]), and
nates or modified polyacrylates are used instead a series of other measures [466].
of phosphorus compounds [476]. However,
EDTA should not be used because it is poorly
biodegradable and can remobilize heavy metals 14.5. Special Methods of Wastewater
from the sediment. The use of sequestering Treatment
agents can be almost avoided by performing an
extraction step with formic or hydrochloric acid The usual methods of wastewater treatment can
before bleaching, eliminating hardness and hea- also be applied to the textile finishing industry. A
vy metals from the material. special case is, however, the removal of dyes.
In reactive dyeing, the use of salt can be Apart from paper dyeing, the presence of dyes in
avoided when continuous or semicontinuous wastewater to this extent is specific to the textile
processes are used instead of exhaustion process- industry.
es. In the case of reactive dyes that have a low salt
sensitivity, the amount of salt can be lowered Biological Treatment. As mentioned in
without yield losses [469]. Sulfites and sulfates Section 14.3, textile wastewater is frequently
are also formed in the oxidation of sodium poorly biodegradable. This is of minor impor-
dithionite (hydrosulfite), which is used both as tance if textile wastewater represents a relatively
a stripping agent for faulty dyeing and for reduc- small part of the total wastewater of a municipal
tion of vat dyes. Thiourea dioxide or reductones biological sewage treatment plant. Nevertheless,
such as hydroxyacetone are alternatives to hy- textile wastewater can be subjected satisfactorily
drosulfite. The disadvantages of both chemicals to biological treatment even if it is not mixed with
are overreduction in the case of vat dyes of the municipal wastewater. Because of the different
indanthrone type and changes in shade [477]. textile processing program, textile wastewater
Hydroxyacetone, which is easily degradable, is has a complex and rapidly changing composi-
being used increasingly in indigo dyeing. Sulfide tion. For this reason, preceding equalization of
formed when dyeing with sulfur dyes must be composition in adequately dimensioned balanc-
oxidized before discharge. The use of low-sulfur, ing tanks is required for optimal purification. In
prereduced dyes, which are reduced by glucose, addition, a certain temperature compensation is
lowers the electrolyte load and avoids the re- achieved, extreme pH values are avoided by
quired sulfide oxidation [471]. internal neutralization, etc. The balancing tanks
also eliminate the need for design of the treat-
Multiple use of Exhausted Dye Liquors is ment plant based on maximum wastewater va-
usually restricted to dyes with high exhaustion lues, serve charge of the biological treatment
yield and exhibit low interactions with the aux- plant on work-free weekends, and represent safe-
iliaries remaining in the liquor. Examples are the ty stages in case of breakdown. The COD value of
dyeing of cotton with indigo or sulfur dyes and the wastewater has been reported to be reduced
Vol. 36 Textile Dyeing 317
almost 50 %, and the mineral oil concentration by tionic precipitating agents are used. With dyes
70 %, by appropriate design of the balancing containing sulfonic acid groups, these agents
tank, introduction of adapted microorganisms, form compounds that are poorly soluble in water
and additional aeration [481]. The pilot plant and and flocculate [461], [468], [496–498]. In both
the operation of a one-stage aerated biological cases, the sludge can be separated by flotation or
sewage treatment plant run by the finisher of sedimentation.
cotton and blended fabrics are described in
[482]. Adaptation of microorganisms in the Oxidation. The disadvantage of precipita-
one-stage plant was shown to considerably im- tion and flocculation is the production of large
prove treatment efficiency in comparison with amounts of sludge, which must be treated and
the pilot plant and the results at the start of disposed of. Chemical processes, especially oxi-
operation. Biological treatment plants can be dation and reduction, usually do not have this
improved by combination with preceding or disadvantage. The oxidizing agents used in prac-
subsequent precipitation – flocculation [483], tice or in research projects for the treatment of
[484] and addition of activated carbon or cheaper textile wastewater (especially for the removal of
brown- coal cokes in the activated sludge part residual color) are chlorine [487] or hydrogen
[485–487]. Pilot experiments on the decoloriza- peroxide, the latter usually together with iron(II)
tion of the outflow from a biological sewage sulfate (Fenton’s reagent) [499–501], ozone
treatment plant using an activated carbon [502–504], or UV irradiation [505], [506]. A
fixed-bed reactor show a bacterial degradation combination of ozone and UV irradiation also
of the dye, which occurs in addition to purely exists. The disadvantage of chlorination is the
adsorptive processes [488]. Highly loaded waste- formation of organic chloro compounds.
water (e.g., partial streams from pretreatment and Fenton’s reagent effectively destroys water-
desizing), is very suitable for anaerobic treat- soluble dyes. However, it also nonspecifically
ment. Partial streams from dyeworks are not oxidizes organic pollutants expressed as COD,
easily degradable anaerobically, especially in the leading to a high consumption of peroxide and
presence of better degradable substrates [489], correspondingly high costs. Ozone reacts specifi-
[490]. cally with dyes, especially at neutral and acidic
pH. Thus, other water components such as sur-
Precipitation – Flocculation. Chemical factants and thickeners are hardly attacked.
precipitation – flocculation belongs to the gen- Wastewater treated with oxidizing agents shows
erally accepted technological conventions and is better degradability and a lower toxicity for bac-
used for extensive wastewater treatment in many teria. The reaction products of ozone treatment
branches of industry. The advantages are in- include saturated and unsaturated carboxylic
creased elimination of contaminants, easy com- acids (e.g., oxalic, malonic, maleic, and phthalic
binability with other processes, and relative in- acids) [507]. For the special treatment of waste-
sensitivity of these processes to substances that water from sulfur dyeing, see Section 4.5.6.
are toxic for bacteria and to fluctuations in
wastewater composition [491]. The usual inor- Reduction. Sodium dithionite is the agent of
ganic precipitating agents are lime, aluminum choice for reductive decolorization. Under suit-
and iron salts [e.g., iron chloride sulfate, iron(II) able reaction conditions, not only azo dyes but
and iron(III) chloride]. Instead of direct dosing also dyes based on other chemical structures (e.
into the wastewater, electrochemical production g., anthraquinone or formazane dyes) [461],
of the metal cations or their hydroxides by cor- [508] can be permanently reduced. Treatment
responding sacrificial electrodes is possible. with iron(II) sulfate – lime, which uses the re-
Apart from reducing the contaminant load (COD, duction potential of divalent iron, represents a
BOD, heavy metals, and mineral oils), dyes are combination of reduction and precipitation. This
also eliminated, at least partially. These dyes stage precedes the biological wastewater treat-
include vat, disperse, sulfur, direct, and acid ment plant [509]. Divalent iron ions can be
dyes, as well as pigments [492–495]. Reactive produced electrochemically on activated iron
dyes are not adequately removed by the usual electrodes, which can also reduce hexavalent
inorganic precipitants. For this purpose, polyca- chromium from wool dyeing [473]. Both direct
318 Textile Dyeing Vol. 36
and indirect cathodic dye reduction [i.e., via an line than permitted for discharge. Apart from
iron(II) – iron(III) – triethanolamine redox sys- strong acids such as sulfuric or hydrochloric acid,
tem] is possible by electrolysis with higher cur- CO2 is also well suited to neutralization and can
rent strengths [510]. In purely chemical methods be used in the pure state [516] or as a component
of treatment, which proceed without the use of of flue gas [517]. In comparison with mineral
precipitants, no elimination of heavy metals (e.g., acids, the advantages of neutralization with CO2
from metal- complex dyes) occurs. are lower chemical costs, less material corrosion,
no salting, and more safety in dosing.
Adsorption. The most important adsorbent
in wastewater treatment is activated carbon. A
distinction is made between the stirring process
with powdered carbon and the percolation pro-
14.6. Recycling of Water and Valuable
cess with granulated carbon [455], [466], [487], Substances
[511]. The former has already been mentioned in
connection with biological treatment. Besides Recycling of Water. Because of high costs
the actual adsorption, biological processes (i.e., for treatment or discharge of industrial and
combinations of aerobic and anaerobic degrada- wastewater, reuse of water occasionally appears
tion) also play an important role. Apart from reasonable. The multiple use of dye liquors was
water-soluble dyes, polar substances are prefer- mentioned in Section 14.4. Similarly, slightly
entially adsorbed to activated carbon. As a result loaded rinsing baths can be reused in many cases
of the limited adsorption capacity and high cost, without previous treatment. For universal appli-
activated carbon should be used preferably for cability, however, purification, usually a combi-
the treatment of less loaded wastewater (e.g., in nation of several processes, is required. Some of
fine purification for reuse or as safety filters). these are given below:
Cheaper adsorbents under investigation are cok-
ing coal, peat, kieselguhr, activated alumina, 1. Weakly loaded wastewater
clay, chitin, and other natural substances. Syn- Powdered activated carbon
thetic polymers and ion exchangers are suited to Polyaluminum chloride precipitation and
the separation of polar and nonpolar water com- sedimentation
ponents. As with activated carbon, periodic re- Multilayer filter [518]
generation is required [487]. For the selective 2. Total wastewater
separation of heavy-metal cations, AOX, and Charcoal-supported biology in stirred loop
dyes by polymeric diaza crown ethers, cyclodex- reactor
trins, calixarenes, and curcubituril, see [512], Adsorption in stirred loop reactor on pulver-
[513]. ized brown coal
Polyaluminum chloride precipitation and
Membrane Separation. The separation of sedimentation
contaminants by using membrane techniques Fixed-bed filtration with granulated brown
(e.g., reverse osmosis, nano- or ultrafiltration) coal [486], [519]
results in no final decrease in contamination.
Concentrates with the separated contaminants 3. Total wastewater, mainly from reactive dyeing
must be treated further by using known techni- Precipitation with cationic precipitating
ques, while the clean permeates can be dis- agents and flotation
charged or reused in the plant [514], [515]. Fixed-bed filter with sand and brown coal
Membranes that are applied include those made [520]
of cellulose acetate, polyamides, and polysul- 4. Wastewater from polyester dyeing
fones, and the robust, dynamic membranes made Electrocoagulation
of zirconium(IV) hydroxide – polyacrylates on Filtration [494]
porous ceramic or steel carriers [487].
5. Total wastewater
Neutralization. Textile wastewater must be Precipitation – flocculation – filtration
neutralized since the pH is frequently more alka- Nanofiltration [521]
Vol. 36 Textile Dyeing 319
Toxicity for Warm-Blooded Animals and ing health is very low. An exception is the risk of
Occupational Health. In general, dyes have a allergies, which exists for a few dyes. In com-
low toxicity for warm-blooded animals. Of 4500 parison with worldwide dye consumption, the
tested commercial products, 82 % had an LD50 number of skin allergies due to dyes is negligibly
(rat, oral) of > 5000 mg/kg and < 1 % had a small [553]. The dyes with increased allergic
value of < 250 mg/kg [546]. According to the potential are essentially those listed below
ChemG, only 13 known textile dyes are consid- [554–556].
ered toxic (LD50 < 200 mg/kg oral and LC50
< 25 mg/m3 inhalation), several of which are no Colour Index Dye class
longer produced [547]. Studies on rats to deter- Disperse Yellow 1, 9 nitro dye
mine the subchronic toxicity of eight commercial Disperse Yellow 39, 49 methine dye
products with an LD50 > 2000 mg/kg showed no Disperse Yellow 54, 64 quinoline dye
Disperse Orange 1, 3, 76 azo dye
measurable effects in the case of 22 daily doses Disperse Red 11, 15 anthraquinone dye
during 28 days of 1000 mg/kg each [548]. A Disperse Red 1, 17 azo dye
carcinogenic effect of 13 textile dyes, mainly Disperse Blue 1, 3, 7, 26, 35 anthraquinone dye
azo dyes, has been detected in animal experi- Disperse Blue 102, 106, 124 azo dye
Acid Violet 17 azo dye
ments [548–550]. In metabolism, aromatic
amines may be formed by the enzymatic reduc-
tive cleavage of azo dyes. According to a rec- In textile dyehouses, especially in dyeing
ommendation of the German MAK Commission kitchens, additional exposure to inhalable dust
(1988), azo dyes that release carcinogenic ary- should be considered. Apart from skin irritation,
lamines of the MAK groups III A 1 and III A 2 respiratory or nasal problems and itching of the
under reductive conditions should be treated like eyes can occur, especially due to reactive dyes.
the released amines themselves. In the GefStoffV Remedial action can be taken by means of good
[551], this recommendation led to consequences occupational hygiene and dust-free working con-
with regard to classification, labeling, packaging, ditions [557], [558], [559].
and contact in the factory. The important repre-
sentatives involved are dyes based on benzidine
and its congeners. The members of the Ecologi- References
cal and Toxicological Association of the Dye-
stuff and Pigment Industry (ETAD) have agreed 1 H. Vogler, Textilveredlung 27 (1992) 352 – 358.
voluntarily to neither produce nor market benzi- 2 S. M. Edelstein, H. C. Borghetty: The Plictho of Gioan-
dine dyes. Up to now the use of benzidine dyes ventura Rosetti, The MIT Press, Cambridge – London
and the importation of textiles dyed with them 1969.
have been banned only in Sweden. In India, the 3 Ullmann, 4th ed. 11, 99 – 134.
4 H. Schweppe: Handbuch der Naturfarbstoffe, Vorkom-
production of benzidine dyes has been banned men, Verwendung, Nachweis, Ecomed Verlag, Lands-
since February 1993. In Germany, the sale of berg 1993.
textiles dyed with dyes that are able to cleave 5 Kirk-Othmer, 3rd ed., 8, 351 – 373.
under formation of carcinogenic amines and can 6 F. Brunello: The Art of Dyeing in the History of Mankind,
come into contact with skin will be banned from Neri Pozza, Vicenza 1973, English Translation by Phoe-
January 1996 on (2nd and 3rd Ordinance for nix Dyeworks, Cleveland, OH.
Amendment of Consumer Goods Ordinance 7 G. Fieler: Farben aus der Natur, Eine Sammlung alter
from July 15, 1994, BGBl. 1670 – 1671, and und neuer F€arberezepte für das F€arben auf Wolle, Seide,
Baumwolle und Leinen, M. H. Schaper, Hannover 1978.
from December 16, 1994, BGBl. 3836). Benzi- 8 R. J. Adrosko: Natural Dyes and Home Dyeing, a
dine and its metabolites could be detected in the Practical Guide with over 150 Recipes, Dover Publ.
urine of workers who had contact with benzidine Inc., New York 1968.
dyes and had inhaled their dust. In plants with a 9 E. Bemiss: The Dyers Companion, vol. 2, New London
high standard of industrial hygiene, the results 1806, 3rd. enlarged ed. New York 1973. C. G. Gilroy: A
were negative [552]. Practical Treatise on Dyeing and Calico-printing, 2nd
In the case of fast dyeing – since the migration ed., New York 1846.
of dyes on and through the skin is estimated at 10 P. Richter, Wirkerei- Strickereitech. 40 (1990) no. 3 to
41 (1991) no. 10.
most at a few micrograms – the risk of endanger-
Vol. 36 Textile Dyeing 321
kontinuierlich arbeitend,’’ Text. Prax. Int. 48 (1993) Hochveredlung von Zellulose,’’ Melliand Textilber. 11
131 – 132. (1972) 1278 – 1289.
50 MCS: ‘‘Neue Strangf€arbemaschine,’’ Melliand Textil- 70 H. Paulsen: ‘‘Energiebilanzen in der Textilveredlung,’’
ber. 74 (1993) 566. Melliand Textilber. 74 (1993) 550 – 556.
51 ‘‘ADR’s Annual Buyers’ Guide to Garment Dyeing/ 71 S. M. Burkinshaw, W. J. Marshall: ‘‘Continuous Dyeing
Washing Machinery and Stone/Chemical Suppliers,’’ of Piece Goods Using Radiofrequency Heating,’’ part I,
Am. Dyest. Rep. 82 (1993) no. 5, 38 – 45. J. Soc. Dyers Colour. 102 (1986) 263 –268.
52 Thies: ‘‘Trommelf€arbeapparat für Fertigkonfektion,’’ 72 P. Lennox-Kerr: Int. Dyer Text. Printer Bleacher Finish.
Melliand Textilber. 67 (1986) 723. 171 (1986) 20 – 21.
53 J. Park: ‘‘Developments in Dyeing Process Control,’’ 73 U. Einsele: ‘‘Neuere Methoden zum F€arben von Poly-
Rev. Prog. Color. Relat. Top. 15 (1985) 1 – 5. propylen – 1. Mitteilung: F€arben mit Hilfe von Binde-
54 On-Line-Steuerungen in der Textilveredlung, lecture mitteln,’’ Melliand Textilber. 72 (1991) 847 –851.
held at Fachhochschule Reutlingen. 74 W. Rüttiger: ‘‘Das Ausnutzen des Waschwirkungs-
55 W. Rüttiger, P. Toldrian: ‘‘Einheitliche Verfahrensdar- grades – eine Einführung in das Beherrschen von
stellung zur Automatisierung und Optimierung der char- Waschprozessen,’’ Text. Prax. 34 (1979) 1380 – 1387,
genweisen F€arbung,’’ Text. Prax. 27 (1972) 674 – 678, 1544 – 1551, 1629 – 1643.
719 – 722. 75 W. Rüttiger, U. Kirner: ‘‘Die Geschwindigkeit des
56 Sepa: ‘‘Offene Prozessleittechnik für die Textilvere- Wasserstoffperoxide-Eigenzerfalls als wichtige verfah-
dlung,’’ Text. Prax. Int. 47 (1992) 674. renstechnische Kenngr€oße in der Textilveredlung,’’
57 J. H. Heetjans: ‘‘Handhabungs- und Transportsysteme in Text. Prax. 25 (1970) 21 – 30.
der Garnf€arberei,’’ Chemiefasern/Textilindustrie 39/91 76 D. W. Ravensberger, R. B. M. Holweg: ‘‘Monitoring and
(1989). Control of Hydrogen Peroxide Dosing,’’ J. Soc. Dyers
58 G. Hofmann: ‘‘Automatisches Beschicken von Colour. 109 (1993) 72 – 75.
F€arbeapparaten und Garnveredlung,’’ Chemiefasern/ 77 BASF: Ratgeber Cellulosefasern, Schlichten, Vorbe-
Textilind. 42/94 (1992) 61 – 63. handeln, F€ arben, Verlag BASF AG, Ludwigshafen
59 J. Ehlert: ‘‘Rationalisierung in der Textilf€arberei,’’ 1977, p. 319, 357.
Deutscher F€ arberkalender 1971, Deutscher Fachverlag, 78 K. van Wersch: ‘‘Anlagen für das F€arben nach dem Pad
Frankfurt 1970. Batch-Verfahren,’’ Melliand Textilber. 73 (1992) 431 –
60 E. Voss: ‘‘Erfahrungen mit pH-Automaten für die 432.
F€arbung von Stück- und Konfektionsware, sehr hohe 79 U. Denter, E. Schollmeyer: ‘‘Verfahrensanalyse und
Ausziehgrade für Polyamid und Wolle in der Badf€ar- Entwicklung einer Testf€arbemethode für die Rezeptier-
bung,’’ Melliand Textilber. 74 (1993) 564 –566. ung der KKV-Reaktivf€arbung von Baumwollgeweben
61 K. Tiedemann, G. Grüninger, W. Rüttiger: ‘‘Methoden (AIF 7997),’’ Melliand Textilber. 74 (1993) 251.
zur On-Line-überwachung der Wasserstoffperoxidkon- 80 Suderba: ‘‘Space-dyeing-Maschine für sechs Farben,’’
zentration für die Bleiche und Küpenf€arbung,’’ Text. Prax. Int. 48 (1993) 1006.
Deutscher F€ arberkalender 1993, Deutscher Fachverlag, 81 Carbonell: ‘‘Praxiserfahrungen beim Versuch, automa-
Frankfurt 1992, pp. 140 – 172. tische Prozeß-Steuerungen auf die Erfordernisse einer
62 H. Fuchs: ‘‘Erkenntnisse beim einbadigen Pigmentf€ar- computerintegrierten Fertigung umzugestalten,’’ Text.
ben und Ausrüsten,’’ Text. Prax. Int. 49 (1994) 507 – Prax. Int. 47 (1992) 468 – 472.
510. 82 Qualico: ‘‘Schnellste kontinuierliche Feuchtekontrol-
63 W. Kambach: ‘‘Kontinuierliches Aufwickeln von Tex- len,’’ Text. Prax. 48 (1993) 247.
tilbahnen zu Großkaulen,’’ Text. Prax. Int. 48 (1993) 83 J. Rieker, T. Guschlbauer: ‘‘Farbabl€aufe in der Kon-
36 – 38. tinue-F€arberei und Materialdichteunterschiede in Gewe-
64 A. Günther: ‘‘Geringere Abwasserbelastung durch neue ben – Kann die On-Line-Farbmessung helfen?’’ Mel-
Konstruktionen bei Teppich-, F€arbe- und Druckanla- liand Textilber. 74 (1993) 1256 –1260.
gen,’’ Text. Prax. Int. 48 (1992) 848 –852. 84 W. Rüttiger: ‘‘Meßwerte im Computer für die Vere-
65 Farmer Norton: ‘‘Neues Vakuum-Flottenauftragssys- dlungspraxis,’’ Text. Prax. 41 (1986) 555 – 562, 776 –
tem,’’ Text. Prax. Int. 48 (1993) 129 – 130. 781.
66 J. Polster: ‘‘Foulardtechnik – tema con variazioni,’’ 85 O. Annen, H. Gerber: ‘‘Probleme bei der übertragung
Melliand Textilber. 74 (1993) 1173 – 1174. von Laborergebnissen in die Praxis,’’ Melliand Textil-
67 K. van Wersch: ‘‘Kontrollierte Applikation von ber. 75 (1994) 406 – 411.
F€arbeflotten,’’ Textilveredlung 28 (1993) 218 – 223. 86 Roaches: ‘‘Neue infrarotbeheizte Laborf€arbemaschinen
68 P. Salzmann, W. Schindler: ‘‘Die gemeinsame Applika- entwickelt,’’ Text. Prax. Int. 48 (1993) 131.
tion von Küpenfarbstoff und Reduktionsmittel beim 87 ‘‘ITMA 91 – Labor- und Musteranlagen für die Tex-
Kontinuef€arben ohne Zwischentrocknung,’’ Melliand tilveredlung,’’ Melliand Textilber. 73 (1992) 180 –
Textilber. 74 (1993) 525 – 529. 183.
69 W. Rüttiger, W. Rümens, G. Burkhardt, H. Petersen: 88 J. Oegarra: ‘‘On-Line-Qualit€atskontrolle bei der Aus-
‘‘übersicht der industriellen Verfahrenstechniken der ziehf€arbung,’’ Melliand Textilber. 74 (1993) 538 – 549.
Vol. 36 Textile Dyeing 323
89 K. Stommel: ‘‘Einsatz von Laborger€aten in der Textil- 109 H. G. Dejong: ‘‘Yarn-to-yarn Friction in Relation to
veredlungsindustrie,’’ Melliand Textilber. 45 (1964) some Properties of Fiber Materials,’’ Text. Res. J. 63
283 – 286. (1993) 14 – 18.
90 O. Annen, H. Gerber, B. Seuthe: ‘‘Das F€arbeverhalten 110 G. Bühler: ‘‘Garnreibwerte. Ein altes, jedoch immer
von Viskose- und Modalfasern im Vergleich zu noch nicht ganz bew€altigtes Problem in der Praxis der
Baumwolle,’’ J. Soc. Dyers Colour. 108 (1992) Maschenwarenherstellung,’’ TPI Text. Prax. Int. 48
215 – 261. (1993) 108 – 113.
91 E. Floegel: Statistik in BASIC, Hofacker-Verlag, Holz- 111 P. Offermann, G. Putzger: ‘‘Qualit€atsanalyse im Garn-
kirchen 1986. veredlungs- und textilen Fertigungsprozeß,’’ Melliand
92 M. Warmes: ‘‘The Central Dye Preparation Station – A Textilber. 74 (1993) 237 – 242.
Necessity for an Efficient Process Cycle in the Dye- 112 U. Scholze, J. Trauter: ‘‘Auswirkungen der Haarigkeit
house,’’ International Textile-Bulletin 2/82 (1982) . von Rohgarnen und der Fasereigenschaften auf das
93 Then: ‘‘Das Farbküchensystem AMC-CKM,’’ Text. Webverhalten geschlichteter Kettgarne (Part 1),’’ TPI
Prax. Int. 48 (1993) 1009. Text. Prax. Int. 48 (1993) 773 – 779.
94 H. P. Locher, M. Firmann: ‘‘Verbesserte Produktions- 113 J. P. Rust, S. Peykamian: ‘‘Yarn Hairiness and the
sicherheit in der Foulardf€arberei durch photometrische Process of Winding,’’ Text. Res. J. 62 (1992) 685 –689.
Kontrolle der Farbans€atze,’’ Textilveredlung 26 (1991) 114 TPI Text. Prax. Int. 48 (1993) 122.
393 – 398. 115 W. L€obel: ‘‘Weiterentwicklungen der Restfeuchtemes-
95 J. Rieker, U. Scherschel-Gaedke: ‘‘Zur Problematik der sung von Textilien nach dem konduktometrischen Ver-
photometrischen Bestimmung von Farbstoffkonzentra- fahren,’’ Melliand Textilber. 73 (1992) 771.
tionen in F€arbeb€andern,’’ Text. Prax. Int. 48 (1993) 116 W. Rüttiger: ‘‘Regel- und Steuerprobleme bei der kon-
980 – 982. tinuierlichen Textilausrüstung,’’ Melliand Textilber. 47
96 J. Rieker: ‘‘Labor- und Farbmessungen,’’ Melliand Tex- (1966) 552 – 559, 680 – 690.
tilber. 73 (1992) 258 – 261. 117 W. Rüttiger, G. Schmidt: ‘‘Krumpf und Verformung,
97 Datacolor: ‘‘Integrierte Farbdatenverarbeitung,’’ Che- zwei wesentliche Faktoren zur Gütesicherung von
miefasern/Textilind. 43/95 (1993) 70. Maschenware,’’ Melliand Textilber. 61 (1980) 526 –
98 K. van Wersch: ‘‘On-Line-Farbmessung in der Konti- 532.
nuef€arberei aus der Sicht des Maschinenbauers,’’ ITB 118 A. Eickmeier, U. Beller, D. Knittel, E. Schollmeyer:
Veredlung 36 (1990) no. 2, 21 – 42. ‘‘Untersuchungen von Polymeren im oberfl€achennahen
99 W. Pape: ‘‘Farbmessung in der Produktion,’’ Melliand Bereich mit dem Verfahren der Akustomikroskopie,’’
Textilber. 73 (1992) 152 – 155. TPI Text. Prax. Int. 48 (1993) 534 –536.
100 J. Rieker, E. Furthmüller: ‘‘Untersuchung der farbme- 119 L. Andrews: ‘‘Charakterisierung von Texturen gesch-
trischen Abmusterung mit Pass/Fail-Formeln,’’ Text. mirgelter Textilgewebe mit Hilfe der Statistik dritter
Prax. Int. 42 (1987) 422 – 423. Ordnung,’’ Melliand Textilber. 74 (1993) 231 – 233.
101 J. Rieker, K. Hilscher: ‘‘Über die visuelle Relevanz von 120 A. Lehnen: ‘‘Untersuchung der Zusammenh€ange
Farbstoffkonzentrationsunterschieden auf gef€arbten zwischen Ergebnissen der subjektiven Beurteilung von
Textilien,’’ Text. Prax. Int. 49 (1994) 499 –501. Teppichoberseitenstrukturen sowie deren Ver-€ander-
102 B. Wulfhorst, K. Meier: ‘‘Untersuchungen an einem ungszust€ande und optoelektronisch meßbaren Kennwer-
kurzen Hochtemperaturheizer,’’ Chemiefasern/Texti- ten,’’ TPI Text. Prax. Int. 48 (1993) 104.
lind. 43 (1993) no. 95, 40 – 45. 121 R. H. Peters: Textile Chemistry, vol. III, The Physical
103 Melliand Textilber. 74 (1993) 204. Chemistry of Dyeing, ‘‘Chapt. 2’’, Importance of Physi-
104 Y. G. Bryant: ‘‘Neue Fasern als temperaturgesteuerte cal Properties of Fibers, Elsevier, Amsterdam –Ox-
W€armefluß-Sperre,’’ Tech. Text. 35 (1992) T 88 – T 89. ford – New York 1975, pp. 23 – 26.
105 J. Gacen, D. Cayuela, J. Maillo, T. Rodriguez: ‘‘Einfluß 122 M. Peter, H.-K. Rouette: Grundlagen der Textilveredlung,
der thermischen Vorbehandlung auf die Feinstruktur von Handbuch der Technologie, Verfahren, Maschinen, 13th
thermofixiertem Polyester,’’ Melliand Textilber. 74 ed., Deutscher Fachverlag, Frankfurt 1989, ‘‘Chap. 5.1’’.
(1993) 797 – 801. 123 W. Albrecht: ‘‘Welche Bedeutung haben die physika-
106 H.-J. Flath, C. Scholz: ‘‘Charakterisierung zug€anglicher lischen Eigenschaften von Cellulosefasern für ihr
Strukturanteile in Cellulosefasern,’’ Melliand Textilber. F€arbeverhalten,’’ Melliand Textilber. Int. 51 (1970)
74 (1993) 219 – 221. 1437 – 1448.
107 W. Rüttiger: ‘‘Mechanische Zustands€anderungen von 124 H. Rath: Lehrbuch der Textilchemie, 3rd ed., ‘‘Chap.
Baumwolltextilien bei der Alkalikaltbehandlung, part 1: I. A. Chemie und Physik der Cellulose und ihrer Begle-
Grunderscheinungen der mechanischen Vorg€ange und itstoffe’’, Springer Verlag, Berlin 1972.
ihre Deutungsm€oglichkeiten über Faserstrukturmo- 125 W. Bubeth (ed.): Textile Faserstoffe – Beschaffenheit
delle,’’ Melliand Textilber. Int. 51 (1970) 1449 – 1465. und Eigenschaften, Springer Verlag, Heidelberg 1993.
108 R. V. Meyer, E. Haug, G. Spilgies: ‘‘Elastane – Chemie, 126 P. Richter: ‘‘F€arben von alkalisierten Polyesterfasern
Eigenschaften, Einsatzgebiete,’’ Melliand Textilber. 74 und Polyester-Microfasern,’’ Chemiefasern/Textilind.
(1993) 194 – 198. 41/93 (1991) 1118 – 1125.
324 Textile Dyeing Vol. 36
127 H. Gerber: ‘‘Kennwerte zur Charakterisierung des 147 D. Hildebrand, Text. Prax. Int. 25 (1970) 292 – 296,
f€arberischen Verhaltens von Reaktivfarbstoffen,’’ Tex- 351 – 354, 428 – 430, 492 – 495, 621 – 624; 26
tilveredlung 28 (1993) 405 – 411. (1971) 45 – 47, 431 – 433, 564 – 567.
128 M. Harris: Handbook of Textile Fibers, Textile Book 148 M. R. Fox, H. H. Sumner in C. Preston (ed.): The Dyeing
Publ., New York 1954. of Cellulose Fibers, Dyers’ Company Publications
129 W. Rüttiger: ‘‘Eine Zustandsgleichung für Cellulosefa- Trust, Bradford 1986, pp. 142 – 195.
sern als Erfassungsm€oglichkeit für L€angung, Krumpf, 149 P. Rys, H. Zollinger, Helv. Chim. Acta 49 (1966) 749 –
Knitterbildung und -erholung,’’ Textilveredlung 2 754.
(1967) 428 – 435. 150 J. P. Luttringer, P. Dussy, Melliand Textilber. 62 (1981)
130 D. Fiebig, H. Herlinger, B. Kastl: ‘‘Strukturver€anderun- 84 – 94.
gen bei Cellulosematerialien durch Netz-/Trockenpro- 151 A. H. M. Renfrew, J. A. Taylor, J. Soc. Dyers Colour.
zesse,’’ TPI Text. Prax. Int. 48 (1993) 789 – 794. 105 (1989) 441 – 445.
131 P. R. Brady: ‘‘Diffusion of Dyes in Natural Fibers,’’ Rev. 152 H. H. Sumner, T. Vickerstaff, Melliand Textilber. 42
Prog. Color. Relat. Top. 22 (1992) 58 – 78. (1961) 1161 – 1166.
132 B. Reichst€adter, O. Pajgrt: ‘‘Struktur und Eigenschaften 153 U. Ruf, W. B. Egger, Textilveredlung 13 (1978) 304 –
von Chemiefasern und Eigenschaften der fertigen Tex- 308.
tilien,’’ Chemiefasern Text. Anwendungstech. 20 (1970) 154 S. Abeta, K. Akahori, U. Meyer, H. Zollinger, J. Soc.
877 – 884. Dyers Colour. 107 (1991) 12 – 19.
133 P. Ehrler: ‘‘Pr€azisionsgewebe: Notwendigkeit verfah- 155 M. Matsui, U. Meyer, H. Zollinger, J. Soc. Dyers Colour.
renstechnischer Modifikationen,’’ Tech. Text. 35 (1992) 104 (1988) 425 – 431.
T 94 – T 97. 156 BASF, DE-OS 4 216 591, 1992. (J. Schulze et al.).
134 L. Vangheuwe: ‘‘Methode zur Bestimmung des dyna- 157 M. Peter, H. K. Rouette: Grundlagen der Textilvere-
mischen Moduls von Garnen,’’ Melliand Textilber. 74 dlung, 13th ed., Deutscher Fachverlag, Frankfurt a. M.
(1993) 717 – 718. 1989, pp. 510 – 516.
135 H. Grams: ‘‘Neues Websystem,’’ Melliand Textilber. 74 158 A. H. M. Renfrew, J. A. Taylor, Rev. Prog. Color. Relat.
(1993) 198 – 201. Top. 20 (1990) 1 – 9.
136 J. Rieker, W. Braun: ‘‘Kontinuierliche Messung von 159 D. M. Lewis, J. Soc. Dyers Colour. 109 (1993) 357 –
Kante/Mitte/Kante-Unterschieden an Webware nach 364.
dem Durchstr€omungsstaudruck-Prinzip,’’ Melliand Tex- 160 N. S. Knaggs, Am. Dyest. Rep. 81 (1992) no. 11, 109 –
tilber. 68 (1987) 749 – 752. 111.
137 D. H. Abrahams: ‘‘Reducing Cracks Creases Chafes,’’ 161 J. Shore, Rev. Prog. Color. Relat. Top. 21 (1991) 23 –42.
Am. Dyest. Rep. 63 (1974) no. 9, 32 – 36. 162 J. R. Aspland, Text. Chem. Color. 23 (1991) no. 12,
138 G. Heidemann, H.-J. Berndt: ‘‘Effektivtemperatur und 30 – 32.
Effektivspannung, zwei Meßgr€oßen zur absoluten Bes- 163 J. J. Porter, Text. Chem. Color. 25 (1993) no. 2, 27 –37.
timmung des Fixierzustandes von Synthesefasern,’’ 164 J. R. Aspland, Text. Chem. Color. 23 (1991) no. 11,
Melliand Textilber. 57 (1976) 485. 41 – 45.
139 G. Heidemann, H.-J. Berndt: ‘‘Die substrat- und pro- 165 M. I. Khalil, A. Bendak, S. S. Aggour, Am. Dyest. Rep. 70
zeßspezifischen Gr€oßen der Fixierung von Synthesefasern, (1981) no. 10, 31.
eine Analyse am Beispiel der Thermofixierung von Poly- 166 D. R. Lemin, E. J. Vickers, T. Vickerstaff, J. Soc. Dyers
esterfasern,’’ Chemiefasern/Textilind. 24/76 (1974) 46. Colour. 62 (1946) 132.
140 A. Kretschmer: ‘‘Grenzwerte der Flottenbeladung von 167 Report of the Commitee on Direct Dyes, J. Soc. Dyers
fl€achigem Textilgut beim Foulardieren,’’ Text. Prax. 25 Colour. 62 (1946) 280 – 285; 64 (1948) 145 –146.
(1970) 217 – 218. 168 J. Varghese, N. Bhattacharyya, A. S. Sahasrabudhe,
141 E. D. Dresden: ‘‘Transparenzmessung – eine Colourage 36 (1989) no. 3, 16 – 31.
M€ oglichkeit zur Kontrolle von Veredlungsvorg€angen,’’ 169 F. Weiss: Die Küpenfarbstoffe, Springer Verlag, Wien
TPI Text. Prax. Int. 48 (1993) 230 – 231. 1953. M. R. Vox: Vat Dyes and Vat Dyeing, Chapman
142 W. Rüttiger: ‘‘Ein plausibler Mechanismus für das En- and Hall, London 1948.
tstehen von Falten in Ablage-F€arbeaggregaten,’’ Len- 170 U. Baumgarte, Textilveredlung 4 (1969) 821 – 832.
zinger Ber. 45 (1978) 160 – 171. 171 U. Baumgarte, Textilveredlung 2 (1967) 896 – 907.
143 Deutsches Textilforschungszentrum Nord-West e. V.: 172 T. Bechtold, E. Burtscher, D. Gmeiner, O. Bobleter,
‘‘Lauf- und Liegefalten,’’ Krefeld 1977. Melliand Textilber. 72 (1991) 50 – 54. T. Bechtold, E.
144 Z. Gesamte Textilind. 58 (1956) 504 – 505. Burtscher, A. Amann, O. Bobleter, Angew. Chem. 104
145 Bayer-Faser-Institut, company brochure, Bildung und (1992) 1046 – 1047.
Fixierung von Falten – Dralon, VII f 1, Leverkusen, 173 U. Baumgarte, Melliand Textilber. Int. 55 (1974) 953 –
Feb. 1967. 962.
146 K. Venkataraman: The Chemistry of Synthetic Dyes, 174 T. Vickerstaff: The Physical Chemistry of Dyeing,
vol. 6: ‘‘Reactive Dyes,’’ Academic Press, New York Oliver & Bayd, London 1954.
1972. 175 U. Baumgarte, Textilveredlung 15 (1980) 413 – 424.
Vol. 36 Textile Dyeing 325
176 U. Baumgarte, Melliand Textilber. 59 (1978) 311 –319. 196 C. Heid: ‘‘Hydron-Blau, der Indigo des 20. Jahrhun-
177 E. I. Valko, J. Am. Chem. Soc. 59 (1941) 1433 – 1437. derts,’’ TPI Text. Prax. Int. 33 (1978) 285 – 287. C.
178 BASF-Ratgeber Cellulosefasern: Schlichten, Vorbehan- Klopfstock: ‘‘F€arben von Frottiermaterialien mit Imme-
deln, F€arben, Ludwigshafen 1977. dial-, Hydrosol-, Cassulfon-, Hydron-Blau- und Indanth-
179 U. Baumgarte, H. Schlüter, Melliand Textilber. 62 ren-Farbstoffen,’’ TPI Text. Prax. Int. 32 (1977) 1119 –
(1981) 555 – 561. 1121, 1230 – 1232. W. Titzka: ‘‘Einsatz von Schwe-
180 P. Richter: ‘‘Kontinuef€arben von Baumwollkettgarn mit felfarbstoffen in der Cord-F€arberei,’’ Melliand Textil-
Indigo,’’ Textilveredlung 10 (1975) no. 8, 312 – 316. ber. 60 (1979) 254 –256.
181 BASF, Continuous Dyeing of Cotton Warp Yarn with 197 G. Krauzpaul: ‘‘Die Schwefel- und Schwefelküpenfarb-
Indigo, Technical Information, Ludwigshafen 1985. stoffe in der Ausziehf€arberei aus der Sicht des Prakti-
182 J. A. Greer, G. R. Turner: ‘‘Indigo Denims: the Practical kers,’’ TPI Text. Prax. Int. 42 (1987) 140 –142.
Side,’’ Text. Chem. Color. 15 (1983) no. 6, 101 – 107. 198 H. M. Tobin: ‘‘Jet Dyeing with Sulfur and Vat Colours,’’
183 L. Haas: Indigo-F€arberei: Verfahrens- und maschinen- Am. Dyest. Rep. 68 (1979) no. 9, 26, 28.
technische L€osungen, Int. Text. Bull. Veredlung 2 (1990) 199 H. Bernhardt: ‘‘Welche Problematik wird durch die
45 – 50. Substantivit€at bei Klotzprozessen mit Schwefelfarbstof-
184 C. Heid, K. Holoubek, R. Klein: ‘‘100 Jahre Schwe- fen ausgel€ost? Gibt es dafür Probleml€osungen?’’ Int.
felfarbstoffe,’’ Melliand Textilber. 54 (1973) 1314 – Text. Bull. 33 (1987) 5 – 6, 8 – 9, 12, 16, 19. H.
1327. Bernhardt: ‘‘Der Einsatz des Taschencomputers bei der
185 E. Krusche: ‘‘Die Bedeutung der Schwefelfarbstoffe Rezepterstellung in der Kontinuef€arberei mit Schwefel-
heute und in der Zukunft,’’ Text. Prax. 23 (1968) farbstoffen,’’ Int. Text. Bull. 33 (1987) 46, 50, 54, 57.
342 – 344. 200 C. Heid: ‘‘Neue Fixierm€oglichkeiten von wasserl€osli-
186 D. G. Orton: ‘‘Sulfur Dyes,’’ in O. K. Venkataraman chen Schwefelfarbstoffen,’’ Z. Gesamte Textilind. 69
(ed.): The Chemistry of Synthetic Dyes, vol. VII, Aca- (1967) 106 – 108. Cassella Farbwerke, DE 1 619 403,
demic Press, New York 1974, pp. 26 – 33. 1967 (C. Heid, W. Gunzert).
187 Colour Index, vol. 3, pp. 3649 – 3704 (1971) , vol. 4, 201 R. Klein: ‘‘Ph€anomen Denim,’’ Textilveredlung 10
pp. 4475 – 4501 (1971) , vol. 6 (Revised Third Edi- (1975) 112 – 117.
tion), pp. 6375 – 6385 (1975) . 202 Cassella Farbwerke, DE 1 276 596, 1963 (M. Stuhlmil-
188 C. Heid: ‘‘Chemismus und Anwendung der wasserl€osli- ler, G. B€ottiger, C. Heid).
chen Schwefelfarbstoffe,’’ Melliand Textilber. 45 (1964) 203 ‘‘Probleme und Probleml€osungen textiler Abw€asser,’’
648 – 652, 833. Chemiefasern Textilind. 28/80 (1978) no. 1, 85 – 89. J.
189 W. Prenzel: ‘‘Der heutige Stand der Schwefelf€arberei,’’ M. Marzinkowski, W. Keiler: ‘‘Konzepte zur Vermei-
Chemiefasern Textind. 24/76 (1974) 293 – 302. dung von Abwasserbelastungen in einem Textilvere-
190 C. Heid: ‘‘Neue Anwendungsm€oglichkeiten von Hydro- dlungsbetrieb,’’ Chemiefasern Textilind. 41/93 (1991)
sol- und Hydrosol-Licht-Farbstoffen beim kontinuierli- 895 – 901.
chen und halbkontinuierlichen F€arben cellulosehaltiger 204 B. Kerres, G. Valk: ‘‘Verfahren zur Beseitigung von
Stückware,’’ Z. Gesamte Textilind. 70 (1968) 626 – 630. Geruchsbel€astigungen aus dem €offentlichen Kanalnetz
191 W. Titzka: ‘‘Das F€arben mit Schwefelfarbstoffen unter bei Einleitung von F€arbereiabw€assern mit Schwefelfarb-
besonderer Berücksichtigung der Reduktions- und Oxi- stoffen,’’ Melliand Textilber. 66 (1985) 588 – 590.
dationsmittel,’’ TPI Text. Prax. Int. 33 (1978) 1387 – 205 B. Smith, J. Rucker: ‘‘Water and Textile Wet Proces-
1390. sing – Part II,’’ Am. Dyest. Rep. 76 (1987) 68 – 78.
192 M. H€ahnke: ‘‘Die Schwefelf€arbung in €okologisch an- 206 C. Oehme: ‘‘Abwasserkl€arung nach dem Katox-F-Sys-
spruchsvoller Umwelt, Internat. Veredler-Jahrbuch,’’ tem,’’ TPI Text. Prax. Int. 33 (1978) 1076 – 1077. B.
Dtsch. F€ arber-Kal. 96 (1992) 154 – 156. H€oke: ‘‘Die Reinigungsleistung des Katox F-Verfah-
193 L. Tigler: ‘‘Sulfur Dye Oxidation,’’ Am. Dyest. Rep. 61 rens,’’ Textilbetrieb (Würzburg) 96 (1978) no. 6, 92 –
(1972) no. 9, 46, 107. 94; nos. 7, 8, 60 – 62. G. Wysocki: ‘‘Katox-
194 C. Heid: ‘‘Die Verbesserung der Wasch- und Peroxid- F€allungsverfahren für die Reinigung von Abw€assern der
waschechtheit von F€arbungen mit Schwefel- und Textilveredlungsindustrie: Technologie und Wirtschaf-
Schwefelküpen-Farbstoffen durch Solidurit IH,’’ Mel- tlichkeit,’’ Chemiefasern Textilind. 26/78 (1976) 353 –
liand Textilber. Int. 51 (1970) 322 – 325. C. Heid: 356.
‘‘Theorie und Praxis der Verbesserung der Wasch- und 207 W. Schwindt, G. Faulhaber, A. J. Moore, Rev. Prog.
Peroxidwaschechtheit von F€arbungen mit Schwefel- und Color. Relat. Top. 2 (1971) 33.
Schwefel-Küpenfarbstoffen,’’ Melliand Textilber. 59 208 T. Lever, J. Soc. Dyers Colour. 108 (1992) 477 – 478.
(1978) 247 – 254. 209 H. U. von der Eltz, H. Walbrecht, Dtsch. F€ arber-Kal. 77
195 C. Heid: ‘‘Die Anwendung von Fibradurit FS bei Schwe- (1973) 79 – 129.
felschwarzf€arbungen zur Vermeidung von Fas- 210 H. U. von der Eltz, Textilveredlung 7 (1972) 692 – 697.
ersch€adigungen w€ahrend des Trocknens und Lagerns.’’ 211 H. Rath: Lehrbuch der Textilchemie, 3rd ed., Springer
Z. Gesamte Textilind. 67 (1965) 364 – 367. Verlag, Berlin 1972.
326 Textile Dyeing Vol. 36
212 U. Baumgarte, Rev. Prog. Color. Relat. Top. 5 (1974) 241 A. C. Welham, J. Soc. Dyers Colour. 102 (1986) 126 –
17 – 32. 131.
213 R. H. Peters: Textile Chemistry, vol. 3, Elsevier, Am- 242 I. D. Rattee, J. Soc. Dyers Colour. 69 (1953) 288 – 295.
sterdam 1975. 243 D. de Meulemeester, I. Hammers, W. Mosimann, Aach-
214 A. Sch€affer: Handbuch der F€ arberei, vol. 1, Konradin- ener Textiltagung 1989; Melliand Textilber. 71 (1990) 69.
Verlag R. Kohlhammer, Stuttgart 1949. 244 F. Beffa, G. Back, Rev. Prog. Color. Relat. Top. 14
215 Ullmann, 4th ed., 22, p. 656. (1984) 33 – 42.
216 H. Vollmann: ‘‘Phthalogen Dyestuffs,’’ in K. Venkatara- 245 G. Schetty, W. Kuster, Helv. Chim. Acta 44 (1961) 2193.
man (ed.): The Chemistry of Synthetic Dyes, vol. 5, H. Pfitzner, Melliand Textilber. 35 (1954) 649 – 651.
Academic Press, New York 1971, p. 283. 246 G. Schetty, J. Soc. Dyers Colour. 71 (1955) 705.
217 M. Peter, H. K. Rouette, Grundlagen der Textilvere- 247 J. A. Bone, Schriftenr. Dtsch. Wollforschungsinst. Tech.
dlung, 13th ed., Deutscher Fachverlag, Frankfurt 1989. Hochsch. Aachen 93 (1984) 170 – 178.
218 E. El€od, H. Reutter, Melliand Textilber. 19 (1938) 67 – 248 W. Mosimann, Textilveredlung 17 (1982) 289 – 295.
72. 249 C. Mancheno, H.-W. Hensen, I. Souren, H.-K. Rouette,
219 J. D. Leeder, J. A. Rippon, F. E. Rothery, I. W. Stapleton, Melliand Textilber. 71 (1990) 875 – 882.
Proc. Int. Wool Text. Res. Conf. 7th vol. V, Tokyo, 1985, 250 G. v. Hornuff, H. J. Flath, Faserforsch. Textiltech. 12
vol. V, 99 – 108. (1961) 559 – 567.
220 J. D. Leeder: ‘‘The Cell Membrane Complex and its 251 D. M. Lewis, Melliand Textilber. 67 (1986) 717 –723.
Influence on the Properties of the Wool Fibre,’’ Wool Sci. 252 D. M. Lewis, J. Soc. Dyers Colour. 98 (1982) 165 –175.
Rev. 3 (1987) 3 – 35. 253 K. Hannemann, F. Grüner, Int. Text. Bull. Veredlung 38
221 V. Sideris, L. A. Holt, I. H. Leaver, J. Soc. Dyers Colour. (1992) no. IV, 22 – 31.
106 (1990) 131 – 135. 254 H. Angelmahr, F. Bartsch, TPI Text. Prax. Int. 47 (1992)
222 H. Zahn, Proc. Int. Wool Text. Res. Conf. 6th Pretoria 455 – 456.
1980, suppl. p. 1. 255 A. Würz, Melliand Textilber. 42 (1961) 439 – 444.
223 M.-L. Klotz, U. Altenhofen, H. Zahn, Textilveredlung 21 256 H. Baumann, Textilveredlung 14 (1979) 515 – 522.
(1986) 119 – 121. 257 D. Schwer, H. Ritter, K. Zesiger, Textilveredlung 16
224 H. Zahn, Lenzinger Ber. 42 (1977) 19 – 34. (1981) 479 – 484.
225 Forschungsprojekt des DWI: Interne Lipide der Wolle: 258 H. Flensberg, W. Mosimann, H. Salathe, Schriftenr.
Zusammensetzung, Ver€anderung und Bedeutung bei Dtsch. Wollforschungsinst. Tech. Hochsch. Aachen 93
Vergilbung und bei Veredlungsprozessen von Wolle (1984) 150 – 169.
(AIF-Nr. 7160). 259 D. M. Lewis, Rev. Prog. Color. Relat. Top. 19 (1989)
226 D. M€ausezahl, Textilveredlung 5 (1970) 839 – 845. 49 – 56.
227 H. Zollinger, G. Back, B. Milicevic, A. N. Roseira, 260 W. Mosimann, Am. Dyest. Rep. 80 (1991) no. 3, 26, 28,
Melliand Textilber. 42 (1961) 73 – 80. 30, 32, 34, 62.
228 F. Hoffmann, Rev. Prog. Color. Relat. Top. 18 (1988) 261 F. Blum, Bayer Farben Rev. 7 (1964) 1 – 9.
56 – 64. 262 R. Hofstetter, Melliand Textilber. 72 (1991) 366 –373.
229 F. Hoffmann, W. Langmann, H. Elberzhager, M. 263 F. Shimizu, K. Jyoko, I. Sakaguchi, Sen’i Gakkaishi 32
Schnee, Int. Text. Bull. F€arberei/Druckerei/-Ausrüstung (1976) 388 – 393.
no. 3 (1978) , 205, 206, 211, 212, 217, 218. 264 H. Putze, TPI Text. Prax. Int. 39 (1984) 1051 – 1054.
230 H. Flensberg, W. Mosimann, H. Salathe, Melliand Tex- 265 A. Liddiard, J. Soc. Dyers Colour. 99 (1983) 56 – 59.
tilber. 65 (1984) 472 – 477. 266 R. Rohrer, Textilveredlung 20 (1985) 85 – 87.
231 D. Hildebrand, H. Zahn, SVF Fachorgan Textilveredl. 267 K. Y. Chu, J. R. Provost, Rev. Prog. Color. Relat. Top. 17
13 (1958) 376 – 385. (1987) 22 – 28.
232 K. Reincke, Melliand Textilber. 74 (1993) 408 – 417. 268 A. Kremer, TPI Text. Prax. Int. 47 (1987) 746 – 757.
233 W. Ender, A. Müller, Melliand Textilber. 19 (1938) 269 A. Kremer, H. Kremer, Melliand Textilber. 73 (1992)
182 – 183. 580 – 582.
234 F. R. Hartley, J. Soc. Dyers Colour. 85 (1969) 66 – 71. 270 M. I. Guljarani, Rev. Prog. Color. Relat. Top. 22 (1992)
235 O. K. Dobozy, Am. Dyest. Rep. 62 (1973) no. 3, 36 – 48, 79 – 89.
76 – 77. 271 R. H. Peters, J. Soc. Dyers Colour. 61 (1945) 95 –100.
236 D. M. Lewis, G. Yan, J. Soc. Dyers Colour. 109 (1993) 272 A. Anton, Text. Chem. Color. 13 (1981) 46 – 50.
193 – 197. 273 G. Kühnel, H. J. Flath, R. G€artner, Melliand Textilber.
237 P. Spinacci, N. C. Gaccio, 12th IFVTCC Congr., Bu- 72 (1991) 288 – 290;360 – 362.
dapest 1981, pp. 10 – 13. 274 J. A. Coates, V. Ellard, I. D. Rattee, J. Soc. Dyers Colour.
238 P. A. Duffield, R. D. D. Holt, Textilveredlung 24 (1989) 96 (1980) 14 – 18.
40 – 45. 275 I. D. Rattee, S. So, Mater. Sci. Monogr. 21 (1984) 575 –
239 L. Benisek, Textilveredlung 12 (1977) 406 – 415; J. 584.
Soc. Dyers Colour. 94 (1978) 101 – 105. 276 B. Catiore, R. Hagege, Bull. Sci. Inst. Text. Fr. 2 (1973)
240 G. Meier, TPI Text. Prax. Int. 31 (1976) 898 – 901. 209.
Vol. 36 Textile Dyeing 327
277 G. Kühnel, Dissertation, TU Dresden 1989. 311 D. Dornig, H. Sehm, Melliand Textilber. 74 (1993)
278 F. Hoffmann, Chemiefasern/Textilind. 31/83 (1981) 212 – 215.
762 – 768. 312 Faserstoff-Tabellen according to P. A. Koch, Chemie-
279 B. von Falkai, H. Wilsing, TPI Text. Prax. Int. 33 (1978) fasern/Textilind. 43 (1993) no. 6, 508 – 522.
1324 – 1330. 313 K. H. Meyer, Melliand Textilber. 6 (1925) 737 – 739; V.
280 D. Dornig, Dissertation, TU Dresden 1974. Kartaschoff, Helv. Chim. Acta 8 (1925) 928 –942; 9
281 E. El€od, T. Schachowsky, Melliand Textilber. 23 (1942) (1926) 152 – 173.
437 – 440. 314 T. Vickerstaff: The Physical Chemistry of Dyeing,
282 T. Iijima, H. Zollinger, Teintex 32 (1967) 245 – 263. Oliver & Boyd, London 1954.
283 H. Zollinger, G. Back, B. Milicevic, A. N. Roseira, 315 R. H. Peters: Textile Chemistry, vol. 3: The Physical
Melliand Textilber. 42 (1961) 73 – 80. Chemistry of Dyeing, Elsevier, Amsterdam 1975.
284 E. Sada, H. Kumazawa, T. Ando, J. Soc. Dyers Colour. 316 H. Braun: ‘‘Particle Size and Solubility of Disperse
98 (1982) 121 – 125. Dyes,’’ Rev. Prog. Color. Relat. Top. 13 (1983) 62 – 72.
285 V. S. Praptowidodo, K. Hamada, T. Iijima, Angew. 317 H. Leube, Text. Chem. Color. 10 (1978) no. 2, 32 –39,
Makromol. Chem. 144 (1986) 159 – 165. 39 – 46.
286 J. Meybeck, P. Galafassi, Appl. Polym. Symp. 18 (1971) 318 F. Jones, J. Soc. Dyers Colour. 100 (1984) no. 2, 66 –72.
463 – 472. 319 G. L. Baughman, T. A. Perenich, Text. Chem. Color. 21
287 D. Schwer, Textilveredlung 23 (1988) 296 – 301. (1989) no. 1, 33 – 37.
288 W. Beckmann, F. Hoffmann, H.-G. Otten, Melliand 320 H. Leube, W. Rüttiger, Melliand Textilber. 59 (1978)
Textilber. Int. 54 (1973) 641 – 646; J. Soc. Dyers 836 – 842.
Colour. 88 (1972) 354 – 360. 321 T. M. Baldwinson, Rev. Prog. Color. Relat. Top. 15
289 W. Langmann, Melliand Textilber. Int. 54 (1973) 654 – (1985) 6 – 14.
659. 322 H. Gerber, Melliand Textilber. 69 (1988) 195 –200.
290 H. Beiertz, Am. Dyest. Rep. 68 (1979) no. 6, 22 – 26. 323 A. Keil, H. Noack, H. J. Flath, Textiltechnik 40 (1990)
291 F. Hoffmann, Rev. Prog. Color. Relat. Top. 18 (1988) 264 – 267, 318 – 320, 382 – 384, 432 – 437.
56 – 64. 324 R. Turner, Text. Chem. Color. 15 (1983) no. 9, 180/61 –
292 B. C. Burdell, Rev. Prog. Color. Relat. Top. 13 (1983) 188/69.
41 – 49. 325 D. M. Nunn (ed.): The Dyeing of Synthetic Polymer and
293 O. Annen, J. Carbonell, Textilveredlung 15 (1980) Acetate Fibres, Dyers Comp. Publ. Trust, Bradford
296 – 302. 1979.
294 H. Scheidegger, H. Flensberg, R. Bauhofer, Textilver- 326 F. Somm, R. Buser, Int. Dyer Printer 170 (1985) no. 12,
edlung 13 (1978) 302 – 304. 6 – 7.
295 J. R. Aspland, Text. Chem. Color. 25 (1993) 19 – 23. 327 H. Gerber, Textilveredlung 8 (1973) 449 – 456.
296 J. Shore, J. Soc. Dyers Colour. 87 (1971) 37 – 48. 328 A. Maier, AATCC Int. Dyeing Symp., Washington
297 J. Guthrie, J. Appl. Polym. Sci. 27 (1982) 2567 – 2575. 1977, pp. 66 – 69.
298 C. C. Cook, Rev. Prog. Color. Relat. Top. 12 (1982) 329 R. A. Walsh, Text. Chem. Color. 7 (1975) no. 10, 184/
73 – 89. 35 – 187/38.
299 T. F. Cooke, H. D. Weigmann, Rev. Prog. Color. Relat. 330 Disperse Dye Comm., J. Soc. Dyers Colour. 93 (1977)
Top. 20 (1990) 10 – 18. 228 – 237.
300 O. Annen, Textilveredlung 19 (1984) 8 – 11. 331 M. Hammoudeh, E. Sch€onpflug, Melliand Textilber. 52
301 H. Egli, Textilveredlung 2 (1967) 856 – 864. (1971) 1063 – 1068.
302 Bayer, Musterkarte Telon-S-Verfahren Sp 502, 332 BASF Manual: Dyeing and Finishing of Polyester Fibers
Leverkusen. B 363 e, pp. 384 – 501, 1975.
303 R. Weber, Melliand Textilber. 58 (1977) 48 – 51. 333 J. Park, Rev. Prog. Color. Relat. Top. 15 (1985) 26 –27;
304 W. Hartmann, Am. Dyest. Rep. 69 (1980) no. 6, 21 – T. M. Baldwinson, 6 – 14.
22. 334 G. R. Turner, Text. Chem. Color. 15 (1983) no. 9, 61 –
305 M. Mitter, Chemiefasern/Text. Anwendungstech. 31 69.
(1981) 55 – 56, 558. 335 E. Podogrocka, Melliand Textilber. 70 (1989) 198 –199.
306 I. Strelecky, Ciba Rundsch. 1968, no. 2, 40 – 44. 336 K. Poulaikis et al., Chemiefasern/Textilind. 41 (1991)
307 W. R. Remington, E. K. Gladding, J. Am. Chem. Soc. 72 142 – 147.
(1953) 2553. 337 W. Saus, D. Knittel, E. Schollmeyer, TPI Text. Prax. Int.
308 M. Greenhalgh, A. Johnson, R. H. Peters, J. Soc. Dyers 48 (1993) 32 – 36; Text. Res. J. 63 (1993) no. 3, 135 –
Colour. 78 (1962) 315 – 321. 142.
309 N. J. Bhatt, E. H. Daruwalla, Textile Res. J. 34 (1964) 338 F. Jones, J. Kraska, J. Soc. Dyers Colour. 82 (1960)
435 – 444. 333 – 338.
310 G. Valk, G. Stein, A. El Bendak, Melliand Textilber. 57 339 Ch. Guth, Textilveredlung 14 (1979) 270 – 274.
(1976) 166; 58 (1977) 580 – 582. G. Valk, G. Stein, 340 AATCC Palmetto Section, Text. Chem. Color. 11 (1979)
Melliand Textilber. 59 (1978) 593 – 594. no. 12, 270/23 – 282/35.
328 Textile Dyeing Vol. 36
341 Nippon Kayaku, JP 59 066 585, 1982 (N. Mitsuro). 371 A. V. Hill, Proc. R. Soc. London B 104 (1928) 39, 65.
342 J.-H. Chiao-Cheng, B. M. Reagan, Text. Chem. Color. 15 372 W. Beckmann, 11th Int. Textile Seminar, Kingston,
(1983) 12 – 19. Ontario, 1968, Book of Papers, p. 97; Z. Gesamte Tex-
343 C. A. Li, Chem. Abstr. 100 (1984) no. 24, 193 415. tilind. 71 (1969) 603.
344 W. Griesser, H. Tiefenbacher, Textilveredlung 28 (1993) 373 S. Rosenbaum, J. Polym. Sci. Part A 3 (1965) 1949.
no. 4, 88 – 96. 374 M. Williams, R. Landel, J. Ferry, J. Am. Chem. Soc. 77
345 M. Laufer, Textilveredlung 28 (1993) no. 4, 96 –101. (1955) 3701.
346 P. Richter, Chemiefasern/Textilind. 41/93 (1991) no. 9, 375 R. Asquith, H. Blair, N. Spence, Text. Res. J. 47 (1977)
1118 – 1125, E 129 – 133. 446; J. Soc. Dyers Colour. 94 (1978) 49.
347 W. Beckmann, H. Hamacher, Chemiefasern þ Text. 376 S. Rosenbaum, Text. Res. J. 34 (1964) 159.
Anwendungstech. Text. Ind. 23 (1973) no. 5, 436 –439. 377 D. Balmforth, C. Bowers, T. Guion, J. Soc. Dyers
348 C. Renard, Melliand Textilber. 54 (1973) 1328 –1335. Colour. 80 (1964) 577.
349 J. Cegarra, F. J. Carrion, P. Puente, Melliand Textilber. 378 D. G. Evans, G. J. Bent: ‘‘Basic Dyes on Acrylic Fibres’’
65 (1984) 405 – 409. J. Soc. Dyers Colour. 89 (1973) 292.
350 C. Grardel, Ind. Text. (Paris) 1155 (1985) no. 5, 519 – 379 J. Neary, R. Thomas, Am. Dyest. Rep. 46 (1957) 625.
520. 380 I. Holme, Rev. Prog. Color. Relat. Top. 1 (1970) 31.
351 H. Beiertz, Chemiefasern/Textilind. 42/94 (1992) no. 1, 381 S. Cohen, A. Endler, Am. Dyest. Rep. 46 (1957) 625; 47
64 – 67, E 1 – 3; H. Beiertz, K. H. R€ostermundt, TPI (1958) 325.
Text. Prax. Int. 48 (1993) no. 2, 135 –137. 382 S. Heimann, F. Feichtmayr, Z. Gesamte Textilind. 68
352 G. Reinert, V. Misun, Melliand Textilber. Int. 74 (1993) (1966) 509.
1007 – 1014. 383 F. Hoffmann, Melliand Textilber. 59 (1978) 239.
353 Report of Committee: ‘‘Dyeing Properties of Disperse 384 C. Zimmermann, A. Cate, Am. Dyest. Rep. 83 (1972)
Dyes, I Cellulose Acetate,’’ J. Soc. Dyers Colour. 80 150.
(1964) 237 – 242; ‘‘II Cellulose Triacetate,’’ J. Soc. 385 Bayer, CA 793 184, 1968 (W. Beckmann, J. Nentwig, H.
Dyers Colour. 81 (1965) 209 – 210. Rudolf, J. Schneider).
354 H. Leube, Z. Gesamte Textilind. 70 (1968) no. 4 to 71 386 M. Dullaghan, A. Ultee, Text. Chem. Color. 8 (1976) 22.
(1969) no. 2; English version see: Dyeing and Finishing 387 S. Shukla, M. Mathur, J. Soc. Dyers Colour. 109 (1993)
of Acetate and Triacetate and their Blends with Other 330.
Fibres, BASF Manual S 388 e. 388 J. Leddy, Am. Dyest. Rep. 49 (1960) 272.
355 D. Blackburn in D. M. Nunn (ed.): The Dyeing of 389 D. G. Evans, C. J. Bent: ‘‘Basic Dyes on Acrylic Fibres
Synthetic Polymer and Acetate Fibres, Comp. Publ. Comm.’’ J. Soc. Dyers Colour. 88 (1972) 220.
Trust, Bradford 1979, pp. 76 – 128. 390 F. Hoffmann, Rev. Prog. Color. Relat. Top. 18 (1988) 56.
356 R. H. Peters: ‘‘The Physical Chemistry of Dyeing,’’ 391 AATCC Metropolitan Sect., Text. Chem. Color. 8
Textile Chemistry, vol. 3, Elsevier, Amsterdam 1975. (1976) 165.
357 Stanford Research Inst.: Chemical Economics Hand- 392 J. Park, J. Shore, J. Soc. Dyers Colour. 97 (1981) 223. J.
book, Fibers 5 433 000 D, Menlo Park, Sept. 1993. Park: A Practical Introduction to Yarn Dyeing, Society
Comite International de la Rayonne et des Fı̀bres Synthe- of Dyers and Colourists, Bradford 1980.
tiques, Bruxelles, Brochures 1993. 393 W. Biedermann, Rev. Prog. Color. Relat. Top. 10 (1979)
358 T. A. Field, Am. Dyest. Rep. 41 (1952) 475. 1.
359 R. Raue, Rev. Prog. Color. Relat. Top. 14 (1984) 187. 394 F. Hoffmann, M. Schnee, H. Schubert, Melliand Textil-
360 W. Beckmann in D. M. Nunn (ed.): The Dyeing of ber. 65 (1984) 478.
Synthetic Polymer and Acetate Fibres, The Dyer’s 395 F. Hoffmann, Text. Chem. Color. 22 (1990) 11.
Company, Bradford 1979, p. 359 ff. 396 A. Kretschmer, TPI Text. Prax. Int. 44 (1989) 1098,
361 I. Holme, Rev. Prog. Color. Relat. Top. 13 (1983) 10. 1316; 45 (1990) 225; 46 (1991) 1220.
362 F. Jones, Rev. Prog. Color. Relat. Top. 4 (1973) 64. 397 W. Beckmann, K. Jakobs, Bayer Farben Rev. 16 (1968)
363 H. Sumner in A. Johnson (ed.): The Theory of Coloura- 1.
tion of Textiles, ‘‘chap. 2’’, Society of Dyers and Colour- 398 F. Hoffmann, H. Schubert, J. Fiegel, TPI Text. Prax. Int.
ists, Bradford 1989. 47 (1992) 233.
364 O. Glenz, W. Beckmann, Melliand Textilber. 38 (1957) 399 P. Dorsch, H. Wilsing, K.-H. Peters, Melliand Textilber.
296, 783, 1152. 62 (1981) 188.
365 W. Beckmann, J. Soc. Dyers Colour. 77 (1961) 616. 400 R. Rohner, H. Zollinger, Text. Res. J. 56 (1986) 1.
366 S. Rosenbaum, Text. Res. J. 33 (1963) 899. 401 U. Meyer, J. Zhang, H. Zollinger, Textilveredlung 19
367 U. Mayer, W. Ender, A. Würz, Melliand Textilber. 47 (1984) 39.
(1966) 653, 772. 402 U. Reinehr, G. H€afner, A. Nogaj, Chemiefasern/Texti-
368 G. Alberghina, M. Amato, S. Fisichella, J. Soc. Dyers lind. 35 (1985) no. 87, 588.
Colour. 105 (1989) 163. 403 G. Müller, Textilveredlung 10 (1975) 438.
369 H. Zollinger, Text. Res. J. 59 (1989) 264. 404 L. Witt, P. Toldrian, Chemiefasern/Textilind. 28 (1978)
370 P. R. Brady, Rev. Prog. Color. Relat. Top. 22 (1992) 58. no. 80, 469.
Vol. 36 Textile Dyeing 329
405 J. Shore, Rev. Prog. Color. Relat. Top. 10 (1979) 33. 438 W. Baumann et al., Melliand Textilber. 67 (1986) 562 –
406 W. Beckmann, W. Langmann, Dtsch. Textiltech. 18 566; J. Soc. Dyers Colour. 103 (1987) 100 –105.
(1968) 243. 439 R. Broßmann et al., Melliand Textilber. 67 (1986) 499 –
407 H. Gerber, H. Lehmann, F. Somm, Melliand Textilber. 502; J. Soc. Dyers Colour. 103 (1987) 38 – 42.
Int. 54 (1973) 77. 440 A. Berger-Schunn et al., Melliand Textilber. 67 (1986)
408 L. Kostova, R. Iltscheva, R. Detscheva, Textilveredlung 638 – 639, 716 – 717, 812 – 813; J. Soc. Dyers Colour.
27 (1993) 398. 103 (1987) 138 – 139, 140 – 141, 272 – 274.
409 I. Hardalov, J. Mikhailova, J. Soc. Dyers Colour. 109 441 T. v. Chambers et al., Melliand Textilber. 69 (1988)
(1993) 369. 755 – 758; J. Soc. Dyers Colour. 105 (1989) 214 – 218.
410 R. Weber, Text. Prax. 21 (1966) 670. 442 Brit. Occup. Hyg. Soc., Technical Guide no. 4, part 1
411 W. Ingamells, J. Soc. Dyers Colour. 96 (1980) 332. and 2 (1985).
412 P. Ackroyd, Rev. Prog. Color. Relat. Top. 5 (1974) 86. 443 A. Berger-Schunn et al., Melliand Textilber. 70 (1989)
413 R. Detscheva, R. Iltscheva, K. Dimov, Textilveredlung 9 690 – 693; J. Soc. Dyers Colour. 107 (1991) 270 – 273.
(1974) 312; 10 (1975) 318. 444 J. Soc. Dyers Colour. 88 (1972) 220 – 222.
414 A. L€apple, A. Schneider, Textilveredlung 10 (1975) 63. 445 P. J. Smith, Rev. Prog. Color. Relat. Top. 24 (1994) 31 –
415 I. Holme, Rev. Prog. Color. Relat. Top. 7 (1976) 1. 40.
416 D. M. Nunn (ed.): The Dyeing of Synthetic-polymer and 446 TVI-Verband: Water/Wastewater Investigation 1992
Acetate Fibres, Dyers Comp. Publ. Trust, Bradford (Association of the Textile Finishing Industry), Frank-
1979. furt a. M. 1993.
417 M. Peter, H. K. Rouette: Grundlagen der Textilvere- 447 Arbeitsbericht der ATV-Arbeitsgruppe Textilvere-
dlung, 13th ed., Deutscher Fachverlag, Frankfurt a. M. dlungsindustrie (Working Report of the ATV Working
1989. Group Textile Finishing Industry), Korresp. Abwasser
418 H. W. Partridge, Rev. Prog. Color. Relat. Top. 6 (1975) 36 (1989) 1074 – 1084.
56. 448 Gesetz zur Ordnung des Wasserhaushaltes, Wasser-
419 BASF: technical information TI/T 138 e, Ludwigshafen haushaltsgesetz, Neufassung vom 12.2.1990, BGBl. I
1986. (Water Resources Act, revised February 12, 1990, Fed-
420 BASF: technical information TI/T 151 e, Ludwigshafen eral Law Gazette), p. 205
1985. 449 Abwasserherkunftsverordnung vom 3.7.1987, ge€andert
421 G. Biehler, Chemiefasern/Textilind. 29/81 (1979) 848 – am 27.5.1991, BGBl. I. (Wastewater Origin Decree,
853. July 3, 1987, revised May 27, 1991, Federal Law Ga-
422 H. Leube, Melliand Textilber. 46 (1965) 743 – 749. zette), p. 1197.
423 J. Shore, Rev. Prog. Color. Relat. Top. 6 (1975) 7 –12. 450 Allgemeine Rahmenabwasserverwaltungsvorschrift
424 J. Shore in [416], pp. 393 – 403. über Mindestanforderungen an das Einleiten von Ab-
425 R. H. Peters: Textile Chemistry, vol. 3: The Physical wasser in Gew€asser, Neufassung vom 29.10.1992,
Chemistry of Dyeing, Elsevier, Amsterdam 1975. GMBl 1992 (General Legal Framework on Minimum
426 B. D. Gupta, A. K. Mukherjee, Rev. Prog. Color. Relat. Requirements on Discharge of Wastewater into Surface
Top. 19 (1989) 7 – 19. Waters, revised October 29, 1992, Joint Ministerial Law
427 Ullmann, 3rd ed. 7, 46 – 54. Gazette 1992), pp. 1265 – 1266.
428 BASF Manual Dyeing and Finishing of Polyester Fibres 451 38. Abwasserverwaltungsvorschrift über Mindestanfor-
B 363 e, 1975. derungen an das Einleiten von Abwasser in Gew€asser
429 J. Shore in D. M. Nunn (ed.): The Dyeing of Synthetic- (Textilherstellung) vom 5.9.1984, GMBl. [38th Waste-
polymer and Acetate Fibres, Dyers Comp. Publ. Trust, water Ordinance on Minimum Requirements for the
Bradford 1979. Discharge of Wastewater into Surface Waters (Textile
430 M. Peter, H. K. Rouette: Grundlagen der Textilvere- Processing), September 5, 1984, Joint Ministerial Law
dlung, 13th ed., Deutscher Fachverlag, Frankfurt a. M. Gazette] 1984, p. 348.
1989. 452 Bundesratsdrucksache 181/93 (Printed Matter of the
431 BASF Manual Dyeing and Finishing of Cellulose Fibres German Bundesrat), pp. 13 – 21.
B 375 e, pp. 383 – 414, 1975. 453 612. Verordnung des Bundesministers für Land- und
432 K. H. Rostermundt, TPI Text. Prax. Int. 47 (1992) no. 7, Forstwirtschaft über die Begrenzung von Abwassere-
649 – 654; and XIX – XXIII. missionen aus Textilveredlungs- und Behandlungsbe-
433 S. M. Doughty, Rev. Prog. Color. Relat. Top. 16 (1986) trieben, BGBl. 207. Stück v. 24.9.1992 (612. Ordinance
25 – 38. of the Federal Minister for Agriculture and Forestry on
434 W. Haertl, Textilveredlung 24 (1989) no. 6, 214 – 218. Limitations of Discharge from Textile Finishing and
435 D. Blackburn, Int. Dyer Text. Printer, Bleacher Finish. Processing Plants, Federal Law Gazette, September 24,
171 (1986) no. 1, 13 – 14. 1992), pp. 2828 –2835.
436 A. Berger-Schunn: Praktische Farbmessung, Muster 454 The Water Act (London. HMSO).
Schmidt, G€ ottingen 1991. 455 I. G. Laing, Rev. Prog. Color. Relat. Top. 21 (1991) 56 –
437 ISO/CD 787–26 (Draft). 71.
330 Textile Dyeing Vol. 36
456 P. Cooper, J. Soc. Dyers Colour. 108 (1992) 176 –182. 490 W. Marte, W. Keller, Textilveredlung 26 (1991) 224 –
457 H. Reetz, Melliand Textilber. 72 (1991) 932 –933. 230.
458 The Government of Japan, Environment Agency: An- 491 G. von Hagel, Korresp. Abwasser 33 (1986) 908 –915.
nual Book, Quality of the Environment in Japan in 1992. 492 T. R. Demmin, K. D. Uhrich, Am. Dyest. Rep. 77 (1988)
459 B. Smith, J. Rucker, Am. Dyest. Rep. 76 (1987) 68 –78. 13 – 14, 17 – 18, 32.
460 Sewerage Bureau of Osaka Municipal Government: The 493 W. C. Tincher, Text. Chem. Color. 21 (1989) 33 – 35.
Sewerage Law and Regulations for Control of Water 494 A. E. Wilcock, S. P. Hay, Can. Text. J. 108 (1991) 37 –
Quality, Osaka 1990. 44.
461 U. Sewekow, Melliand Textilber. 70 (1989) 589 –596. 495 A. E. Wilcock, M. Brewster, W. C. Tincher, Am. Dyest.
462 U. R€ossner, Textiltechnik (Leipzig) 38 (1988) 661 –665. Rep. 81 (1992) 15 – 22.
463 B. Smith, Am. Dyest. Rep. 78 (1989) 26 – 32. 496 G. Schulz, D. Fiebig, H. Herlinger, Textilveredlung 23
464 W.-D. Kermer, Melliand Textilber. 69 (1988) 586 –590. (1988) 1 – 4.
465 B. M. Müller, Rev. Prog. Color. Relat. Top. 22 (1992) 497 G. Schulz, H. Herlinger, G. Mayer, Textilveredlung 25
14 – 21. (1990) 23 – 27.
466 J. Park, J. Shore, J. Soc. Dyers Colour. 100 (1984) 383 – 498 A. H€ovelmann, S. C. Bidinger, A. Linder, TPI Text.
399. Prax. Int. 48 (1993) 507 – 509.
467 J. Wolff, H. Henk, Textilveredlung 25 (1990) 213 –218. 499 K. H. Gregor, Melliand Textilber. 71 (1990) 976 –979.
468 W. Beckmann, U. Sewekow, TPI Text. Prax. Int. 46 500 U. Sewekow, Melliand Textilber. 74 (1993) 153 –157.
(1991) 346 – 348, 445 – 449. 501 D. L. Michelsen, W. W. Powell, R. M. Woodby, L. L.
469 F. Hoffmann, H. Schubert, J. Fiegel, TPI Text. Prax. Int. Fulk, AATCC Technical Conference, Book of Papers,
47 (1992) 233 – 237. Atlanta 1992, pp. 135 – 150.
470 R. Puk, D. Sedlak, TPI Text. Prax. Int. 47 (1992) 238 – 502 J. M. Green, C. Sokol, Am. Dyest. Rep. 74 (1985) 50 –
245. 51, 67.
471 J. M. Marzinkowski, Chemiefasern/Textilind. 41/93 503 M. Kolb, B. Müller, B. Funke, Vom Wasser 69 (1987)
(1991) 895 – 901. 217 – 223.
472 P. A. Duffield, K.-H. Hoppen, Melliand Textilber. 68 504 J. Carriere, J. P. Jones, A. D. Broadbent, AATCC
(1987) 195 – 202. Technical Conference, Book of Papers, Atlanta 1992,
473 P. A. Duffield, R. R. D. Holt, J. R. Smith, Melliand pp. 231 – 236.
Textilber. 72 (1991) 938 – 942. 505 M. Pitroff, K. H. Gregor, Melliand Textilber. 73 (1992)
474 W. Sebb, TPI Text. Prax. Int. 44 (1989) 841 – 843. 526 – 529.
475 F. Conzelmann, P. Wurster, A. Zahn, TPI Text. Prax. Int. 506 H. Reissig, T. Jentsch, R. Fischer, Gew€ asserschutz,
44 (1989) 644 – 649. Wasser, Abwasser 125 (1991) 275 – 304.
476 G. R€ osch, TPI Text. Prax. Int. 45 (1990) 495 – 499. 507 G. Schulz, H. Herlinger, F. U. G€ahr, T. Lehr, TPI Text.
477 W. Beckmann, J. Pflug, TPI Text. Prax. Int. 38 (1983) Prax. Int. 47 (1992) 1055 – 1062.
160, 165 – 168. 508 M. Kolb, P. Korger, B. Funke, Melliand Textilber. 69
478 R. Teichmann, Melliand Textilber. 74 (1993) 900 –902. (1988) 286 – 287.
479 H.-U. von der Eltz, TPI Text. Prax. Int. 45 (1990) 727 – 509 M. Kolb, B. Funke, A. Baur, N. Peschen, Korresp.
731. Abwasser 32 (1985) 986 – 987.
480 D. Fiebig, D. Soltau, TPI Text. Prax. Int. 43 (1988) 644, 510 E. Burtscher et al., Melliand Textilber. 74 (1993) 903 –
649 – 650; 44 (1989) 533 – 535; 44 (1989) 1124 – 907.
1126. 511 J. J. Porter, Am. Dyest. Rep. 61 (1972) 24 – 27.
481 D. Frahne, S. Koscielski, Melliand Textilber. 68 (1987) 512 H.-J. Buschmann, E. Schollmeyer, Melliand Textilber.
594 – 596. 72 (1991) 543 – 544.
482 N. Athanasopoulos, Melliand Textilber. 71 (1990) 513 H.-J. Buschmann, Chemiefasern/Textilind. 42/94 (1992)
619 – 628. 408 – 411.
483 U. Sewekow, G. Diesterweg, Textilveredlung 26 (1991) 514 D. Tegtmeyer, Melliand Textilber. 74 (1993) 148 –151.
142 – 146. 515 U. Sewekow, AATCC Conference, Book of Papers,
484 A. Wilking, D. Frahne, Melliand Textilber. 74 (1993) Montreal 1993, pp. 235 – 246.
897 – 900. 516 W. Peukert, Seifen, o€le, Fette, Wachse 114 (1988) 474 –
485 C. Oehme, Melliand Textilber. 67 (1986) 582 – 588. 477.
486 J. Janitza, S. Koscielski, H. Schnabel, TPI Text. Prax. Int. 517 Text. Horizons 1987, 58 – 59.
46 (1991) 1216 – 1219. 518 K. Roennefahrt, Melliand Textilber. 70 (1989) 203 –
487 P. J. Halliday, S. Beszedits, Can. Text. J. 103 (1986) 206.
78 – 84. 519 J. Küßner, J. Janitza, S. Koscielski, TPI Text. Prax. Int.
488 E. Thomanetz, D. Bardtke, E. K€ohler, GWF, Gas-Was- 47 (1992) 736 – 741.
serfach: Wasser/Abwasser 128 (1987) 432 – 441, 520 P. Wragg, J. Soc. Dyers Colour. 109 (1993) 280 –282.
475 – 481. 521 S. N. Gaeta, U. Fedele, Desalination 83 (1991) 183 –
489 M. Seekamp, Textilveredlung 25 (1990) 125 – 129. 194.
Vol. 36 Textile Dyeing 331
522 G. M. Elgal, Text. Chem. Color. 18 (1986) 15 – 20. 546 R. Anliker, Textilveredlung 16 (1981) 431 – 438.
523 F. Richartz, TPI Text. Prax. Int. 46 (1991) 567 –572. 547 K. H. Leist, Ecotoxicol. Environ. Saf. 6 (1982) 457 –
524 W. Hess, Bild Wiss. 29 (1992) 84 – 88. 463.
525 E. Spachmann, E. Tillig, TPI Text. Prax. Int. 45 (1990) 548 R. A. Moll, Melliand Textilber. 72 (1991) 836 –840.
129 – 130. 549 IARC Monographs on the Evaluation on the Carcino-
526 J. Trauter, Melliand Textilber. 74 (1993) 559 – 562. genic Risks to Humans 48 (1990) 139 –147.
527 J. J. Porter, Text. Chem. Color. 22 (1990) 21 – 25. 550 U. S. Dep. of Health and Human Serv., National Toxi-
528 D. Kuiper, C. A. Brandon, H. G. Spencer, G. L. Gaddys, cology Program, Technical Report Series no. 285 (1992)
TPI Text. Prax. Int. 40 (1985) 1124 – 1126. 11 – 13.
529 A. Ersvell, C. J. Brouckaert, C. A. Buckley, Desalination 551 GefStoffV vom 26.8.1986, in der Fassung vom
70 (1988) 157 – 167. 26.10.1993, BGBl. I (GefStoffV, August 26, 1986, ver-
530 G. M. Shaul, T. J. Holdsworth, C. R. Dempsey, K. A. sion October 26, 1993, Federal Law Gazette), 1782 –
Dostal, Chemosphere 22 (1991) 107 – 119. 1810.
531 U. Pagga, D. Brown, Chemosphere 15 (1986) 479 –491. 552 R. Anliker, D. Steinle, Textilveredlung 25 (1990) 42 –
532 G. B. Michaels, D. L. Lewis, Environ. Toxicol. Chem. 5 49.
(1986) 161 – 166. 553 O. P. Hornstein, Melliand Textilber. 70 (1989) 222 –
533 T. Ogawa, C. Yatome, E. Idaka, H. Kamiya, J. Soc. 227.
Dyers Colour. 102 (1986) 12 – 14. 554 K. L. Hatch, Text. Res. J. 54 (1984) 644 – 682, 721 –
534 K. Ackermann, D. Frahne, Melliand Textilber. 63 (1982) 732.
66 – 69. 555 B. M. Hausen, K. H. Schulz, DMW Dtsch. Med. Wo-
535 C. Harmer, P. Bishop, E. Holder, P. V. Scarpino, Proc. chenschr. 109 (1984) 1469 – 1475.
Ind. Waste Conf. 46th, Lewis Publishers, Chelsea, 556 B. M. Hausen, A. Kleinheinz, H. Mensing, Allergo J. 2
Michigan 1992 pp. 217 – 228. (1993) 13 – 16.
536 G. M. Shaul, C. R. Dempsey, K. A. Dostal, R. J. 557 J. M. Wattie, J. Soc. Dyers Colour. 103 (1987) 304 –
Liebermann, Proc. Ind. Waste Conf. 41st, publ. 1987, 307.
603 – 611. 558 G. A. Heath, W. Dyson, Text. Chem. Color. 22 (1990)
537 H. R. Hitz, W. Huber, R. H. Reed, J. Soc. Dyers Colour. 25 – 31.
94 (1978) 71 – 76. 559 P. Rosenthal, Int. Text. Bull. 36 (1990) 58 – 66.
538 D. Brown, P. Laboureur, Chemosphere 12 (1983) 397 –
404.
539 D. Brown, B. Hamburger, Chemosphere 16 (1987)
1539 – 1559. Further Reading
540 W. C. Tincher: Dyes in the Environment: Dyeing Wastes
in Landfill, Final Report, Georgia Institute of Technol- M. Bide: Dyeing, ‘‘Kirk Othmer Encyclopedia of Chemical
ogy, Atlanta 1988. Technology’’, 5th edition, John Wiley & Sons, Hoboken,
541 D. Brown, H. R. Hitz, L. Sch€afer, Chemosphere 10 NJ, online DOI:10.1002/0471238961.0425051907121522.
(1981) 245 – 261. a01.pub2.
542 R. Anliker: ‘‘Organic Colorants’’ in M. Richardson (ed.): G. Buxbaum, G. Pfaff (eds.): Industrial Inorganic Pigments,
Toxic Hazard Assessment of Chemicals, The Royal 3rd ed., Wiley-VCH, Weinheim 2005.
Society of Chemists, London 1986, pp. 167 – 187. W. Herbst, K. Hunger, G. Wilker: Industrial Organic Pig-
543 E. A. Clarke, R. Anliker, Rev. Prog. Color. Relat. Top. ments, 3rd. ed., Wiley-VCH, Weinheim 2004.
14 (1984) 84 – 89. R. Lang (ed.): Dyes and Pigments – New Research, Nova
544 D. Brown, Ecotoxicol. Environ. Saf. 13 (1987) 139 – Science Publishers, Boca Raton, 2008.
147. R. W. Sabnis: Handbook of Biological Dyes and Stains –
545 R. Anliker, E. A. Clarke, P. Moser, Chemosphere 10 Synthesis and Industrial Applications, Wiley, Hoboken,
(1981) 263 – 274. 2010.