The Nature of Printing Inks

Inks are colored, usually liquid, materials for writing or printing. They are used for many reasons,
primarily as a tool to convey a message and give instant decoration. Inks are extremely versatile
and can be applied to a wide variety of different surfaces, whatever their texture, size or shape.
Paper, plastic, metal, glass and textiles will all accept ink. Printing inks are applied to such
surfaces by printing presses of various designs. Ink films, unlike paint films, are very thin varying
from 2 to 30 µm depending on the print process. Inks consist essentially of two components, the
colorant, an insoluble solid or a dye, and the vehicle, a liquid in which the colorant is suspended
or dissolved. The combined components form a fluid capable of printing from a printing press.
The secondary function of the vehicle is to 'dry' and bind the colourant firmly to the substrate.
Although the primary functions of an ink are to convey a message or decorate, it is of no value if
it will not transfer to the substrate nor adhere satisfactorily after printing. In addition to (1) its
visual characteristics, therefore, an ink is formulated to:
(2) Print by a given process;
(3) Dry under specified conditions;
(4) Adhere to a given material;
(5) have specific resistance properties, dictated by the intermediate processing of, and the final
end use of the printed matter.

Visual Characteristics of ink:

The visual characteristics of an ink are defined in terms of its color, its transparency or opacity
and its gloss and are largely determined by the quantity and nature of colorant(pigment or dye)
used.

The color of inks:

Color is a complex concept and needs to be described in three interrelated ways. Firstly, the 'hue’
of a color indicates what kind of a color it is, i.e. red, blue, green, etc. Secondly, the 'strength' of a
color is a measure of its intensity or saturation. The third property is its 'purity' which indicates
how bright or dark it is.
There are many factors that affect each of these parameters to one degree or another. Clearly, the
chemical structure of the colorant has a fundamental effect on its hue, but so do particle size,
surface characteristics and the amount of colorant contained in a given ink film. In general, the
higher the concentration of a particular colorant, the greater the strength of the color, although in
many cases an optimum concentration occurs beyond which there is no further increase in
strength.
The types of resins, oils or solvents used in the ink vehicle can alter the hue or purity of a
particular colorant. This may be due to the color of the vehicle itself or because different ink
vehicles develop different colors when dispersing the same colorant. Sometimes additives
selected to aid dispersion can cause alterations in hue and strength.
The choice of ink vehicle can be very important in affecting the practical strength of an ink. The
ink vehicle must be capable of keeping the colorant particles dispersed otherwise they may settle
out and there will be a tendency towards loss of strength. Also, an ink vehicle that penetrates the
substrate will take some of the pigment with it, effectively lowering its strength. Similarly, a slow
drying solvent can cause increased penetration into absorbent stocks with the same end result.
Generally, therefore, higher amounts of resin in the vehicle and faster drying solvents give better

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hold-out and greater color strength.

The transparency and opacity of printing inks

To achieve the desired visual appearance, inks need to have varying degrees of opacity and
transparency. One of the major influences on the transparency of an ink is the choice of colorant
and the degree to which it is dispersed.

Different colorants behave differently towards light. The more opaque colorants have a greater
tendency to reflect and refract light, and this is influenced by particle size and refractive index.
Thus, the high refractive index and the particle size of titanium dioxide ensure that it effectively
reflects, refracts and, therefore, scatters light of all visible wavelengths, making it one of the most
opaque pigments in use in printing inks. Soluble dyes, on the other hand, have a relatively low
refractive index and small particle size and give highly transparent ink films.
The ink vehicle can influence the opacity of an ink by its pigment dispersing properties and in
some cases by its intrinsic refractive index which can influence the amount and degree of light
scattering. Its interaction with the substrate can also influence the transparency/opacity of the ink
film.

The gloss of printing inks

The gloss of an ink is a measure of its ability to reflect incident light and depends to a large extent
on whether or not the ink forms a smooth film on the surface of the substrate and masks any
irregularities. When an ink penetrates a substrate it tends to lose gloss. The degree of gloss
depends on the nature of the colourant, its particle size, shape and surface characteristics and the
amount of resin and its ability to form a continuous film. In general the more resin that is present
in relation to the colorant, the higher the gloss will be. The choice of resin can also be critical to
gloss through its ability to disperse pigment the better the pigment dispersion, the better the
gloss. Also, thicker ink films will be more likely to hide substrate surface defects.
Solvent choice is also important in controlling gloss, as it can affect pigment dispersion, hold out,
the percentage of resin in the ink at its printing viscosity and the ink's flow characteristics. If the
solvent is not a true solvent, a poor flowing ink can result which can affect gloss. Careful control
of drying may also be needed to ensure optimum gloss development, as solvents that evaporate
too fast may cause poor flow out and loss of gloss. Alternatively, too slow drying on absorbent
stocks can lead to excessive penetration with-a resultant loss of gloss.
Additives such as plasticizers can often improve gloss by aiding ink flow and hence giving a
smooth film. Waxes, widely used in printing inks, tend to reduce gloss because they move to the
surface of the ink film forming an uneven profile which scatter the incident light, creating a matt
finish.

The nature of Printing inks as determined by the printing process:

The formulation of a printing ink and its physical appearance are determined greatly by the
method by which the image is produced and the transfer of the inked image on to the substrate to
be printed.

Flexographic and Gravure Inks:

Inks which are printed by the flexographic and gravure printing processes are characterized by
their extremely fluid nature. They are generally termed liquid inks.
The fluidity of gravure inks allows the recessed cells of the gravure cylinder to be filled rapidly:
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Similar fluidity is required for the flexographic process as the inking systems depend upon an
engraved cylinder metering the ink on to the raised rubber image. Both inking systems involve
only a short time and distance between the bulk volume supply of the ink and the accurately
metered film of ink on the printing image. Therefore, highly volatile solvents can be used and
most flexographic and gravure inks are fast drying and the ink is transferred to the substrate as
quickly as possible.
Liquid inks are printed on a wide range of substrates from absorbent stocks, where they dry by
absorption and evaporation, to nonabsorbent ones, where they dry through their film forming
ability and evaporation drying to which they are particularly suited.
Neither print process puts any significant constraints on pigment choice, but flexography requires
careful selection of the solvent which in turn limits the choice of resin systems. Resin choice,
together with specific additive selection, can influence the printability, with certain systems giving
better inking and transference.

[Liquid inks: Liquid inks are used in flexographic and gravure printing processes. They are
extremely fluid in nature and have viscosity less than 1 poise. The high fluidity of gravure inks
allows the recessed cells of the gravure cylinder to be filled rapidly and the ink is drawn by the
substrate by means of capillary action. The flexographic process also uses inks of high fluidity
since the ink is metered on to the raised rubber image via an engraved cylinder. In both inking
systems the distance between the bulk volume supply of the ink and the image carrier is very
short and the ink is transferred to the substrate very quickly. Liquid inks are, therefore, fast drying
and dry mainly by evaporation of the solvent (one of the constituents of the vehicle). The solvents
used in liquid inks are therefore highly volatile. The raw materials comprising a liquid inks are
generally pigment or dye, solvent, plasticizer and resin. Because low viscosity allows the pigments
to settle out, liquid inks are formulated at concentration higher than that required in the press. The
printer dilutes the ink with a suitable solvent in the press. ]

Lithographic and Letterpress inks

When compared to the fluid nature of f1exographic and gravure inks, lithographic and letterpress
inks are much more viscous and paste-like. Although the mechanisms of image generation of the
latter processes are very different, the thick nature of these inks is determined primarily by the
method by which the image is inked and then transferred to the substrate.
Both processes use a series of inking rollers which can meter accurately a very thin, uniform film
of this viscous ink to give the characteristic high image definition. Because of the time this lakes
and the large area of ink film exposed on the rollers, lithographic and letterpress inks have to be
formulated on relatively non-volatile solvents so that they do not evaporate during the long
transfer sequence through the roller chain on the press.
The choice of raw materials for lithographic inks, including pigments, vehicles and additives, is
greatly influenced by the printing process mainly because of the presence of water and the
planographic imaging technique used.
[Paste ink: Paste inks are used in letterpress and lithographic printing processes. They are highly
viscous (100-300 poise) and paste-like. Both processes use a series of inking rollers which can meter
accurately a very thin, uniform film of this viscous ink to the image carrier. Because of the time
taken and the large area of .ink film exposed on the rollers, lithographic and letterpress inks are

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made with relatively nonvolatile solvents so that they do not evaporate during the transfer of ink
over the rollers on the press. The inks are slow drying and dry mainly by absorption, oxidation-
polymerization and evaporation. The raw materials comprising a paste in are generally pigment,
solvent, resin, oil and drier(optional). Paste inks are made ready for the press and the printer
seldom adds anything to the ink. ]
Screen inks
In screen printing, the ink is forced through the open areas of a stencil supported on a mesh of
synthetic fabric, stretched across a frame. The ink is forced through the mesh on to the substrate
underneath by drawing a squeegee across the stencil. The Inks have to remain fluid and coherent
on the mesh before printing, transfer through the mesh without sticking it to the substrate, flow to
make the ink film continuous and so avoid the pattern of the mesh but maintain the image, and
then dry rapidly once applied to the substrate. Inks which are able to print by this method are
characteristically of household paint consistency. They are intermediate in viscosity between the
fluid, liquid, flexographic and gravure inks and the paste-like lithographic inks.

Screen inks can be formulated to dry by a variety of different methods depending upon the type
of substrate, which can range from absorbent papers and boards to non-absorbent plastics and
metals. The most widely used technique is evaporation, although there are limitations on the
volatility of the solvent which can be used. They tend to be intermediate between liquid and paste
ink in order to ensure adequate print definition and stability on the screen.

The Drying characteristics:

An ink in its supply form is a liquid but after application it is required to change to a solid. There
are many mechanisms by which the liquid ink is transformed into a solid permanent mark. This
change of state is referred to as ink drying and can be physical, chemical or a combination of both
processes.

Absorption drying:
An ink dries by absorption when it penetrates by capillary action between the fibres of a substrate
and also when it is absorbed into the substrate itself. The ink remains liquid but because of the
degree of penetration is effectively dry.

Oxidation drying:
An ink dries by oxidation when the oxygen in the atmosphere chemically combines with the resin
system converting it from a liquid to a solid. The system used generally depends upon
catalytically induced autoxidation. The process is relatively slow, taking several hours, and the
ink film will remain tacky for a long time. To overcome this problem on absorbent substrates, the
technique of quicksetting has been developed which combines absorption drying with that of
oxidation. The inks contain a fluid component which can separate from the rest of the inks and be
preferentially absorbed into the substrate leaving a film of ink on the surface which is dry to the
touch but still soft and moveable. However, as autoxidation proceeds, the ink film becomes hard
and tough.
The oxidation process can be affected by a number of factors, including pigments and additives,
as well as the printing process and the substrates. The inkmaker’s task is to produce carefully
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balanced formulations which ensure that high quality printing and high production speeds can be
maintained whilst the drying process proceeds at a satisfactory rate.

Evaporation drying
A wide range of ink is formulated to dry by the physical removal of volatile solvents from the ink
formulation, leaving the resin material behind to bind the pigment to the substrate. The rate of
drying depends upon the evaporation rate of the solvents selected and also the affinity of the
resin system for the solvents. Generally, the greater the affinity of the resin for the solvents the
slower the rate of solvent release. This can greatly affect the properties of the ink especially with
respect to printability, drying speed and retention of solvents in the ink film. Each type of ink
requires a very careful balance of properties if the characteristics of the ink are to meet the
requirements of the printing process and the end use of the printed article.

Chemical drying
There are other chemical reactions used by the ink maker beyond oxidation drying to convert a
liquid into a solid. Some systems comprise a polymersable compound which requires the
presence of a catalyst and sometimes heat to set off a chemical cross-linking reaction. Other rely
on the reaction of atleast two different chemical types which when mixed together combine to
produce a solid that binds the colourant to the substrate. Each of the various systems used has its
own specific conditions under which the chemical reactions occur and give the dry ink films
required. They can be two-part inks which have to be mixed prior to use and once mixed they
have limited usable life. Alternatively, systems are available which are stable under normal
ambient conditions. When in use, the chemical reaction is initiated and the process turning the
liquid to a solid proceeds.

Radiation induced drying

There are several forms of radiation used to dry inks. These include ultraviolet radiation, infra-
red, electron beams, microwave and radio frequency. Each drying method determines the
chemistry of the ink vehicle and the nature of the printing ink used.
Ultraviolet or UV: drying employs a process known as photopolymerisation; UV inks contain
photoinitiators which absorb UV radiation and in so doing produce highly active chemical
compounds known as free radicals. These free radicals initiates chain reaction with the ink
vehicle, which rapidly polymerizes and changes from a fluid to a highly cross-linked solid, the
dried ink film. While there are other photochemical reactions which can be used as the basis of
UV inks, the majority dry by this mechanism. It is the rapid cure of UV that is its major benefit
and this has been exploited principally in the lithographic printing of cartons to eliminate the
extended drying of the autoxidation process.
Short and medium wave infrared radiation is used as a means of efficiently providing heat and is
widely used to bring about the evaporation of volatile solvents. It can also be applied in
lithographic printing to assist penetration and to speed up the autoxidation of conventional quick
setting inks.

Electron beam: is similar to UV but uses a beam of high energy electrons to generate the free
radicals needed to bring about rapid polymerisation of the ink vehicle. Inks cured by this
technique are very similar to UV inks but do not include photoinitiators.
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Microwave and radio frequency radiation: are used to dry inks that contain a high proportion of
very polar molecules such as water. Radiation is absorbed by the polar molecules and the ink
heats up very rapidly. The water evaporates and leaves a solid ink film behind.

Quick-set:
Whilst quick-set drying is usually associated with sheetfed lilhography, both heat-set and cold-set
formulations use the mechanism for part of their drying. The quick-set vehicle consists of two
phases which have limited compatibility. One phase is a suspension of resin in drying or non-
drying oil, the other phase is low viscosity mineral oil or high boiling range petroleum distillate.
The two components must remain stab1e and compatible to enable pigment dispersion and
printing to take place. However once printed on an absorbent stock, the capillary action of the
stock draws in the low viscosity phase leaving the high viscosity phase on the surface. After the
print has set oxidation/polymerization drying can take place within any drying oils or alkyds
present. Both heat-set and cold-set formulations do have a degree of quickset mechanism as the
formulations often include varnishes and oils which have a much-higher viscosity to the reducing
solvents used to reduce the viscosity.
Heat-set:
Heat-set inks dry by evaporation of the solvent phase in high temperature ovens. The solid phase
is usually a high viscosity colloidal suspension of resins and alkyds in low viscosity drying or
semi-drying oils. These varnishes are reduced in viscosity by petroleum distillate, usually in the
260-330°C boiling range. The high temperatures (up to 50°C) that can be encountered on the roller
train of high speed presses necessitate the use of non-volatile solvents. However the lighter
fractions can evaporate at these temperatures causing possible increases in ink tack and viscosity
and it is necessary to formulate to prevent this happening.
It is the correct balance between press stability and fast drying in the ovens that is the key to the
success of heat-set web offset inks. The use of latent solvents with low resin solubility improves
solvent release from the ink film. Other additives such as slip aids and waxes may also have a
detrimental effect on drying, causing a thin layer of wax to form on the surface of the ink film
which retards solvent evaporation, due to the solvent retention properties of waxes.

The adhesive nature of printing inks:

One of the fundamental functions of an ink is that it adheres and binds the colourant to the
substrate on which it is printed and keeps it there during the lifespan of the printed product.
Colorants have little or no effect on the adhesive nature of the inks although if they are not
adequately bound by the vehicle, may be because of poor dispersion, the ink will not exhibit good
adhesion.
It is the type of resin used in the ink that will determine its adhesive characteristics. On absorbent
substrates, adhesion is influenced by the degree of ink penetration. Pigments do not tend to be
absorbed and if too much of the resin is drawn into the substrate, this can leave the pigment
underbound. Under these circumstances, the pigment can powder off.
On non-absorbent substrates, adhesion is primarily controlled by the film forming ability of the
resin and its molecular affinity for the substrate. The choice of resin for a specific substrate is
therefore extremely important, although its performance can be modified by applying other
techniques. The correct blend of solvents can influence adhesion by creating better wetting of the
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substrate and improved flowout. Some solvents can actually be used to soften the surface of the
substrate enabling the ink film to key more readily. Adhesive properties can also be influenced by
using surface active and chemical additives. Such materials modify the surface of the substrate
either through chemical reaction or by physical interaction.

The Resistance properties of printing ink:

All inks have to resist certain forms of chemical and physical attack during their lifespan. Firstly,
the raw materials must withstand the manufacturing process used to make the ink in the first
place. Having manufactured the ink, it must be able to withstand the rigours of the printing
process. For example, it may have to perform under conditions of high shear and in the presence
of fount solutions in lithographic printing.
After printing, the ink may then have to withstand cutting, creasing gluing and forming before the
printed article is finally completed and ready for use. The ink film may then be subjected to new
influences such as filling with abrasive products and heat sealing with heated jaws in direct
contact with the ink film. The ink may also have to withstand the chemical nature of the packaged
product or the environmental conditions in which it is placed. By their very nature, inks need to
have specific chemical and physical resistance properties.

Lightfastness
The degree of resistance to light will depend on the exposure, application and life expectancy of
the ink. The action of light can cause a colour to become weaker, dirtier and/or change its shade.

The light resistance of an ink is primarily determined by the lightfastness of the colourant used.
Colourants can be placed in broad classes of lightfastness and before attempting to use a
colourant in any application, its lightfastness against a shaded scale. i.e. blue wool scale, should
be checked. A few pigments, including carbon black, ultramarine and some iron oxides, can be
considered permanent, but the remainder are all to
some extent fugitive.

In general, lightfastness of a pigment decreases with its degree of dilution by other pigments,
especially white. Highly concentrated coloured inks have batter resistance to light because of the
self masking action of the pigments. Hence inks of pastel shades are generally not as lightfast as
the stronger colours.

The lightfastness of a colourant will vary according to the type of resin into which it is dispersed.
The amount of resin used can also have an effect on lightfastness. In general, the greater the
amount of binding material present the better is the resistance to light. Thus screen printing,
which can print a thick film of ink with a high ratio of resin to colourant, produces the most
lightfast image of all the printing processes.

Heat resistance
Printed packages sometimes have to resist excessive heat in their processing or application and
the choice of resin and pigment are both critical to the heat resistance properties of the ink.
Pigments vary in their ability to resist heat. Heat can dirty a colour, cause strength loss and alter
shade. Pigments must be evaluated and chosen so that they will with stand temperatures

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encountered both during manufacture and end use of the printed article.

Abrasion resistance
Most printed articles are subject to different forms of rub and abrasion during their life cycle. All
types of printing inks are formulated with this in mind.

The degree to which a dried ink film can resist abrasive forces depends greatly on the degree to
which the pigment is bound. The more resin that is present the greater is the ink's resistance to
abrasion, and the hardness and flexibility of the ink film will affect its ability to withstand
abrasion and mechanical wear. Additives such as waxes, which promote surface slip, are used
extensively to increase the scuff resistance of inks. By their very nature, most printing inks contain
some wax of some kind.

Product resistance
Ink in its many applications in the packaging field has to be able to withstand contact with the
substances packaged. Colourants vary widely in their resistance to acids, alkalis, oils, fats,
detergents and other substances and must therefore be selected with the end use of the ink in
mind. Resins also have differing resistance properties and must be evaluated in conjunction
with the colourants to determine their suitability for a particular application. Specific additives
can be used to impart specific product resistance properties. For food packaging work, ink
components must be selected to avoid odour and taint problems.
Weathering
An ink will have to withstand attack from physical and chemical forces when it is exposed to the
weather, or chemical elements. Pigments must be selected for resistance to the environment and
in the case where specific chemical contaminants are present, it is essential to choose pigments
which will resist these. Some pigments become more fugitive when exposed to moist or acid
conditions. Attempts to correlate accelerated weathering tests with actual conditions are
continuously being made, but in general they can only be used as a guideline. Reliable ink
formulations are arrived at by careful selection of both pigments and binders, in combination
with detailed formulation experience.

Raw material:

Materials have been grouped under the following headings:

1. Colourant (Pigment, Dyestuff)
2. Vehicle
2.1. Solvent
2.2. Resin
2.3. Oil
2.4. Additives
2.4.1. Drier
2.4.2. Plasticizer
2.4.3. Waxes
2.4.4. Wetting agents
2.4.5. Antisetoff compounds
2.4.6. Shortening compounds
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 2.4.7. Reducers
2.4.8. Stiffening agents
2.4.9. Antiskinning agents
2.4.10. Defoamers for aqueous inks.

Pigment:

Pigments are finely divided particles relatively insoluble in the medium in which they are
employed. These particles when adequately dispersed in the medium absorb and scatter light. If
the absorption is selective, the pigment will be colored. Pigments may be entirely inorganic or
organic; they may also be metallic (usually calcium or barium) salts of complex acids or consist of
organic dyes laked on to inorganic substances.

A wide variety of pigments is available for use in printing inks. Many are usable in inks
for every process, although a few are suitable only for lithographic inks and some others
are suitable only for non lithographic inks.

Lithographic printing usually deposits a thinner ink film than other printing processes.
To obtain sufficient color strength on the printed material, lithographic inks must be
more highly pigmented than other inks.

It is convenient to divide pigments into four classes: carbon black, organic pigments, white
inorganic pigments, and colored inorganic pigments.

Carbon Black:
Most important black pigments. All types of carbon black are included under the above
classification. They are pigments of extremely fine particle size, with colour varying from a
grey masstone with blue undertone, to a dense jet black masstone with brown undertone
dependent on the method of manufacture. Non-rubber varieties, used in printing inks, are
produced in pellet, bead, densed or fluffy form. They are chemically inert, extremely fast to heal,
light, acids, alkali, solvents and soap. Most grades however do contain a small Proportion of
volatile material, the effect of which may become apparent on dispersion.

Furnace black

Almost all carbon black is today produced by the furnace process, and most of this production is
allocated to the rubber compounding industry for vehicle tyre manufacture. Some is produced by
the slow vertical process in which oil is sprayed and burned under controlled conditions. The
carbon is collected by cyclonic or electrostatic methods. Finer blacks are manufactured by a faster
vertical process, where hot gas and oil are combined under pressure to disintegrate or crack.
Carbon Black produced by this process is not exposed to air and therefore absorbs little oxygen.
Newer types of treated furnace black have replaced channel black in most applications. They
undergo a further process which bonds them with oxygen and other surfactants to obtain required
surface characteristics.

Channel Black

Now produced in only a few locations throughout the world as it requires natural gas, which is
more valuable as fuel than as a source of Carbon Black. Natural gas consists of a mixture of
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gaseous hydrocarbons, predominantly methane. It is burnt in a series of small luminous flames
which impinge on a water-cooled inverted-U-shaped channel. A layer of fine Carbon Black is
deposited. The particles are continuously removed by scrapers and conveyed to beading, densing
and packaging plant. They have a dense black appearance with brown undertone. Channel blacks
possess good wetting characteristics. They have a high oil absorption caused by their porosity and
very large surface area. This wetting is aided by the low pH that channel blacks normally have,
caused by the formation of a volatile absorbed layer of between 10 and 15% by weight, including
moisture. Oxygen absorbed during manufacture can be chemically bonded to produce 'long flow'
channel blacks having optimum colour, density, flow, gloss and dispersion. A disadvantageous
effect of Channel Black in inks is the tendency to absorb both driers and alkali blue toner over a
period of time.

Lamp Black

Creosote and tar residues are burned in a hooded flue, with a limited amount of air, to a smoky,
sooty gas. It was formerly allowed to settle in cooling chambers, to be swept and bagged. Today
it is normally collected by more modern methods. It has a large particle-size compared with
channel black and it flocculates to form chain-like structures.
Formulation of carbon black: Carbon 90-99%
Volatiles 1-10% . Almost pure carbon.
Organic Pigments:
The growing demand for process color printing makes these pigments increasingly important.
Organic pigments provide a wide selection of colors. Many have high color strength, and inks
made with them print clean tones. Most of them have a low specific gravity and small particle
size that help produce inks with good working properties. Most organic pigments are easily
wet by varnishes-more easily than with water, which is essential for lithographic inks. Most
organic pigments are easy to grind, and they produce inks with low abrasion characteristics.
Some organic pigments cause problems. A few produce inks that are short; it is necessary to
remedy this with the proper varnish or extender. Pigments that dissolve or bleed into water
and pigments that are easily wet with water are unsatisfactory for litho inks. Some pigments
sublime (change from a solid to a vapor) because of the heat generated in the delivery pile. The
vapor may transfer to the next sheet or even penetrate several nearby sheets before it cools and
resolidifies, producing a tint of the pigment. Sublimation is usually undesirable, but heat-
transfer printing inks for textiles require pigments that sublime.

If a pigment and varnish into which it is ground have nearly the same index of refraction, a thin
film of the resulting ink is transparent. If the index of refraction of the pigment and varnish are
widely different, a thin film of the resulting ink is opaque. Inorganic pigments usually produce
opaque inks because their refractive index is much higher than that of the organic varnishes that
carry them. Organic pigments usually produce transparent inks, used for process colors. If opacity
is required, an opaque pigment such as titanium dioxide must be added.

Chemical structure:

The chemistry of organic pigments is very complicated. Most of them are derivatives of
benzene, naphthalene, or anthracene, all of which are carbon ring compounds. Some
pigments contain four or five rings in one molecule. In addition, pigment molecules contain
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certain groupings of atoms, called chromophoric groups, which are responsible for the
pigment color. Examples of such groups are =C=NH,-CH=N-, and –N=N-. These
chromophoric groups must be in such positions in the molecules that the electrons can
change energy levels when they are illuminated. The aromatic rings are major contributors to
the chromophore. Electrons in the chromophoric group may exist in several energy levels,
and when white light strikes a film of ink containing an organic pigment, electrons change
energy levels, absorbing specific wavelengths of light. The pigment color is due to the
wavelengths that are not absorbed by the chromophoric group but instead are reflected to
the viewer’s eyes.

A dye is soluble in common solvents, while a pigment is insoluble. Pigments are usually
preferred in printing inks to prevent bleeding of the printed product. Dyes are converted to
pigments through several different chemical reactions.

Basic dye pigments are made by reacting basic dyes with phosphomolybdic acid
(H3PO4.12MoO3) or phosphotungstic acid (H3PO4 .12WO3). When reacted with both, they are
known as PMTA pigments. The resulting pigments have good fastness to light, yet still have
strong, brilliant colors. Pigments in this group include the rhodamines, Victoria blue, and the
red, violet, blue, and green PMTA pigments.

Azo pigments are a large group of organic pigments. They are made by a chemical reaction
between an aromatic amine and nitrous acid, followed by a coupling of the diazonium salt.
Azo pigments include diarylide yellow, lithol rubine, red lake C, toluidine red, Hansa
yellow, DNA orange, and naphol red.

The most important cool-shade ink pigments are the phthalocyanine pigments, which
include cyan blue and cyan green. Copper phthalocyanine, called phthalocyanine
blue, phthalo blue, or cyan blue, is produced in two shades, one called red-shade and
the other green-shade cyan blue. The green-shade cyan blue makes an excellent cyan
for process color work. If chlorine is introduced into the molecules of cyan blue, the
result is a brilliant green pigment, called cyan green. This, too, is produced in two
shades. All the phthalocyanine pigments are fast to light and alkalies. They are highly
insoluble, resisting bleeding. Inks made with them dry easily. Phthalocyanine
pigments are made by heating phthalic anhydride with urea and cuprous chloride,
Cu2Cl2.

Flushed pigments:

Organic pigments for printing inks are usually prepared as flushed pigments. The color is
commonly prepared as a dye, then converted to a pigment by precipitating from a water
solution. The mixture is filtered, washed, and pressed to remove most of the water. The
water in the wet pigment filter cake (also called press cake) can be removed by a process
known as flushing. The wet pigment is mixed with a viscous varnish, such as a linseed
alkyd, in a large dough mixer. The varnish gradually replaces the water adsorbed on the
pigment surface, and the pigment passes from the aqueous phase to the oil phase. The
displaced water collects during the mixing operation and can he poured off by tilting the
dough mixer. The rest of the water is removed by heating under vacuum. The mixture
remains very short until practically all of the water is removed, when it suddenly changes
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to the consistency of a heavy-body paste ink. The flushed pigment is sold in this form to
the ink manufacturer.

Flushed pigments have advantages and disadvantages. Flushed pigments do not contain
grit or unground, dry particles, and they are easily mixed with other ink ingredients. They
have high color strength and low moisture content.
Some pigments, such as alkali blue, dry to a hard horny texture with reduced color
strength when prepared as a dry pigment. Flushed pigments suffer a lack of flexibility in
vehicle formulation, the requirement of a relatively large inventory to ensure uniformity of
color, an opacity insufficient for many uses, and a number of color and body changes that
occur during manufacture and storage. Organic pigments are commonly flushed with an
alkyd or rosin ester varnishes. The use of such flushed pigments improves the fast-setting
properties of quickset inks.

Dry Color:

If instead of flushing, the filter cake is dried in an oven, and crushed and ground, the
powdered product is referred to as dry color. These must be ground with a varnish to
prepare a printing ink.

Pigment chips:

In addition to dry color and flushed pigment, pigments are sold in the form of chips,
pigment dispersed in a solid resin. Chips are mixed into solvent or varnish to dissolve the
resin binder, dispersing the pigment and making the ink. Chips are usually used for
preparing liquid inks-flexo and gravure inks--for packaging. They produce inks with
exceptional color strength, transparency, and gloss.
Pigment chips containing an organic pigment (60% by weight) in acrylic resin (40%)
produce water-based flexo inks with greater gloss, transparency, and color than inks from
dry color. Use of these chips is more costly than the more familiar dispersions that are let
down (diluted) to form a press-ready ink.

Coated or Rosinated Pigments

Pigment suspensions are usually treated with rosin or a rosin derivative before the
pigment is made into a press cake. Flushing or drying causes the rosin to coat the
individual particle, improving transparency of the pigment and giving a darker
masstone to the ink. The pigments are also called "rosinated" pigments. (A resin is an
amorphous, translucent, fusible, or thermoplastic substance; rosin is a natural resin
obtained from pine trees.)

White Pigments

The major white pigments are titanium dioxide, calcium carbonate, and clay. There are
no white organic pigments.

The most Important white pigment is titanium dioxide, TiO2. It is insoluble and
chemically inert with excellent resistance to heat and light. It comes in two crystalline
forms, anatase and rutile. Rutile is bluer, more opaque, and harder than anatase. Rutile is

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used to make opaque tints from
transparent inks. Anatase is preferred in gravure inks because it is less abrasive. Many
grades are available.

Calcium carbonate (CaCO3) is available as ground limestone or as precipitated calcium

carbonate. Ground limestone, available in many grades, ranges from very hard to soft.
Printing inks usually use the precipitated form, a product with controlled, uniform
properties, which is made by reacting a solution of calcium hydroxide (lime)
with carbon dioxide.

CaCO3 CaO + CO2

CO2 + Ca(OH)2 CaCO3 + H2O

Clay is a complex aluminosilicate, found extensively in nature. The hexagonal platelike

form, kaolin, is the principle fom used in printing inks. It has low opacity and is used
largely as an extender for letterpress and screen inks.

Like calcium carbonate, clay, treated clays, fumed silica, and barium sulfate are
sometimes used as extenders. Other white pigments, such as alumina hydrate, gloss white,
magnesia, and zinc oxide are rarely used in printing inks.

Inorganic colored pigments:

Before discovery of the synthetic organic dyes in the mid-19th century, printers and
painters had only inorganic pigments and natural dyes extracted from plants and some
animals. The inorganic pigments were usually dull and dirty in hue, while the organic
pigments were costly and fugitive to light.

Most of the colors used now are synthetic organic colors, which have overcome the disadvantages.
Some old inorganic colors are still used, and many new synthetic inorganic colors have been
developed.

The principal colored inorganic pigments used in printing inks are the iron blues. While the
iron blues have different shades, they are essentially the same chemically, consisting of
ferric ferrocyanide. They are produced by adding a solution of potassium or sodium
ferrocyanide to a solution of ferrous sulfate. A light-blue precipitate of ferrous ferrocyanide
is formed:

K4Fe(CN)6 + 2FeSO4 Fe2[Fe(CN)6) + 2K2SO4

The light-blue precipitate is converted into a deep-blue precipitate of ferric ferrocyanide

by the addition of hydrochloric acid (HCl) and an oxidizing agent such as sodium
dichromate (Na2Cr2O7) or sodium chlorate (NaClO3). The net effect of this reaction is to
oxidize the ferrous ion, Fe2+, to ferric ion, Fe3+. The oxidation changes the precipitate to
ferric ferrocyanide Fe4[Fe(CN)6]3. The different shades of iron blue are produced by
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changing the acidity of the
solution temperature, and
heating time during the
oxidation.

The iron blues are lightfast and

have high tinctorial strength,
but less than that of some
organic blue pigments. Dilute acids do not affect iron blues, but alkalies destroy their
color. They may be mixed with most other pigments, except those that are reducing
agents or are alkaline in nature. The iron blues include Prussian blue, bronze blue, Milori
blue and Chinese blue.

In the past, chrome and lead pigments have been used (chrome yellow, molybdated chrome
orange, and others), but the potential health hazards and the problems of disposing of
materials containing lead and chromium have virtually eliminated their use in printing
inks. They have been replaced in
most applications by organic pigments.

Pigment Flocculation and Bleeding :

A good pigment consists of very tiny particles. These are dispersed throughout the varnish
when the ink is ground on an ink mill. If something causes these particles to clump together
to form fewer but larger particles, the pigment is said to flocculate. Flocculation may occur
when a lithographic ink contacts water on the press. If a pigment flocculates, the ink
becomes short or pasty, causing stripping of the ink from the ink rollers and piling on
rollers and plate. Luckily, most pigments do not flocculate.

Pigment flocculation may be explained as follows: pigment particles are surrounded by

an adsorbed film of varnish molecules, even after the dampening solution becomes
emulsified in the ink. Some pigments, however, are more easily wet with water than
varnish, and in the presence of water, they take on an adsorbed film of water. The
pigment particles then become more polar, since water molecules are highly polar. Polar
particles have an electrical attraction for each other, and they join together or flocculate.

Pigments for lithographic inks must be chosen so that they do not bleed into the
dampening solution-they must not be soluble in water or in dilute acid solutions. This
requirement is no problem with inks for other printing processes, where the inks do not
come in contact with water.

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Fluorescent Pigments:
There is sometimes confusion between luminosity, fluorescence and phosphorescence. A
phosphorescent material is defined as one that has the ability to emit light in total darkness,
following Pigment dispersed, ink Pigment flocculated, inkexcitation by various
light sources. relatively fluid no longer flows readily

Feature Activated by After-glow

Phosphorescence Any light source 2 hours
Fluorescence UV light None
Luminosity Radioactive chemicals Long

Fluorescence is a process of photo-luminescence by which light of short wavelengths, either in the

UV or visible regions of the electromagnetic spectrum, is absorbed and reradiated at longer
wavelengths. This re-emission occurs within the visible region of the spectrum and is manifested
as colour. Fluorescent pigments are transparent organic resin particles containing dyes in solid
solution. These comprise various yellows, oranges, reds and greens and a single blue.

Properties
Powders are created by pulverizing solutions of fluorescent basic or reacted dyes in resins.
Therefore they can be unstable, not very heat resistant and able to be ground away in dispersion
equipment. Dazzlingly bright colours giving a fluorescent effect in daylight. Mainly in the yellow
orange and red portions of the spectrum. They appear most brilliant in the dark with a UV source
of radiation to illuminate them. Fluorescent dyes/daylight pigments powders have the property
of converting short-wave visible radiation into longer wavelengths giving very brilliant colours.
Blue, indigo and violets are extremely rare for daylight fluorescence.

Uses
Any type of printing advertising and packaging where the effect is strongly to catch the eye. The
drawing power of fluorescent displays, e.g. price-changes, or warnings or sheer attraction (e.g.
soap powder boxes) to the product can lead to requests for fluorescent printing inks. Their use
was confined until the 1960s to screen inks for poster work but, more recently, all the properties
have been improved, so by the late 1970s fluorescents were used in litho, letterpress, flexo and
gravure systems. Their stability has improved and they can be heat resistant up to 2000C in some
cases; light fastness has also been considerably improved. Due to the range of inks for printing
purposes most reds, yellows, greens and orange fluorescents are available each one in about 8–10
different forms. Useful for safety labels, greeting cards, price changes and brilliant tri-chromatic
inks.

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Metallic Pigments: (Refer Class notes)

Aluminium
CI Pigment Metal 1;
Properties
Brilliant silvery powders (called linings) or pastes which have high hiding power. Some tend to
tarnish on exposure and they will not resist alkali or acid. They are inert in hydrocarbon solvents.

Uses
Non-leafing grades are used as linings or pastes in all types of ink, either alone or with another
colour to produce a ‘metallic’ colour effect. Many hundreds of ready-made pastes are available on
the market these days, suitable for all types of manufacture. One of the latest innovations are
water-stable silvers for aqueous flexo use.

Copper Powder, Bronze Powder

CI Pigment Metal 2;
Properties
Brilliant reddish gold to greenish gold; copper or copper–zinc alloys prepared for printing use.
Available in many grades differing in particle size, leafing and covering power. Coarser powders
generally are brighter while finer powders are matter and more opaque. Special non-tarnish
grades for all types of printing are now available already pasted into different oils, solvents, or
media. They are sensitive to heat, humidity, and either strong acid or alkaline media. Stabilized
paste forms should be used when possible.

Uses
Decorative printing inks, particularly for packaging, mostly on paper. Manufacture and formula
Powder, flaked by ball or stamp milling with stearic acid for leafing grades or other fatty acid
lubricants for the non-leafing grades. The shade depends on the composition of the alloy.

Colour Copper (%) Zinc (%)

Copper 100 0
Pale gold 90 10
Rich pale gold 85 15
Rich gold 80 20
Green gold 70 30

Dyes:

If the coloring agent is soluble in the medium in which it is being used, it is called a dye. Dyes are
normally pure organic or metallo organic complexes. The color of a dye is produced by selective
absorption but since no discrete particles are present, no scatter occurs and the system is
transparent.

Dyestuffs are largely used in liquid inks, coatings and lacquers. Special disperse dyes are used in
both liquid and paste inks for heat transfer printing. In this application the choice of printing
process is of minor importance compared with the subsequent operation of transferring the

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dyestuff from paper to the textile by sublimation. Other dyestuffs used in paste inks include acid
dyestuffs for double tone and invisible inks, but by far the largest use has been in cheque security
inks. Basic dyestuffs in the free-base form dissolve in fatty acids to form oil-soluble toners and can
be used as toners for black inks.

In order to distinguish between the various types of dyestuff used increasingly in printing inks it
is advisable to consult the Colour Index published by the Society of Dyers and Colourists jointly
with the American Association of Textile Chemists and Colorists. Dyes are classified for specific
usage and may be included in more than one entry; for example, food dyes include acid, solvent
and natural dyes as well as pigments. This is followed by a classification of dyes by chemical
composition and a comprehensive alphabetical index.

The classification used in the Colour Index is:

Acid dyes Leather dyes

Azoic dyes Mordant dyes
Basic dyes Natural dyes
Developers Oxidation bases
Direct dyes Pigments
Disperse dyes Reactive dyes
Fluorescent brighteners Solvent dyes
Food and drug dyes Sulphur dyes
lngrain dyes Vat dyes

Acid Dyes:

The name 'acid dye' was originally used to indicate the presence of sulphonic acid or other acidic
groups in the molecular structure. However, since acidic groups are present in other types of dye,
their presence is not a sufficient distinguishing factor. They are regarded as anionic dyes, soluble
in water, mainly insoluble in organic solvents. Selected dyes are soluble in alcohol, ketones and
esters. They give very bright hues, with lightfastness ranging from poor to very good.

Chemically they are azo, anthraquinone, triphenylmethane azine, xanthenes, ketonimine, nitro
and nitroso compounds. For example eosin is a red dye with poor lightfastness.

The most popular acid dyes in current use in ink manufacture are:
Acid Yellow, Acid Orange , Acid Red , Acid Green; Acid Blue, Acid Violet etc.

Basic Dyes:

The first dyes produced from coal tar were basic dyestuffs. These cationic dyes have maintained
popularity with the printing ink industry due to their brilliant shades and high tinctorial strength.
However, their lightfastness is poor and curtails much of their usefulness. They are soluble in
water and alcohol, but have low solubility in most other organic solvents.

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These dyes are often used in conjunction with a mordant or laking agent such as tannic acid,
usually in amounts equivalent to weight of the dye. This lakes the dyes in situ and not only fixes
the dry ink, but also makes it more water resistant and helps the dye to develop its full colour and
strength. Rhodamine B, Auramine, Victorian Blue and Methyl violet are few examples.

Solvent Dyes:

Often known as metal complex dyes. These are dyes in which solubility in all organic solvent or
solvents is a characteristic physical property. They are drawn from a number of chemical groups
and include what are sometimes described as oil dyes or fat dyes. The chemical constitutions
associated with solubility in organic solvents include acid dyes of the azo chromium complex.
xanthene classes and the base salt form of certain basic dyes, sulphonic acid groups are usually
absent, but dyes soluble in alcohols include salts formed between sulphonated dyes (usually
sulphonated azo or phthalocyanine and organic high molecular weight bases such as diaryl-
guanidine, mono and di-cyclohexylamine and di- isoamylamine).

The properties of these dyes are strongly Influenced by their solubility in a particular solvent, so it
is usual to use mixed solvents to obtain the optimum solvency and properties. The range of
extremely bright colours with fair lightfastness makes them popular in a number of applications
like golds on foil and uses where better lightfastness than that of a basic dye is required. They are
generally used in flexographic and gravure printing inks. Some examples are: C1 Solvent orange,
Neozapon Yellow, Induline (spirit soluble), Nigrosine (free base) etc.

Disperse Dyes:

All disperse dyes are primary, secondary or tertiary amines of three main types: amino azo
benzene, aminoanthraquinone, and nitrodiaryl amines. None of these contains solubilising
sulphonic acid groups. A limited number are similar in structure to vat dyes.

Their main use in the printing industry is in heat transfer inks for printing on textiles, especially
on to synthetic fibres. It is referred to either as heat-transfer printing, or sublistatic printing. The
dyes are dispersed in a printing vehicle and printed on paper by letterpress, lithography,
flexography, gravure or screen printing. They are subsequently transferred to the fabric under
heat and pressure. The dye sublimes and its vapour phase penetrates the fabric where it
condenses. Bright, saturated colours result relative to the substantivity between dye and fibre,
implying chemisorption or chemical bonding to the fibres.
There are hundreds of dyes of this type, and many of them are used in commercial heat transfer
printing. It should be noted that disperse dyes do not necessarily transfer with the same strength
or hue on every fibre even when the optimum temperature and pressure for the particular
substrate are applied, also that mixtures of disperse dyes can, under certain conditions, have a
catalytic effect which may cause premature fading. Sublistic transfers can also be printed to
transfer images to thermopastics, metal, carpets and plastic bottles. Sometimes the dye vapour is
made to cross relative large gaps (1 cm) with the assistance of vacuum. Some examples are: CI
Disperse Yellow 3, CI Disperse Red 4, CI Disperse Blue 3 etc.

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Solvent: Refer class notes.

Oils:

There are three kinds of oils - fatty oils, petroleum or mineral oils and essential oils. The essential
oils are volatile oils with pleasant odour and obtained from various plant exudes and flowers by
steam distillation. Petroleum oil or mineral oils are obtained from crude petroleum by fractional
distillation. Fatty oils are obtained from vegetable and animal sources. They are known as fatty
oils because chemically they belong to the same class of compounds as the fats. Fats and fatty oils
are esters in which the organic acid portion is a fatty acid and the alcohol portion is glycerol. A
fatty acid contains a saturated or an unsaturated alkyl group and a carboxyl group. Since there are
three hydroxyl groups in a glycerol molecule, three molecules of a fatty acid react with one
molecule of glycerol to form the glyceride. Some of these glycerides have high m.p. and are
obtained as solids in the tropical regions. They are called fats e.g. butter-Again, some glycerides
have low m.p. and exist as liquids even in cold countries. These are called fatty oils or simply oils.

The principal fatty acids are stearic acid (C17H35COOH), oleic acid (C17H33COOH), linoleic acid
(C17H31COOH), and linolenic acid (C17H29COOH) and the fat molecules formed are (C17H35COO)3
C3H5, (C17H33COO)3 C3H5, (C17H31COO)3 C3H5, (C17H29COO)3 C3H5 respectively. Stearic acid is a
saturated acid. Oleic acid, linoleic acid and linolenic acid are unsaturated acids with one, two and
three double bonds respectively in a molecule. .
An important property of unsaturated fatty oils is their ability to absorb oxygen from the
atmosphere and polymerise to form elastic films. The amount of oxygen absorbed depends on the
degree of unsaturation in the alkyl groups and this is determined from a measure of the iodine
value of the oil.

Iodine value is defined as the weight in grams of iodine that will combine with 100gms of oil. It is
thus regarded as the measure of the extent of unsaturation of the fatty acid present and indicates
the drying power of an oil. Oil varnish of printing inks dry faster if they contain a high degree of
unsaturation.

Based on their iodine values, oils are classified as drying, semidrying and non-drying oil. A drying
oil is one that contains a large percentage of fat molecules of unsaturated fatty acids. Linseed oil
(I.V.170-205) and tung oil (I.V.-170-187) are examples of drying oil. Linseed oil contains 61.5% of
linoleic acid and 25% of linolenic acid and is widely used in paste inks. Without driers they take
almost a week to dry. Although a high iodine value is an indication of rapid drying ability of an
oil, it is not the sole criterion for quick drying.

The main semidrying oils are sunflower oil (1.V 120-140) and soyabean oil (1. V 103-152). They are
used almost extensively with synthetic resins mainly alkyds. Alkyds modified with semidrying
oils are usually more flexible, are often lighter in color and have better color retention than drying
oils.

Castor oil containing 80 to 87% of ricinoleic acid, oliv oil containing oleic acid and
mineral oil are example of non drying oil.

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Mineral oils are the fractions obtained during refining of crude petroleum above 3500C at
atmospheric pressure. They contain hydrocarbon solvents of high molecular weight and
greater viscosity than heatset oils.They are used alone or in conjunction with rosin
derivatives in newspaper inks.

Heatset oils are linear and alicyclic hydrocarbons obtained by careful fractionation of
petroleum. They are fully hydrogenated at high temperature and pressure in the presence of a
catalyst to convert the olefins into saturated hydrocarbons and the aromatic hydrocarbons into
alicyclic hydrocarbons as unsaturated hydrocarbons may give rise to smoke and may be
carcinogenic. They have b.p 200-3000C and are used to make heatset inks.

News-ink oils
The essential requirement for news-ink oil is that it should be inexpensive. Also it must show
good wetting and dispersion characteristics so that it can produce an ink which has sufficient flow
properties without flying or misting, together with good binding qualities, adequate penetration
and speedy setting. The oils that fulfill these requirements are dark brown mineral oils, some of
which are fairly viscous, but for normal newspaper black inks a viscosity of between 0.8–1.0 Pa s
at 210C (700F) is recommended. Such a viscosity gives a reading of about 4000 seconds on a
Redwood No. 1 and 400 seconds on a Redwood No. 2 viscometer, which are the instruments
normally used in the UK for measuring the viscosity of lubricating oils. The more viscous oils are
measured on similar instruments at temperatures of 600C (1400F) and 93.30C (2000F). The flash
point for such oils ranges from about 1590C (3500F) to above 2000C (4000F).
Test methods vary with suppliers and are covered both by the Institute of Petroleum (known as IP
Standards) and the American Society for Testing Materials (ASTM Standards).
Mineral oils used in inks for newspaper production have fairly high aromatic contents, which
may be as low as 22% but can be double that figure. The balance is made up of naphthenes and
paraffins as well as small percentages of other unsaturated polycyclic and olefinic hydrocarbons.
News ink oils have to be produced at very low cost and are made in specialized refinery process
using selected feed stocks of lower petroleum distillates or residues, which give products with a
relatively low aniline point. As these are products with a high flash point they do not present
handling or storage problems. Recent tests have indicated that there may be some health hazards
associated with these oils, especially in the fine mists around the rollers of a fast-running press.
Certain oils therefore are no longer used. Precautions should be taken to avoid prolonged skin
contact with any aromatic petroleum oils.

Oil imparts the properties of drying, elasticity, toughness, adhesion, durability and tack to
the printing ink.

Resin:
Resins are amorphous solids with high molecular weight. They are binders for pigments and
contribute to the properties of adhesion, hardness, gloss and flexibility in an ink.
Resins are of two types - natural and synthetic. A few naturally occurring resins are used in the
preparation of ink vehicles usually after some chemical modification. Most natural resins are
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obtained from vegetable matter. Shellac is an exception. It is obtained from the secretion of an
insect. Synthetic resins are prepared by condensation or addition polymerization.

Natural Resin:
Rosin is an example of natural resin. It is obtained from pine trees. In its natural state rosin
consists of approximately 90% acids & 10% neutral material. The principal acid is abietic acid.

Abietic acid has two reactive centres - a carboxylic acid group and a conjugated diene. About three
quarters of the resin is present in dimeric and one quarter in monomeric form. It is mainly used to
prepare chemically modified rosin derivatives such as ester gum, fumaric resins, resin-maleic
adducts and rosin modified phenolic resins.

Shellac is another natural resin. Its chief constituent is shelloic acid which is insoluble in water.
The addition of an alkali produces a sodium salt which renders it water soluble so that it can be
used water-based flexographic inks

Rosin modified ester: Refer class notes

Ester gum and other esters of rosin
Ester gum is the triglyceride derived from rosin by direct interaction between rosin and an
alcohol, for example glycerol. It is an amber coloured resin with a softening point of
approximately 85–900C ball and ring (BR). It is soluble in aromatic and aliphatic hydrocarbons,
drying oils and most of the usual lacquer solvents with the exception of alcohols. Varnishes made
with ester gum and drying oils have good pigment wetting properties and find applications in
most ink systems. Its low acidity means that it can be used in conjunction with metallic pigments.
In liquid inks careful formulation is required to reduce tack.

Pentaerylthritol ester:
The pentaerythritol ester of rosin is similar to traditional ester gum in appearance, but it has a
higher softening point of 1120C (BR) and quicker solvent release. It also has better water and alkali
resistance. For these reasons it is much more popular than the glycerol ester although it is more
expensive.
The penta-erythritol esters or dimerized and polymerizing rosin acids have even higher melting
points, give harder films and have faster rates of solvent release from an ink film. They find
widespread application in letterpress and lithographic inks and are gaining use in liquid ink
formulae.

Maleic resins and esters

A wide range of rosin maleic and maleic-modified resins are commercially available. Maleic
anhydride reacts with rosin according to the Diels–Alder synthesis. Properties vary with the molar
ratio of rosin to maleic anhydride and with the manufacturing procedure. To alter the solubility
and reduce the acid value of the rosin maleic adduct, maleic-modified resins are prepared by
esterifying carboxylic groups with a polylol such as glycerol or pentaerythritol during an in situ
preparation.
They can roughly be divided into three main classes: glycol soluble, spirit soluble and
hydrocarbon soluble maleic resins.

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Glycol soluble maleics are high acid value maleics are used in steam-set, moisture-set and water
reducible letterpress inks, also for water-based flexo inks, in conjunction with an amine or
ammonia to secure their solubility.

Spirit soluble maleics are medium acid value maleics. Used in alcohol-based gravure and
flexographic inks, in combination with polyamides, nitrocellulose or ethyl cellulose, for printing
on polymer films and foil. They are also used in water-miscible letterpress inks.

Hydrocarbon-soluble maleic resins are very pale. They are used in letterpress and lithographic
gloss inks, tin-printing inks, heat-set inks and overprint varnishes.

Rosin-modified fumaric resins

Fumaric acid is the isomer of maleic acid, therefore rosin-modified fumaric resins are classified
together with maleic resins.
They are used in flexographic and gravure inks, in combination with other resins for non-
absorbent substrates and with glycols for moistureset inks where hardness and gloss are required.
in which the carboxyl groups A and B are trans to one another.

Starch and dextrin

Starch is a commonly occurring natural material, which is synthesized in plants. The main sources
of starch are tapioca, maize, wheat and potato. Starch is a stable white powder at room
temperature. It is insoluble in cold water, but when an aqueous suspension is heated to 60–800C,
and allowed to cool, it forms a gel. Starches with a large particle size are used as anti-set-off
powders in sheet-fed printing; treated water-swellable starches have also been used for anti-set-off

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in lithographic inks. Finely ground potato starch is used to add body and to eliminate excessive
tack in platen inks.

Dextrin is partially hydrolysed starch produced by heating starch alone or in the presence of
hydrochloric acid. This converts it to a yellow-brown colour, which forms a viscous gummy liquid
when dissolved in cold water. It replaced gum arabic in anti-set-off solutions. It is also used as an
adhesive for stamps, etc. and as part of a vehicle system for water colour inks and cheque-book
inks.

Gum arabic
The main use for gum arabic was in lithographic fountain and plate ‘gumming up’ solutions. Gum
arabic, being hydrophilic, helps to keep the non-image areas ink-repellant. To a lesser extent gum
arabic is used in water-based inks to reproduce copies of watercolour paintings.
It is obtained from trees of the acacia species in Africa, especially in the Sudan. It consists of
organic polybasic acids, related to sugars, with an estimated molecular weight of 250 000. It is
readily soluble in water, but dries to give fairly brittle films.

Synthetic Resins
These are amorphous, organic compounds and exist as hard, transparent, brittle solids or viscous
liquids. They are obtained either by condensation or by addition polyrnerisation. Phenol-
formaldehyde, urea-formaldehyde and alkyds are obtained by condensation reaction while vinyl,
acrylic, styrene and polyethylene resins are obtained by addition polymerization. Pure phenolics
are hard resins while alkyds are viscous liquids. They are insoluble in water but dissolve in
organic solvents and oils when heated and form a thin layer of film.
Synthetic resins have many advantages over natural resins. They can be tailor-made according to
the requirement, are purer and cleaner and have more consistency than the natural ones.

Pure Phenolic resins:

Oil soluble, oil reactive pure phenolic resins are prepared by heating a para substituted phenol
with an aqueous formaldehyde solution under reflux in the presence of an alkaline catalyst. The
para substituent must be at least a C4 hydrocarbon chain or a phenyl group. If the substituent is
less than C4 the resin will not be soluble in oil. Properties of the final product depend on the
phenol used, catalyst, molar ratio of reactants and reaction conditions. The active methylol group
reacts with olefinic bonds in tung oil and produce excellent varnish for letterpress and
lithographic inks. They are soluble in aromatic hydrocarbons and have excellent pigment wetting
property and drying speed. They produce very tough and glossy film and have good water,
alkali and weather resistance.
Pure phenolic resins prepared with acid catalysts are soluble in drying oils, specially tung oil, but
due to the absence of methylol groups they do not react with the olefinic groups in the oil.

Rosin modified phenolic resins

When rosin is heated with an oil reactive pure phenolic resin at 150°C, the methylol groups of , the
phenolic resin react with the unsaturated centre of the rosin to develop an ether-like character.
Glycerol or pentaerythritol is then added and the temperature is increased. This results in the
esterification of the carboxylic acid group of the resin by a hydroxyl group of glycerol or

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pentaerythritol. The rosin modified phenolic resins so obtained are soluble in oils and aromatic
hydrocarbons and are used in quickset inks or toluene-based gravure inks. They impart hardness
and water and chemical resistance to the ink.

Alkyd resins
Condensation of glycerol with phthalic anhydride or isophthalic acid yields a polyester known as
an alkyd. When linseed oil is heated with an alkyd (derived from isophthalic acid) a product
known as linseed alkyd is obtained. Instead of linseed oil tung, soya or dehydrated castor oil may
also be used. If the proportion of oil added to the alkyd is below 45%, the product is known as
“short-oil alkyd”. If the proportion of oil is above 55% then the product is known as “long-oil
alkyd”. The properties of the short-oil alkyd are more like the properties of the alkyd while those
of the long-oil alkyds are more like those of linseed oil. Alkyds improve pigment wetting, film
toughness and adhesion of the dried film. They are used in paste inks, liquid inks and screen inks.
Long-oil and medium-oil alkyds are used in heatset web offset inks. Alkyds made with nondrying
oils make excellent plasticizers for nitrocellulose in gravure inks.

Other resins are Hydrocarbon resins, Polystyrene resins and copolymers, Terpene resins, Silicone
resins, Alkylated urea formaldehyde resins, Alkylated melamine formaldehyde resins, Polyamide
resins, Polyimide resins, Chlorinated rubber, Cyclized rubber (isomerized rubber), Vinyl resins
like Polyvinyl acetate , Polyvinyl alcohol, Polyvinyl butyral,
Ketone resins, Acrylic resins, Epoxide resins, Polyisocyanates and polyurethanes, Nitrocellulose,
N/C (cellulose nitrate CN), Ethyl cellulose, Ethyl hydroxyethyl cellulose (EHEC), Cellulose
acetate propionate (CAP), Cellulose acetate butyrate (CAB), Sodium carboxymethyl cellulose
(CMC) etc.

Physical characteristics of resins and their influence on printing ink:

An important criterion for the selection of an ink resin is its melting point. The resin must have a
minimum m.p. of 145-150C and a maximum m.p of 175-1800C. Resins with m.p. higher than 1800C
insoluble in vegetable and mineral oils while those with m.p. lower than 1450C do not develop
sufficient gloss and printability.
As the m.p. of the resin increases so does its viscosity. Resins with m.p. about 150°C have viscosity
about 20 poise in 60% xylol solution and those with m.p. 175-180oC have viscosity about 150 poise.
Resins with viscosity lower than 15 poise are unsuitable for printing inks because they cause too
much tack and penetration of the ink.
When inks containing resins dissolved in volatile solvents dry by evaporation, the major part of
the solvent evaporates but 10% of the solvent is retained by the resin. Although the retained
solvent has an adverse effect of softening the resinous ink layer it offers an added advantage of
making the resin component more compatible with additives such as grease and waxes present in
the ink.The solubility of ink resins in drying oils is determined by finding out the minimum
temperature at which clear resin-oil combinations are obtained under standard conditions. Only
resins that dissolve clearly in oils at temperatures below 260°C are suitable for printing inks. They
influence the stability of the ink on storage, their printability, speed of drying and degree of
penetration. They control the gloss of glossy inks, the hardness, water and alkali resistance of the
printed inks.
Ink vehicles containing resins are prepared by fusing resin and oil gently together. A physically
homogenous solution, known as the varnish, separates out on cooling. Printing ink vehicle strictly
24 |Ink Technology, 2nd  year, 2nd semester 

 
avoids copolymerization of resin and oil because such copolymerization leads to penetration and
loss of gloss.
The viscosity of the varnish produced is the arithmetic mean of the individual viscosity of the oil
and the resin. It has been observed that high viscosity resins yield nontacky vehicles while low
viscosity resins yield highly tacky vehicles. Hence in order to produce workable inks, it is
necessary to lower either the viscosity of the oil or to reduce the relative amount of the oil since
the chemical nature of the resin has no influence on the amount of tack produced by them in ink
vehicles.

Varnishes

The varnish is the part of an ink in which the other materials- pigments, driers, waxes
and modifiers are suspended or dissolved. The varnish must dissolve or disperse these
ingredients and enable inks to dry rapidly and produce high scuff resistance.

The many types of varnishes include mineral oil, soya oil, resin-oil and resin-solvent
varnishes and drying oils modified with alkyd, urethane, or phenolic resins. Besides
these, there are special varnishes for inks that dry with ultraviolet light or electron beams,
and for inks that dry on various types of plastic films.

Additives:

The suspension of pigment in varnish and/or solvent does not usually provide a
satisfactory ink. Many other materials must be added in order to provide good
performance. These additives include plasticizers, wetting agents, anti setoff
compounds, waxes, shortening compounds, reducers, stiffening agents, antiskinning
agents, and antipinhole compounds.

Plasticizers:

The main function of a plasticizer in an ink film is to make the dried more flexible and pliable.
Plasticizers need to be essentially non-volatile in their final ink format. lnks that dry by
evaporation , especially on non-porous surfaces, tend to be brittle, and flexing can crack the film
rupture the adhesion. Plasticizers help to supply elasticity to an ink and allow it to bend or crease
without failing. They do this by acting as solvents for the film former polymer molecules,
maintaining the exact degree of mechanical freedom required.

Many chemical classes of compounds are used as plasticizers in printing ink manufacture. They
are mainly viscous liquids but more solids being used these days as they plasticize without
migration problems effect better heat resistance than liquid ones. Certain plasticizers incorporated
to promote specific properties in the final ink film such as:

(a) increased gloss;

(b) Deep freeze resistance;
(c) to prevent blocking;
(d) extra flexibility;

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 (e) increased adhesion to difficult substrates;
(f) Less discoloration at high temperatures.

Very careful formulation is necessary in the initial choice of plasticizer type, and the percentage
incorporated into the final ink recipe in order to achieve the optimum balance of ink properties for
an efficiently safe and workable plasticized dry ink film. The major use of all these types of
plasticizers is in liquid inks, paste inks having in-built plasticized resins unsuitable for liquid ink
use.
The main families of plasticizers are:
Abietates Phthalates
Adipates Polyesters
Benzoates Polyol esters
Butyrates Ricinoleates
Citrates Sebacates
Epoxidised compounds Stearates
Phosphates Sulphonamides

Plasticizers are commonly used in flexographic and screen printing inks. Trioctyl
phosphate is used in gravure inks.

Waxes:

Most printing inks contain waxes to improve rub and scuff resistance. Waxes are used in
the form of a compound, which is a fine dispersion of several waxes in an appropriate oil
vehicle. They are also used in the form of a micronized, dry powder.

Common classifications of waxes are animal (beeswax, lanolin), vegetable (carnauba,

candellila), mineral (paraffin, microcrystalline), and synthetic (polyethylene,
polyethylene glycols, Teflon). Incorporated into the ink, Wax particles are held to the
printed surface by surface tension. If a wax is too soluble in the ink, if will come out of
solution when the ink cures, form a waxy film on the surface, and prevent the wet ink
from trapping on the dry ink film. This problem is commonly referred to as
crystalization.

Carnauba wax is especially hard and enhances slip in inks and overprint varnishes. The
hard, waxy surface of dried ink containing carnauba resists marring and scratching. It
will also resist dry trapping if the wax is dissolved instead of dispersed.

Petroleum waxes (mineral types) are extracted from crude petroleum. They range from
soft to hard, depending on their chemical structure. High-melting waxes are usually
hard; low melting waxes are often soft. They are used primarily to reduce the tack of
letterpress and lithographic inks and as slip agents. A petroleum wax of very fine
crystalline particle size, microcrystalline wax is particularly effective as a slip agent.
Petroleum jelly, a mixture of liquid and solid hydrocarbons with a consistency similar
to grease, retards the drying speed of letterpress and lithographic inks on the press
rollers. It is also used to reduce ink tack, improve ink setting or penetration into the
substrate, and reduce linting in news inks.

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Fine dispersions of polyethylene waxes or PTFE (Teflon) are added to inks to enhance
slip and rub resistance. Polyethylene wax is tougher than other waxes, such as
microcrystalline wax, but it may lack high surface slip. PTFE produces maximum
surface slip and good heat resistance in heatset inks. Excessive use of wax should be
avoided to prevent problems associated with ink softening and ink viscosity. Increased
drying time, trapping problems, and especially decreased gloss are caused by too
much wax in the ink. Optimum properties are normally achieved by incorporating
about 3% wax, based on total formula weight.

Driers:

Catalysts used to promote oxidation of the drying oils used in letterpress and offset lithographic
inks. In the presence of these, oxidation proceeds rapidly and the ink films dry hard in a few
hours.
The most widely used catalysts are the inorganic salts and metallic soaps of organic acids.
Recently more complex organic derivatives of metals have been introduced to boost the effect of
conventional driers.
Metallic driers are used in two forms:
(1) As oil-soluble soaps, which comprise the liquid driers.
(2) As dispersions of inorganic salts in oils, which comprise the paste driers.

Liquid Driers:

Liquid driers are prepared by the conversion of suitable organic acids to their heavy metal salts
and soaps. These are soluble in oils and/or petroleum solvents to form liquids or soft pastes
which readily mix with oil in inks,

The metals are almost invariably available as salts of complex fatty acids, either singly or as
mixtures. The fatty acids include:
Octoic fatty acids to form octoates; Rosin fatty acids to form resonates; Naphthenic fatty acids to
form naphthenates; Linseed fatty acids to form Iinoleates.

The chemical constituents of the organic acid component can influence dry print odour as well as
the effectiveness of the drier in an ink formulation at a given percentage of metal. The metal
contents range between 3 and 18% except for lead and zirconium which go up to 24%, or even
36%. An addition of between 0.5-4% of driers is the amount normally necessary to achieve
adequate drying in printing ink films.

Factors which affect the efficiency of drying of such films are the surface characteristics and the
pH of the paper, stacking procedures and atmospheric conditions. It is a well-known fact that
inks dry more rapidly at higher temperatures whereas a high relative humidity slows down the
oxidative drying rate, especially when the pH is low.
Cobalt is the most powerful drier, also the most popular. Cobalt acetate can be dissolved and
introduced into the fount as a drying activator also.

Manganese, less vigorous catalytic action than cobalt. Lead A slow acting drier of pale colour.
Cerium, zirconium and lithium driers of medium efficiency and pale colour. They have
replaced lead in many vehicles and are usually used mixed or in conjunction with cobalt or

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manganese soaps. Calcium and zinc are ineffective as-catalysts, having only one valency state,
and are not used much in printing inks except in some whites. Calcium is used in low odour
systems to modify the catalytic action of transition metal driers. Iron is useful in tung oil
varnishes

Paste Driers:
These are prepared by grinding organic salts of lead and manganese in linseed oil varnishes.
Lead acetate and manganese borate are commonly used. It is also possible to prepare pastes by
flushing, but most formula are confidential. The percentages vary but are of the order of 40% lead
acetate, 8% manganese borate. Small amounts of soluble manganese driers may also be added,
but cobalt is seldom used in paste driers.

The slow-drying characteristics of paste driers give a receptive in surface for superimposition;
therefore they are usually used in multi colour process inks. Cobalt driers are inclined to yield
dried prints which are not receptive to overprinting. Paste driers, although they dry inks slowly,
do dry uniformly throughout the film.

Inorganic peroxides have been successfully used as components in paste driers, but great care has
to be taken in respect of fire during their production. These are very useful in lithographic ink,
where the acidity of the fount solution, combined with the pH of the vehicle will liberate oxygen
which is absorbed along the chain of the polymer.
To obtain optimum drying effect in oil based inks, it should be noted that some pigments such as
the PMTA salts require more drier like bronze blue of phthalocyanine require less, because they
accelerate oxidative polymerization. The use of lead in driers is being phased out; lead is being
replaced by other metals such a zirconium.

Chelating Agents:

These are chemicals which react with multivalent metal ions, to form a chelate. This is a type of
atomic cocoon produced by the formation of closed ring of atoms which are attached to a central
multi-valent ion usually metallic. Normally this phenomenon is due to sharing with the
central ion a lone pair of electrons from oxygen or nitrogen atoms in the chelating compound.

Chelating agents are used for locking up unwanted metal ions, to form extremely stable insoluble
or soluble chelates. By chemically binding metal ions in additives, or trace metals in compounds,
it is possible to improve shelf life, colour, clarity and stability. Chelating agents used if water-
based systems are able to improve wetting through softening the water by locking up and
rendering inactive the iron, calcium and magnesium salts.

ANTI-OXIDANTS

Anti-oxidant molecules react with free radicals formed during the autoxidation process and
continue to act until all the anti-oxidant molecules are exhausted. Consequently, any anti-oxidant
incorporated into an ink will delay the initiation of oxidative polymerization drying.

The most common anti-oxidants are the naphthols, substituted phenols, a variety of oximes and
the aromatic amines. Quantities necessary are only a fraction of 1% of the final formulation. Press
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stability of lithographic tin-printing inks is usually improved by the incorporation of a small
quantity of anti-oxidant which is lost during the initial part of the stoving schedule. The oxidation
process then proceeds normally.
Numerous anti-oxidants are marketed for industry and many of them bear manufacturers’ trade
names. Some of the most effective are:
eugenol (extract of oil of cloves)
butylated hydroxyanisole
hydroquinone
methyl ethyl ketoxime
pyrocatechol
butylaldoxime
guaiacol (methyl catechol)
cyclohexanone oxime
butylated hydroxytoluene

Antiskinning Agents

Antiskinning agents are antioxidants that counteract the drying of sheetfed offset inks
so that they will not skin over in the can. If they are sufficiently volatile, they will
not greatly retard the drying of the rest of the ink.

Printers sometimes spray antioxidants onto the plate and blanket of a sheetfed press to
prevent drying or skinning during lunch time. The ink so treated will not dry properly,
but a few sheets run through the press will take most of the treated ink away.

SURFACTANTS

The name surfactant is given to substances which have the property of being adsorbed at surfaces
or interfaces, thereby reducing the surface or interfacial tension. Soaps and detergents act this way
in aqueous systems. This action can be measured and demonstrated by taking the contact angle
(xyz) of a drop of pure water on a non-absorbent surface (Fig. 4.2 (a)). The addition of a very
minute quantity of surfactant decreases the angle of contact considerably, at the same time
increasing the interfacial area (Fig. 4.2 (b)).
The same concept of wetting and spreading applies both to oleo resinous and to aqueous systems.
A contact angle less than 908 enables the vehicle to wet and disperse pigments. Wetting greatly
influences the physical and printing characteristics of an ink. Numerous surfaciants are available,
many of them with trade names. The choice is large so it is left to the ink formulator to select the
best surfactant, and to include in his formulation the optimum amount to obtain the highest
tinctorial strength from pigments. Incorrect use of surfactants can result in decreased adhesion to
some substrates, and can lower the water resistance of a print. Surfactants can promote emulsions;
therefore care must be taken that they do not also cause emulsification of lithographic inks.
Selection must be made with knowledge of the properties of the surfactant, the formulation
objectives and the precise amount needed to attain
those objectives efficiently. This approach discourages indiscriminate use
which can be harmful and costly.
Surfactants normally contain polar and non-polar groupings in the
same molecule. It is the ionic or active portion of the molecule which

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divides surfactants into anionic (which have an active negative charge), cationic (where the
positive charge predominates) and non-ionic classes. Amphoteric surfactants have both positive
and negative centres of charge
Wetting Agent:

Wetting agents promote the dispersion of pigments in ink varnishes. There are many
varieties of wetting agents, and the selection of an appropriate one should be left up
to the ink manufacturer. Wetting agents for lithographic inks must be carefully
selected; otherwise they can cause excessive emulsification of dampening solution
into the ink and associated problems. These problems may be resolved using water-
pick-up control agents. Wetting agents may also reduce the surface tension of
aqueous inks in order to improve the wetting of plastic and foil substrates.

Antisetoff Compounds:

Setoff is often referred to as offsetting, but GATF prefers to reserve the word "offset" for
a method of printing.Various compounds prevent setoff either by protecting the ink
surface or by shortening the ink (decreasing its gelling time). Compounds containing
wax or grease shorten the ink, thereby speeding up its setting. Antisetoff compounds
that contain magnesia also prevent setoff primarily by shortening the ink; however,
addition of such materials often promotes blanket piling.

Starch reduces setoff by slightly roughening the surface of the ink film. The starch is
blown onto the printed-ink; it should never be mixed with the ink. Starch reduces
contact between adjacent sheets and allows more time for the ink to set.

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Solvents that increase the rate at which a paper absorbs an ink vehicle may also
reduce setoff. However, they tend to reduce the gloss of the dried inks and may also
cause chalking on coated stocks. Wax, starch, and magnesia compounds are less
objectionable. The wax compounds, if used in excess, can prevent good trapping of
succeeding colors if the inks dry between printings.

Shortening Compounds

Shortening agents reduce ink flying, or misting. The addition of a wax compound
shortens an ink. The printer should not add such materials except on the advice of
the ink manufacturer because they can interfere with proper ink flow on press and
aggravate ink piling.

Reducers

Heatset oils or other petroleum solvents are occasionally added to soften and reduce
the tack of an ink. A light varnish, such as #0000 litho varnish, boiled linseed oil or a
light linseed isophthalic alkyd, will also reduce the tack of an ink. It is much easier to
reduce the tack than it is to increase it. Presently, this is possible using tack increasers.

Stiffening Agents

For sheetfed inks, body gum-#8, #9, or #10 linseed varnish is used to stiffen an ink that
is too liquid and fails to print cleanly and sharply. It pulls the ink together when the ink
tends to cause scumming or tinting, and it can help prevent chalking on coated stocks.
Heavy-bodied gloss varnish (binding varnish) or gel varnish can also be used for this
purpose.

Defoamers for Aqueous Inks

Defoamers for aqueous inks are surface-active blends of hydrocarbon liquds,

surfactants, metal soaps, hydrophobic silica, and other, with or without silicone
modification. They may be used during the preparation of aqueous inks to prevent foam
buildup and may also be added during application for the same purpose. Interactions
between waxes and defoamers are sometimes encountered, requiring changes in either
the wax or the defoamer.

For others refer class notes.

Rheology of Printing ink:

Rheology is the study of flow and deformation of matter. For good quality printing a letterpress
and lithographic ink must be as stiff as possible but when a printing machine is run at high speed
the stiffness of the ink must be reduced to prevent the paper surface from being torn away from
the body of the paper and to avoid the generation of too much heat on the machine. For these
reasons lithographic and letterpress inks are made ready for the press by the ink maker and the
printer usually does no: make any modification.

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Gravure and flexographic inks, on the other hand, are supplied at a viscosity greater than that
required for use in the press. This prevents the pigments from settling to the bottom of the
container during transportation. The printer adds solvents to adjust the viscosity according to the
press requirement and drying rate.
It has been observed that the rate of penetration of printing ink into paper is directly proportional
to the-fluidity of the ink vehicle but not to the the fluidity of the compounded ink. Also, the
fluidity of the ink vehicle depends on the temperature of the ink. The working properties of the
ink in the press and its penetration qualities on paper is determined by the rheological properties
of the ink. In order to understand the rheology of printing inks one must be familiar with the
following terms -viscosity, Newtonian flow, non-Newtonian flow, thixotropy, visco-elasticity,
tack and length.
Viscosity:
The viscosity (i.e. the resistance to flow) of liquids is temperature dependent. It increases as the
temperature decreases, and decreases as the temperature increases. In letterpress and
lithographic presses most of the mechanical energy is converted into heat energy on the ink
rollers. This increases the temperature of the ink rollers resulting in a decrease in the ink
viscosity. Hence, as the ink passes over the ink rollers, fluidity of the ink increases and the ink
readily flows. As the ink cools in going from roller to plate to paper, its viscosity increases
rapidly. This rapid increase in ink viscosity enables the ink to become stiff again, thus preventing
set-off and loss of dot sharpness on the paper. The introduction of pigments into the vehicle,
however, produces a colloidal solution which showsconsiderable deviations from Newtonian
behavior. Using a variable speed viscometer accurate rheological measurements of an ink can be
made and a graph can be drawn for shear stress against shear rate for different ink composition.
Accordingly, for such non-Newtonian liquids, three types of liquid flow may be differentiated -
pseudoplastic flow with yield value (fig. 2), pseudoplastic flow without yield value (fig. 3), and
dilatant flow (fig. 4). The rheograms obtained are shown below.
Fig2. reveals pseudoplastic flow with yield value where the applied shear stress is greater than a
certain minimum value to start the flow. This minimum force is the yield value and is the
magnitude of the intercept γ0 on the stress axis.
Plasticity is the property of a substance that allows it to be deformed continuously during the
action of a shearing stress which is greater than the minimum required to start flow, and which
allows the substance to retain its shape for a long period when the shearing stress is removed or is
below that required to make the substance yield and the flow is termed as plastic flow. Plastic
flow is characteristic of many inks and so the determination of plastic viscosity is very important
to the ink maker, the coefficient of plastic viscosity (ρ) is the force in dynes per sq cm in excess of
the yield value, tangentially applied that will cause unit velocity gradient.
ρ =( γ-γ0)/D
For practical purpose, the yield value of an ink is the force per unit area required to start the flow.
In other words, it is the amount of shear stress required to break up the structure in the ink and
give rise to an almost Newtonian type of flow. Many liquid such as water and alcohol have no
yield value. This means a very, very small force will begin flow. Inks with very high yield value
will not flow out of the ink fountain. The printer refers to the ink as "hanging back" or "backing
away from the roller." So inks with low yield values are suitable for letterpress and lithographic
processes.
Fig. 3 reveals pseudoplastic flow without yield value and is characteristic of lyophilic colloids that
32 |Ink Technology, 2nd  year, 2nd semester 

 
are thixotropic. These systems flow more readily when stirred or sheared and no thixotropic
build-up occurs once the structure is broken down. The curve shows that the rate of flow increases
faster than the shear stress. The viscosity value is lower when measured at high rates; the flow
begins at a very small shear stress. Since the dispersed phase is lyophilic and appreciably
solvated, some of the dispersion medium may be separated during shearing and consequently the
viscosity appears to fall as the shear stress is increased. At the higher shear rates the curve
becomes approximately linear and the ink maker extrapolates this portion of the curve to the
stress axis (as shown in fig.3) and records this (γ0) value of shear stress as yield value.
Paste inks with low yield value and low viscosity may pose problems of dripping when they are
hand-fed. They may also drip from the sides of the duct and duct blade. This problem is often
encountered with newspaper presses which use low viscosity, long flowing inks with low yield
values. Such inks also produce a greater physical dot gain. But they flow smoothly from the ink
duct, transfer well on the rollers and lay well on the substrate because the low viscosity of the ink
allows it to flow into surface irregularities. Inks with high yield value and high plastic viscosity
can create problem when the ink is transferred from the container to the duct of the press. If the
yield value is lower than the shear stress in the duct, the ink will feed well in the ink duct but will
not lay well on the substrate. However, these inks minimize lateral flow of the impression and so
produce sharp dots and small dot gain. Low viscosity lithographic inks form excessive emulsion
with water and produce scum and water marks but high viscosity inks take up less water and so
minimize scum and water marks. Inks with high yield value and low viscosity feed badly because
of lack of cohesion and so do not allow proper ink transfer.

Fig. 4 shows dilatant flow. When the rate of shear decreases more in proportion to the shear stress,
the material is known as dilatant or shear thickening substance. Dilatancy occurs when the
particles of the fluid come close together. Dilatant inks are highly pigmented with good wetting
and a viscous medium. They show increased resistance to flow if stirred or sheared but when
allowed to stand, they revert to the origina condition and exhibit flow. They are not suitable for
letterpress and offset processes because in fast running presses the ink will not distribute evenly
on the rollers and so will not transfer to the printing surface. Also, at high rates of shear the ink
will clog on the rollers and the printed image appears deficient of pigments. Dilatancy occurs in
highly pigmented paste inks to which varnishes are subsequently added in preparing a printing
ink. It is sometimes formulated into intaglio inks for copper and steel engraving to assist in clean
wiping of the plates

Some quickset varnishes contain resins that do not dissolve well in solvent mixtures. In such
cases, if solvent loss occurs on the rollers the resin becomes part of the dispersed phase and not
the dispersion medium and the tack of the ink is greatly reduced. The ink becomes dilatant, fails
to distribute evenly and transfer well and so piles up on the rollers and plate.

33 |Ink Technology, 2nd  year, 2nd semester 

 
Fig3: Pseudoplastic substance Fig2: Pseudoplastic substance with yield value.

Fig4: Dilatant Substance.

Thixotropy:
Most printing inks thicken on standing and the gel structure can be broken down by
stirring, a phenomenon generally described by thixotropy.

When a thixotropic substance is stirred at a constant shear rate the apparent viscosity falls with
time and eventually attains a constant value (fig 5). At this point the breakdown and build-up of
gel structure are balanced for that particular shear rate. Thixotropy is a time dependent
phenomenon. It is assumed in flow curves such as fig1-4 that the breakdown of structure and its
re-establishment, when the shearing stress is removed are instantaneous. This is true within the
limits of measurement for some materials and curves such as these could be followed upwards
and downwards an indefinite number of times without any variation. For many other matetials,
however, including printing inks, the processes of breakdown and especially set-up take time and
this leads to further complications.

In the flow curve for a thixotropic material readings taken at advancing shear stress differ from
those where the shear stress is being reduced (see Fig. 6) As the stress is increase the structure in
the ink is reduced and the curve AB results. If after B is reached, the stress is progressively
34 |Ink Technology, 2nd  year, 2nd semester 

 
reduced curve BO results because structure recovery takes much longer.

The area in the hysteresis loop may be taken as an indication of the degree of thixotropy existing
in the substance under test. Care should be taken to establish that this thixotropic loop is in fact
real because fluid systems (even if Newtonian) which are subjected to stress will become heated
and yield similar hysteresis loops if the thermostatic control system is inadequate.

Fig5: Thixotropic substance at different shear rates. Fig6: Thixotropic material.

Visco-elasticity:

A purely viscous liquid will move on the application of minimum stress. On removal of the stress
the liquid will not come back to its original position. An elastic solid, on the other hand will come
back to its original form immediately on removal of the stress. No substance is either totally
elastic or viscous and so most substances contain both characteristics. The extent of each
characteristic depends on the molecular structure of the substance and any intra or
intermolecular interaction present. These substances are called visco-elastic and most printing
inks fall within this classification. In printing presses the ink behaves as an elastic substance at
shear stresses below the yield value of the ink and as a viscous liquid at shear stresses above the
yield value. At shear stresses equal to the yield value the ink passes from the ink duct to the ink
rollers. As the ink passes over the ink rollers it is acted upon by a shear stress above the yield
value of the ink and the ink behaves as a viscous liquid. The release of the shear stress during the
separation of the ink rollers and blanket cause the ink to lose its plasticity and regain its original
form i.e., the ink behaves as an elastic material.
The visco-elastic nature of inks becomes more significant with higher pigmentation. The choice of
medium with respect to its molecular nature can have considerable influence; rosin-based
derivatives will behave differently to long polymer chains based for example on linseed oil.

Length of ink:
Length is the ability of an ink to form a string when pulled out by the spatula. A long ink is one
which can be stretched out into a long string while a short ink breaks sooner under the same
conditions. An ink must have a certain length so that it does not back away from the ink fountain
roller. A long ink flows well and distributes evenly on the rollers without piling. Ink that is too
short does not transfer properly while ink that is too long tends to fly or mist. Screen inks must be
short to prevent the ink from stringing when the screen is separated from the substrate. Flying of
an ink depends on the ratio of the length of the ink to its tack. As the length of the ink increases

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the tack of the ink must also be increased to prevent the ink from flying.
Ink length can be expressed as the ratio of viscosity and apparent yield. So in SI unit ink length is
expressed in seconds. Ink shortness is sometimes defined as the inverse value of ink length. So
the tack and length of an ink may be adjusted within limits by changing the viscosity of the
varnish, by varying the constituents of the varnish and by changing the pigment/varnish ratio.
The more viscous is the varnish greater will be the tack of the ink. If the same varnish is used and
the amount of pigment in the ink is increased, the tack of the ink will increase but its length will
decrease. So proper selection and adjustment of these materials are necessary to produce an ink
with the desired tack and length.

Tack:
Tack gives the measure of stickiness of an ink and is due to the forces of cohesion between the ink
particles. Thus greater the cohesive force, higher the tack of the ink and vice versa. Tack is
measured with an instrument called the tackmeter (fig9) or inkometer. The inkometer is a
machine that simulates the rolls on a press. The instrument contains rotating rollers on which a
specified amount of ink is distributed. The tack of the ink produces a pull or torque on one of the
rollers. This force is converted into an electrical signal that is displayed as a digital number. This
number is the tack number.

In letterpress and lithographic presses the ink is applied to the image carrier by means of rollers.
Tack is responsible for ink transfer from one roller to another, from roller to image carrier and
from image carrier to substrate (or image carrier to blanket and blanket to substrate). As the rotating
surfaces move away in opposite directions the ink film between them forms thousands of
filaments or threads. These threads gradually get longer until they are about ten times their
diameter when they split and break into two halves. Each half decreases in length very rapidly
and merges with the main body of the ink on each of the separated surfaces such that about half
of the ink adheres to each surface. Only when the ink is transferred from the rubber blanket to the
paper, some of the ink vehicle is absorbed into the paper and over 50% of the ink stays on the
paper.
In web offset presses a gradual increase in ink tack occurs as the ink is transferred from the inking
rollers to the paper surface. This happens because web offset presses operate at very high speed
and as the machine attains maximum speed it warms up and the ink rollers get heated. This
increases the temperature of the ink to an extent that some of the solvent evaporates. The loss of
solvent from the ink increases the viscosity and tack of the ink. Some of the solvent may be
absorbed by the rollers and blanket and tack increases further. Again when the ink is transferred
to the paper a little solvent is absorbed by the paper surface and tack of the printed film increases
still further. If we start with an ink of very high tack, at this stage the tack of the ink becomes so
high that the ink film refuses to split. Under this condition the paper picks or the coating is pulled
out from coated papers. So inks with low tack numbers are used in web offset press inks.

In sheetfed printing presses inks with tack number 10-16 (measured at 800rpm on an inkometer)
are used. Low tack inks produce high dot gain. So inks with low tack numbers lower than 10 do
not give sharp half tone dots on the plate, blanket and paper and therefore, do not print sharp
images. They cause drying problem and low gloss. Moreover if the tack of the ink is very low then
the ink filaments may string to 3 mm before breaking. Some of these filaments break in two or
more places. In this case free floating ink particles are produced and the pressman refers to this
36 |Ink Technology, 2nd  year, 2nd semester 

 
condition as ink flying.

Tack plays an important role in wet multicolour printing by offset process. Here the first down ink
should have the highest tack and the succeeding colours should have progressively lower tack. A
high tack ink on the paper will trap a lower tack ink. If this is not followed the ink may not trap
on each other properly.

Falling bar viscometer:

For routine control in a printing ink laboratory the falling rod viscometer is now the most widely
used and convenient method of determining the rheology of letterpress and lithographic inks. It
is possible to calculate the plastic viscosity in poises and the yield value in dyne/cm2 .The
numerical values obtained depend upon the precise method of use, but once that is established
repeatable results can be achieved. This makes the instrument suitable for control of batches and
also for the characterization of inks which have been found particularly satisfactory on the
printing machine some specific process.
The apparatus consists of a vertical rod which passes through an annulus. A sample of ink is
placed between them, after which the rod is forced through the aperture by applying weights to it
(see Fig.7). The time of fall is measured at each load. The readings can then be converted into
shearing force (load) and shearing rate (time) by applying appropriate viscometer constants.
A series of pairs of values may be plotted to obtain a rheogram. The apparatus is particularly
useful in the viscosity range of letterpress and offset inks and the concentrated pastes from which
they are often made (approximately 5 pascals to 10 pascals). Materials of this kind are usually
pseudoplastic and many are very thixotropic.
The yield value of an ink is defined as the force applied to produce some significant flow and it is
of interest in predicting, for instance, whether a given ink will feed readily from the duct where
shearing forces may be small. However, it is difficult to make reliable measurements at low rates
of shear to see if a yield value is apparent. The difficulty is commonly overcome by the use of
Casson's equation and charts based upon it may be supplied by the equipment makers. It is
summarised as:
λ1/2=K0+K1D1/2
Where, λ= Shearing stress(N.m-2)(pascal)
D= Shear rate(s-1)
K0=Square root of yield value
K1=Square riit of plastic viscosity.
The application of the Casson equation produces a straight line which can be extrapolated to zero
rate of shear to determine the square root of the yield value. The slope of the line represents the
square root of the plastic viscosity.
Manufacturers’ charts have been prepared so that the loads and their respective times of fall can
be plotted, and the viscosity and yield value directly read off (Fig. 8). It should be noted that these
charts are prepared on the basis of the original dimensions of the instrument which changes with
wear.
Frictional heat is generated when the rod passes through the annulus, and cooling is provided by

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circulating water at constant temperature through a jacket surrounding the aperture.
The recommendation about the performance of measurements varies both in terms of the choice
of loads, and whether they are applied in ascending or descending order. Generally
determinations using high loads produce relatively high figures for yield values and low figures
for plastic viscosity. This effect was found to be reinforced if the loads were applied in descending
order. An article prepared by the Experts Committee in Rheology of the European Association
recommends a maximum load corresponding to a minimum falling time of 5 s (rate of shear
500s-1), or if an electrical timer is in use, this can be reduced to about 1 s (rate of shear 2500 s-1). It is
advisable not to use loads above 2000 g, because excessive heating will occur. The committee also
recommends that the highest load is first applied, then the lowest then the second highest and so
on. in this way the influence of thixotropy is reduced.
Special attention is needed to the cleaning of instruments, because small amounts of dried ink on
the rod or in the annulus will upset the results. It is also important to ensure that all solvent is
removed before a new measurement is made.

Fig.7: Schematic diagram of a falling rod viscometer.

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Fig.8: Chart to determine apparent viscosity from a plot of the weights and times on a falling rod
viscometer.

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Fig 9.1: Typical Tackmeter(drag movement)

Fig9: Tackmeter Principle (torque measurement)

The Manufacturing process:

Most of the printing ink falls into two categories; basically this can be defined as

1. Oleoresinous systems for letterpress and lithographic printing and

2. Volatile solvent/resin systems for flexographic, gravure and most screen printing.

The former are formulated on non-flammable solids dispersed into vehicle containing mineral or
vegetable oils or high boiling point solvents.

The later types of ink can be subdivided into two classes-

a. Those based on water reducible vehicle and
b. Those based on highly volatile and flammable solvents which require special buildings and
plant with flameproof electrics for their manufacture.

The manufacturing of ink can be broken down into the following

operations:
1. Varnish manufacture i.e. vehicle.
2. The manufacture of additives
3. Dispersion of pigments into vehicle using mixing and milling techniques.

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General procedure:

The process of preparing pigment dispersion in a liquid takes place in steps which, although
separate and identifiable, usually occur concurrently.

Firstly, the vehicle or the liquid phase wets the pigment, the solid phase. The liquid, as it is
wetting the pigment, must firstly displace the entrapped air and must satisfy the oil absorption of
the solid; i.e. the amount of vehicle required to just fill the void within each of these particles and
between the particles.

Secondly, the excess vehicle will wet and coat the surface of the agglomerated particles. At this
stage, if nothing else happened, there would be a mass of agglomerated particles wetted with
vehicle, all suspended in the excess vehicle.

The second stage is to mechanically separate the pigment particles by means of dispersion
equipment (Ball mill, bead mill or other high energy milling equipments).

Once separated, further extended mechanical mixing or milling is required to effect dispersion
which is best described as the permanent particle separation of the wetted pigment particle in the
liquid vehicle.

Most printing inks consist of pigment dispersed into varnishes and manufacture is mainly
concerned with the mechanical means of producing these dispersion efficiently, economically,
reproducibly and often very quickly. Usually two techniques are employed: Mixing and Milling.

Mixing: It is the mechanical agitation of pigment and vehicle/varnish together and is usually
continued until no dry pigment is discernible and an agreed level of dispersion has been achieved.

Milling: This is followed by milling, the process by which the pigment/vehicle mixture is refined
and the pigment particles are reduced to a size suitable for the intended printing process.

In some cases these two are combined in the same item of plant.

Primary dispersion for ink production demand that the pigment particles are thoroughly wetted
by liquid phase and that the particles in the finished ink for most process should be in a range
between 5 to 1 μm. If this level of dispersion is not achieved, printing problems will arise.

The Manufacture of oleoresinous system:

Varnish manufacturing: Refer class notes.

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Fig: Temperature/time related cooking cycle.

Manufacture of wax pastes and other additives

The waxes used in the construction of printing inks are as various in their type as in their physical
appearance.

The latest mode is to incorporate micronized versions but these do not always give the desired or
expected results. There are several reasons for this; for example, the particle size may not be large
enough to provide the abrasion resistance required, or the material may not be uniformly
dispersed. The wax content of a finished ink is small and must be thoroughly mixed to give the
necessary protection to the ink film. As a
result, waxes are, more often than not, added as a compound containing between 30 and 40% wax.
The word 'compound' in this context needs to be further defined as the waxes are normally
neither soluble nor
compatible with the vehicle or solvents into which they are dispersed, which will be chosen so
that the final paste is compatible with as wide a range of inks as possible. The only purpose of
making a compound is to reduce the particle size of the wax to a suitable level for incorporation
into the ink and reduce the chances of localized additions of large agglomerates of wax formed by
the attraction of smaller particles due to static forces.

Dispersion methods are crude and are normally by use of a star or rotor high speed mixer or,
alternatively, the wax is heated as a mixture to a temperature around softening point and refined
through a heated three-roll mill until an acceptable reduction in particle size is achieved.

Although waxes are the largest group of materials which need to be added to oleoresinous
systems in small amounts, similar techniques can be used for other minor additions of solid raw
materials which an ink technician may wish to include in his formulation.

With the use of highly accurate electronic balances or those systems linked to a computer base, the
weighing of liquids as ink additives becomes a simple operation, however, dilution with some of
the vehicle,
or the solvent used in the formulation, aids transfer of the material and helps ensure a
homogeneous mix. If the reduction is done in bulk, a simple paddle mixer should be sufficient, but
care needs to be taken to ensure that the reduced additive does not form layers of separated
material and it should be homogeneous before use.

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Manufacture of oleoresinous inks

Until the early 1960s the production of paste inks had followed the traditional path of mixing the
items just sufficiently to wet out the dry pigment and then passing this rough mixture over a
three-roll mill until sufficiently dispersed, i.e. most of the work was done at the milling stage.
With the introduction of faster running printing presses there was a greater need to reduce more
efficiently the particle size and to cost effectively develop the colour potential. As a result the
required levels of dispersion meant that the ink need to be passed over the three-roll mill several
times and this was time consuming and very expensive.

Combined with this, the increasing use of heat-set inks meant that a totally enclosed system was
needed to overcome evaporation of the lower boiling point solvents being used in increasing
quantities. Both these factors led to the introduction of bead mills, which were not only enclosed
but also gave improved rates of production and permitted the easier handling of larger batch
sizes. This method of manufacture is efficient for dispersing most pigment/oleoresinous varnish
mixtures, although it would be premature to suggest that all the problems such as machine
downtime, temperature control and maintenance of gloss in the final inks have been overcome. In
fact some companies use bead mills to disperse the premix and follow this by passing the ink
through a three-roll mill to improve gloss and remove air.

Whatever the equipment being used, the following processes will be carried out when making a
paste ink from dry color and varnish:
• weigh out pigment and vehicle and pre-mix;
• disperse using a three-roll mill or a bead mill;
• incorporate additives and solvents;
• Transfer to bulk or pot-off into tins, buckets or drums, once passed by quality control.
Following the mixing stage, the viscosity of the ink formulation may be further adjusted
depending on the ink type and the nature of the mill to be used for the next processing stage. For
three-roll milling, the mixture should have sufficient structure to ensure shearing takes place, but
should also have sufficient vehicle present to complete the wetting out of the pigment particles.
For bead milling, there is an additional requirement to keep the temperature in the chamber low
enough to avoid changes in shade and opacity with certain yellow and red pigments.
Once the ink is fully dispersed, final additions can be made and the ink technically approved. It
may then be canned manually by passing through a three-roll mill with the roller gap set to give a
high rate of throughput without aerating the ink. Alternatively, a modern ink-filling line may be
used.
An alternative method of manufacture may be used for small to medium sized batches (say up to
100 kg) or when using flushed pigments or special concentrates:
• blend the predispersed base (made from dry colour and varnish as above) or the flushed
pigment or the concentrate, with the extra varnishes and additives required;
• refine the mixture over a three-roll mill;
• transfer to bulk or can.

The range of bases available to the ink formulator will depend on the type of inks being supplied,
but ideally should contain a high pigment concentration and should be as versatile as possible. A
simple mixing process using a paddle or 'butterfly' type mixer is normally used.

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Liquid ink manufacturing:
Special precautions are to be taken during liquid ink manufacturing as the solvents (toluene, C6H6
etc.) used are highly volatile, inflammable and can cause health hazards. So the process is carried
out in enclosed vessels. The MAC (Maximum allowable concentration; of the solvent in the
atmosphere) is to be maintained. Because of the toxicity and flammability special procedure to be
adopted- otherwise the entire process is simple as the viscosity is low.
Manufacture of polymer/solvent systems:
This covers the manufacture of flexographic, gravure and most screen inks. As noted
previously, there are two main types of formulation- water based and solvent based. The
volatile nature of the liquid phase of both solvent and water-based inks requires similar
manufacturing techniques but they are often produced in separate units to avoid contamination.
The highly flammable nature of a large number of the solvents used requires special precautions
44 |Ink Technology, 2nd  year, 2nd semester 

 
to be taken to prevent the risk of fire and explosion. Solvent extraction and containment along
with fresh air ventilation are both used to keep the level of solvents in the atmosphere below the
threshold limit value (TLV). Emissions to the atmosphere need to be studied before plans are
finalized on this subject because in principle they should be avoided.
The area where highly flammable and highly volatile products are manufactured is normally
classified as a Zone 1 flameproof area and every effort must be made to eliminate the risk of fire;
manufacturing equip-
ment and containers must be earthed to eliminate the generation of static electricity; all motors,
lights and switches must be to Class 1 flameproof standards and any hand tools used must be
non-sparking. Further. the clothes worn by operatives should be so manufactured that overalls
do not cause static and protective footwear does not cause sparks.
A number of the materials used in liquid ink formulation could cause a health risk if adequate
precautions are not taken. The extraction systems should keep the overall levels of solvent in the
atmosphere below the 8-hour weighted maximum allowed concentration (MAC), but care must
be taken not to allow pockets of solvent fumes to build up. Face filter masks must be worn if
there is a risk of powder in the atmosphere and gloves are essential to reduce the risk of skin
contact related health problems.

Varnish Manufacture:
It is possible when producing liquid inks on a ball mill to load pigment, resin, solvent and other
ingredients to produce a finished ink from basic raw materials. However, it is more common to
produce varnishes using the resins and solvents before the pigment dispersion process.
Liquid ink varnishes are formulated using a very wide range of resins such as nitrocellulose, ethyl
cellulose, maleic resins, metallic resinates, acrylics. polyamides etc. The solvents used range from
aliphatic and aromatic hydrocarbons to esters, alcohols, ketones and water. Varnishes are normally
produced on high-speed stirrers. In view of the volatility of the solvents used and the heat
generated, it is essential that the stirrers are totally enclosed and where the design allows, water
cooled. The mixers employed are cavitation mixer, rotor stator mixer.

Pigment chips:
An alternate method of producing liquid inks with exception at color strength, transparency, and
high gloss is the use of pigment chips. Chips are produced by dispersing pigment into solid resins
which may also include some plasticizers. Various wetting agents and antioxidants are added to
improve manufacturing time and prevent instability on storage. Chips are solid inks which needs
addition of liquid to make it usable. The steps are pre mixing, dispersion, dry/cooling, final size
reduction.

The initial pre mixing of pigment and resin can be carried out using a Z blade mixer, solvent
and plasticizers being added to give cohesion for producing a viscous paste. The Z arm mixers
incorporate a water jacket for cooling around the mixing pan.

After pre mixing, the material is transferred to a 2roll mill and placed in the nip. There it
forms a plastic band around the rollers which is repeatedly cut off, turned and replaced into
the nip until dispersion is
complete. When using a resin of low softening points (polyamide), close control of roll surface
temperature is desirable. Otherwise it will either become too plastic reducing shear efficiency or

45 |Ink Technology, 2nd  year, 2nd semester 

 
too thick. The pressure applied during milling operation is around 50 tonnes/inch2. After milling
a complete plastic sheet is produced which is allowed to cool during which residual solvent
evaporates off. The sheeted dispersion becomes brittle when dry and is ready to be reduced to a
convenient particle size. An alternative dispersion technique is to blend pigment and resin in a
Banbury ora 3 roll mill.

Manufacturer of dye-based inks:

Dyestuffs are soluble in the solvents and diluents used in the formulation and the method of
manufacture is normally to dissolve the dye in the solvent part of the formulation with constant
stirring. The application of heat will increase the solubility of the dye and therefore lessen the time
taken for the process to be completed. When the dye is dissolved, varnish and other additives are
added to complete the formulation. Once again, care must be taken not to shock-cool the system,
causing the dye to become insoluble.
Mixing Equipment:
The dispersion of the dry materials, pigments, fillers etc. is normally done in a mixing vessel. The
function of the mixer at this stage, is to achieve an accepted level of dispersion before it is further
refined or filtered, also to facilitate the addition of liquid reducers and other additives to already
dispersed material. Paddle mixers find a wide use for mixing all types of ink. They are also used
to agitate or keep products in solution or suspension.

The types of mixers available are numerous but in principle, they fall into fairly simple groups,
mainly determined by the type, viscosity and volatility of the ink to be made. High viscosity
oleoresinous formulations are best dispersed using a low shear premixer, but as the ink viscosity
falls, higher-shear machines give better results. Low-shear equipment employs slow speed
mechanical movement, coupled with a high viscosity product to maximize the shearing effect.

Vacuum premixing has become general practice in the last few years, especially where oil inks are
concerned. The main reasons for this are twofold. First, it is known that air dispersed in inks can
be as high as of the mix and this reduces the efficiency of the premixer considerably .Secondly,
46 |Ink Technology, 2nd  year, 2nd semester 

 
dispersed air can lead to problems in subsequent processing. Heat transfer within the mill is
reduced considerably leading to high processing temperatures which would affect the milling of
some yellows and other heat-sensitive pigments.

Z-arm mixers have been used in the production of viscous pastes for many years and their use in
manufacture of flushed pastes has already been mentioned. Modifications can be made to the
basic mixer, such as the provision of heating/cooling jackets, while vacuum or pressure can be
applied to the mix. In general, they are of heavy construction with relatively powerful motors and
a low operating speed.

The mixer contains two gear-driven Z-shaped blades rotating, usually at different speeds, the
blades almost scraping the bottom and sides of the mixer. The blades rotate in opposite directions,
both towards the centre of the mixer and the whole unit can be rotated through 900 to empty the
contents for further processing. Usually, part or all of the varnish is added to the mixer and then
the pigment and/or filler, added in stages, allowing each addition to be fully wetted out before
the next one is added. As the blades rotate, the mix is kneaded and thus strong internal shear
forces result in a tearing action within the mix. Further shearing occurs between the blades and
the sides and bottom of the mixer. There are Butterfly mixers, high speed impeller mixers, rotor
stator mixer, twin shaft mixer etc.

Cavitation mixer:

A mixer fitted with driven shaft having a saw tooth disc impeller. The impeller acts to keep the
whole mass ofthe charge in motion and it's size and velocity is determined in direct relation tank
diameter.

Rotor-stator mixer:

This type of mixer has a fixed rotor/stator size and is normally operated at only one or two fixed
velocities. The charge size and vessel size is therefore limited. The overall agitation is
comparatively less vigorous than that produced by the cavitation mixer and viscosities must be
kept correspondingly lower. The reduction of solids particles is achieved by their subjection to
shear forces as they continuously pass through the narrow gap between the rotor and stator.

The application of heat by using a jacketed vessel will accelerate both processes although this is
not always advisable when volatile flammable solvents are used unless strict temperature controls
are used. If multi-solvent systems are used, it is prudent to dissolve the resin in true solvents
before adding the diluents. The normal procedure used is to agitate the liquid while adding the
resin gradually to it. After the addition is complete, a further period of agitation dissolves the
resin. For efficient dissolution the agitation must be of sufficient velocity to maintain resin
particle suspension and separation. The liquid will thus act upon the whole surface of the particle,
giving maximum opportunity for the solubilizing process to take place.

Combination of mills and mixers: Carbo mill, Boa mill, dyno mill & STS mill.
Milling equipment:

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Microflow mill
The Microflow dispersion chamber is a stationary horizontal cylinder. The rotor inside the
chamber carries a series of twelve toughened steel blade called ploughs around its periphery and
lies flush with the length of the cylinder. A number of special steel rods held loosely in the rotor
frame acts as the dispersion medium. As the rotor turns, centrifugal force moves the rods to the
outside of the rod where they form a single layer against the ploughs and the inside of the
cylinder dispersion chamber. The grinding rod layer rotates in the position at a lower speed than
the rotor and ploughs. The rotational velocity differential between the ploughs and the rods and
the change of direction of rotation of the rods as they pass over ploughs create intense shear in the
thin layer of product in which they are turning. The ploughs continuously removes the product
from the chamber into the dispersion area ensuring uniformity. By varying the throughput rate,
dwell time can be adjusted. To assure quality, degree of dispersion, fineness required.

Ball mill

Ball mills are container filled with [25-27% volume] steel balls, 40% void.
Advantage of ball mill: l. Cheap. 2. Power consumption is low. 3. Low maintenance costs. 4.
They act as mixer as well as mill. 5. Enclosed structure ensuring evaporation of solvent does
not occur.
Disadvantage: 1. Cumbersome and bulky. 2. Noisy (because of vibration). 3. Problem in
discharging- particularly for thixotropic mill base. 4. Speed restriction for better grinding. 5.
Cannot handle low viscosity material. 6. Only 50-60% of the volume can be used for the batch.
Bead mill:
Bead mills are used for both liquid and paste inks. In this the container is fixed but the internal
rotor moves. A shaft with number of beads helps in making a better dispersion. Enclosed type
bead mills are used for pigment chip manufacturing. Grinding occurs by compression and shear.
Modem mills are enclosed and use glass beads, operated at high speed and use very small
grinding medium.
A recent innovation in this area has been the introduction of what might be termed as ‘horizontal
bead mill’. This mill constructed with its axis horizontal offers the following advantages over the
vertical axis bead mills:
1. The working system is completely enclosed (minimizes the solvent losses and maximizes
environmental protection.
2. Higher throughput than comparable size vertical mill.
3. Interchangeable liners.
4. Easy cleaning and short color change-over time.
5. High viscosity mill bases can be handled and
6. Wear rate is considerably less and thus thinner walls may be used resulting in better cooling
and heat transfer.

48 |Ink Technology, 2nd  year, 2nd semester 

 
 Fig. Tex mill. (Courtesy of CIMACO Draiswerke GmbH)(kind of bead mill)

3-roll mill:
Advantages
1. High output rate.
2. Optimum level of grinding with good wetting.
3. Uniform dispersion at all times.
4. Simple and safe.
5. Continuous automatic operation.
6. High speed utilization especially in inclined 3-roll mill.
6. Rapid and simple color change of the ink due to excellent mixing. Robust and
maintenance free
design.

Fig. 13.14 Saphir triple-roll mill. (Courtesy of Buhler Ltd)

For:

Factors on which the selection of dispersing equipment depends /Factors controlling efficient
working of ball meal and others refer class notes…………..
For Testing and Problems refer to other part of the notes.

49 |Ink Technology, 2nd  year, 2nd semester