United States Patent (19) 11 Patent Number: 4,923,622

Sherman et al. (45) Date of Patent: May 8, 1990

54 FABRIC SOFTENER COMPOSITION: 56) References Cited
CONCENTRATE OF QUATERNARY U.S. PATENT DOCUMENTS
AMMONIUM COMPOUND AND AN OIL
3,793,196 2/1974 Okazaki ................................ 252A8.8
75 Inventors: Rudolf W. Sherman, Knutsford; 3,861,870 1/1975 Edwards .............................. 8/15.6
Philip J. Stainer, Dennis, both of 4,128,484 12/1978 Barford ........... ... 252A8.6
England 4,464,273 8/1984 Parslow et al. ..... 252/8.8
73 Assignee: Imperial Chemical Industries PLC, 4792.405 12/1988 Shermanet al. .252/86
London, England FOREIGN PATENT DOCUMENTS
21 Appl. No.: 245,806 842842 7/1960 United Kingdom .
1379015 1/1975 United Kingdom .
22 Filed: Sep. 19, 1988
Primary Examiner-A. Lionel Clingman
Related U.S. Application Data Attorney, Agent, or Firm-Cushman, Darby & Cushman
63 Continuation of Ser. No. 808,374, Dec. 16, 1985, Pat. 57 ABSTRACT
No. 4,792,409, which is a continuation of Ser. No. A fabric softener concentrate consists of a quaternary
258,994, Apr. 30, 1981, abandoned, which is a continu ammonium salt containing at least one C8 to C30 long
ation of Ser. No. 952,649, Oct. 19, 1978, abandoned. chain alkyl group, for example dimethyl distearyl am
(30) Foreign Application Priority Data monium chloride, and an oil or substantially water
insoluble compound having oily/fatty properties, for
Oct. 22, 1977 (GB United Kingdom ............... 44062/77 example a half refined white oil or an alkyl ester of a
51) Int. Cl........................ C11D 1/62; D06M 13/46; long chain fatty acid. The liquid concentrate can be
DO6M 15/18 dispersed/emulsified in cold water to form a fabric
52 U.S. Cl. ...................................... 252/8.6; 8/115.6; softener composition.
252/8.8
58 Field of Search ........................... 252/8.6; 8/115.6 2 Claims, No Drawings
 4,923,622
1. 2
those prepared by the reaction of a suitable quaternising
FABRIC SOFTENER COMPOSTION: agent, for example methyl chloride, with a mixture of
CONCENTRATE OF QUATERNARY AMMONIUM amines known as FSynprolam' D35 (Registered Trade
COMPOUND AND AN OL F Mark). "Symprolam' D35 comprises 65 to 75% C13 and
5 approximately 35 to 25% C15 amines with approxi
This is a continuation of application Ser. No. mately 50 wt.% straight chain and 50 wt.% branched
06/808,374, filed Dec. 16, 1985, now U.S. Pat. No. chain amines where the branching is predominantly
4,792,409 which is a continuation of Ser. No. 258,994, 2-methyl.
filed Apr. 30, 1981, which is a continuation of 952,649, The oil or compound having oily/fatty properties
filed Oct. 19, 1978 both abandoned. 10 may be selected from a very wide variety of oils or such
The present invention relates to fabric softeners. compounds. The compound or oil may have lubricant
Traditional fabric softeners are based on quaternary properties with regard to the fabrics to be treated. Par
ammonium salts such as dimethyl distearyl ammonium ticularly suitable are mineral oils, for example half re
chloride or an alkyl imidazolinium salt, and generally fined white oil available from Texaco under the descrip
comprise not less than 5% of this active ingredient. It is 15 tion Base Oil 522 or from Gulf oil under the description
necessary to use such an amount of quaternary ammo Gulf Par 940. Other oils which are suitable include
nium salt in order that a fabric softener may be obtained those containing compounds having from 8 to 22 car
having a commercially acceptable viscosity. Fabric bon atoms, for example soya oil, rape seed oil, coconut
softeners are usually somewhat viscous since without oil, sunflower oil.
sufficient viscosity the quaternary ammonium salt may 20 Examples of compounds having oily/fatty properties
tend to separate from the composition. which may be used in accordance with the invention
These quaternary ammonium salts are normally sup are the alkyl esters of long chain fatty acids, for example
plied by the manufacturers in the form of a paste or methyl oleate, butyl stearate, butyl palmitate, glyceryl
slurry containing 75% of the quaternary salt, 15-25% of monostearate and glyceryl mono-oleate, and long chain
a liquid such as isopropyl alcohol and a balance, if any, 25 fatty alcohols. We have found some evidence which
of water, and the paste must be dispersed/emulsified in indicates that the particular oily/fatty compound used
warm to hot water, mixed with coventional additions can beneficially affect the feel of the fabric treated with
such as perfumes, optical brightener, dye etc. in order to the fabric softener.
obtain a complete fabric softener and then cooled again. The quaternary ammonium salt and the oil (or com
The dispersion/emulsification operation must be con 30 pound having oil/fatty properties) may be used in a
ducted carefully since the shear of the stirrer as well as wide variety of proportions in both the fabric softener
the temperature will influence the viscosity of the fabric concentrate and fabric softener composition of the in
softener and, since it is very difficult to thicken the vention. In some cases, the quaternary ammonium salt
product once the dispersion/emulsification is complete, may be the major component. However, where it is
it is necessary that the dispersion/emulsification opera 35 desired to make a cheaper product it is preferred that
tion is carefully controlled to ensure that the correct the lubricant (or oily/fatty compound) which is the
viscosity is obtained. For these reasons it is not always cheaper component should be present in a major
possible for wholesale or retail suppliers of fabric soft amount since it may also have fabric softening proper
eners to make up their own fabric softener for sale. ties and may be used as a substitute for the compara
We have now surprisingly found that a fabric soft tively expensive quaternary salt. A typical fabric soft
ener liquid concentrate can be prepared which may be ener composition according to the invention will be of
readily and easily dispersed/emulsified in cold water to 3 to 20%, more preferably 5 to 10% active, strength (oil
produce a fabric softener with an acceptable commer (or oily/fatty compound) plus quaternary salt) and such
cial viscosity. a softener composition is obviously cheaper to produce
According to the present invention there is provided 45 than one having the same active strength of the quater
a fabric softener concentrate comprising a fatty quater nary ammonium salt alone.
nary ammonium salt and an oil or substantially water It is preferred that the fabric softener concentrate
insoluble compound having oily/fatty properties. should include a lower aliphatic alcohol containing up
The present invention further comprises a fabric soft to 6 carbon atoms, for example, methanol ethanol or
ener composition comprising water, a fatty quaternary 50 isopropyl alcohol as an additive which gives the re
ammonium salt and an oil or compound having oily/- quired viscosity properties and low temperature stabil
fatty properties. ity. The Applicants have found that in some cases it is of
By a fatty quaternary ammonium salt we mean that advantage to the fabric softener concentrate or compo
the quaternary ammonium salt contains at least one long sition to include a surfactant (preferably non-ionic or
chain alkyl group of 8 to 30 carbon atoms, preferably 8 55 cationic) which may assist in stabilising the concentrate
to 22 carbon atoms, and, optionally, at least one lower or composition. Examples of suitable surfactants for use
alkyl or substituted lower alkyl group, for example a in the invention include alcohol ethoxylates, amine
methyl, ethyl or 2-hydroxyethyl group. In this respect ethoxylates and their salts, alkyl phenol and dialkyl
any one or more of the quaternary ammonium salts phenol ethoxylates.
conventionally used in fabric softeners may be used in 60 The fabric softener concentrate of the invention may
the invention and the preferred quaternary ammonium be readily and easily dispersed/emulsified in cold water,
salt is dimethyl distearyl ammonium chloride. Although typically mains water, at a temperature suitably within
this is an example of a quaternary salt having four alkyl the range 5 to 30° C., more suitably 5 to 20 C., with
groups bonded to the nitrogen atom it is to be under out the need for heating and with only light mixing to
stood that the term quaternary ammonium salt as used 65 produce a fabric softener composition of the required
herein extends also to compounds in which the nitrogen active strength, which will generally be in the range 3
aton is part of a heterocyclic ring, such as imidazoline to 20%. Alternatively the fabric softener composition
salts. Other suitable quaternary ammonium salts include may be produced simply by producing a dispersion
 4,923,622 4.
3
/emulsion in water of a quaternary ammonium salt and TABLE 2
an oil (or oily/fatty compound), the latter two compo Constituent Composition L Composition M
nents not having been previously admixed to produce a loz loz
concentrate. The Applicants have found that in some Kemamine Q9702 C
Texaco Base Oil 522 2 oz 1 oz
cases it is desirable to use a solvent, for example isopro Optical brightener (0.2% 10 oz. 5 oz
pyl alcohol, to assist the preparation of the composition solution)
at the preferred relatively low temperature used. Blue dye (0.2 solution) 2 oz. 2 oz.
Perfume 0.95 cc 0.94 cc
The viscosities of the fabric softener concentrate and Water 18 oz 23 oz.
composition depend on both the type and the amount of
oil or oily/fatty compound incorporated therein and it The non-ionic surfactant used was "Synperonic' A2
is an easy matter to produce fabric softeners having a (Registered Trade Mark) which is of similar composi
range of viscosities by varying the time and amount of tion to “Synperonic' A3 (See Example 1).
oil or oily/fatty compound used. It is also found that the Compositions L and M had active strengths of 63%
amount of quaternary salt required to produce a disper 15 and 5-7% respectively and each was found to be of
sion/emulsion of a particular viscosity is less than in the commercially acceptable viscosity and performance.
case where no oil (or compound having oily/fatty prop
erties) is used and these features are important advan EXAMPLE 3
tages of the present invention. The Applicants consider Arquad 2HT (a dihydrogenated tallow dimethylam
that acceptable commercial viscosities are likely to lie in 20 monium chloride) and Texaco Base Oil 522 were mixed
the range of 15 to 40 seconds, more suitably in the range together in various ratios. To 10 g of each mixture iso
20 to 25 seconds, measured at 20° C. in No 4 Ford Cup. propanol was added until a liquid product resulted at
Fabric softener concentrate and compositions ac 23 C. Similarly isopropanol was added to blends of 1 g
cording to the invention can be produced without the of non-ionic surfactant ("Synperonic' A3) and 9 g Ar
need for the very careful control of the mixing opera 25 quad 2HT/Texaco Base Oil 522 mixture to form a liquid
tion which is a feature of prior art preparations. The product. Table 3 shows the weights of isopropanol
invention thus makes it possible for fabric softeners to required:
be produced by manufacturers who, because of their TABLE 3
lack of suitable mixing equipment, were previously OIL:ARQUAD
required to purchase softener because of the difficulties 30 2HT RATIO 5: 10:3 5: 2: 5:3 10:7 O:9
in its manufacture. Conventional additions such as dyes Isopropanol
and optical brighteners may of course be added during required (g)
the production of the fabric softener as desired. Without surfactant 2.75 3.71 2.83 3.70 2.90 4.23 5.61
The following Examples illustrate the concentrate With surfactant 30 15 1.73 1.0 6.77 6.78 5.30
35
and composition of the present invention.
EXAMPLE 1. NOTE: When isopropanol was added to 10 g Arquad
2HT alone, substantial amounts of solid remained
Two fabric softener concentrates were prepared by even after addition of 15 g isopropanol. After 40g
mixing the various constituents in amounts as shown in 40 isopropanol had been added, the product was sub
Table 1 (all parts are by weight): stantially liquid although small amounts of solid
TABLE 1. settled in time. Clearly, the use of an oil reduces
Constituent Concentrate A: Concentrate B;
considerably the amount of solvent required to
produce a stable liquid product.
Kemamine Q9702 C 4 parts 4 parts 45
Texaco Base Oil 522 6 parts 5 parts EXAMPLE 4
Methanol 1 part 2 parts
Isopropyl alcohol Mixtures of Arquad 2HT with two oil/fatty materials
l part
Non-ionic surfactant i part were made. Isopropanol was added to 10 g of each
1 part
mixture or 9 g of mixture and 1 g non-ionic surfactant
("Synperonic' A3) as in Example 3. Table 4 shows the
Kemamine Q 97.02 C is a commercially available 50 weights of isopropanol required:
quaternary ammonium product which is based on 75% TABLE 4
dimethyldihydrogenated tallow ammonium chloride.
The non-ionic surfactant used was "Synperonic' A3 OIL SYNPROL ISOBUTYL
Oil:Arquad 2HT Primarv alcohol PALMITATE
(Registered Trade Mark) which is a commercially 55 Ratio 5: 0.9 9: l: :9
available mixture of detergent alcohol ethoxylates pre Isopropanol
pared from a carefully controlled mixture of C13 and required
C15 alcohols. Without surfactant 7.25 8.62 3.4 7.3 8.2
The two concentrates, which were thin mobile liq With surfactant 7.30 30 3.1 6.1 7.5
uids at room temperature, were dispersed/emulsified in 60
cold water without heating to produce fabric softener "Synprol' (Registered Trade Mark) is a high quality
compositions of commercially acceptable viscosity and primary alcohol and is a carefully controlled mixture of
performance. 67% C13 and 33% C15 alcohols.
EXAMPLE 2 65 EXAMPLE 5
Two fabric softener compositions were prepared by A fabric softener concentrate was prepared by mix
mixing the various constituents in amounts as shown in ing "Synprolam" D35QC (Registered Trade Mark),
Table 2: which is a mixture of quaternary compounds derived
 4,923,622
5 6
from "Synprolam' D35 and comprises approximately phate), 40 wt % Texaco Base Oil 522 and 10 wt %
75% di (C13-C15) dimethyl ammonium chloride and “Synperonic' A3 (Registered Trade Mark) surfactant.
approximately 25% isopropanol, with (a) Texaco 522 EXAMPLE 2
oil, (b) "Synprol', (c) Tung oil, (d) Isobutyl palmitate,
each in ratios of 9:1 and 1:9 by weight. All mixtures 5 A liquid fabric softener concentrate was prepared by
were liquid at 23° C. mixing 10 wt.% of Actisoft TE (a 1-tallowalkyl amido
EXAMPLE 6
ethyl 2-tallowalkyl-3-methyl imidazolinium methosul
phate), 27.25% Kemamine QSML/2, 38.02 wit% Gulf
Varisoft 475 (1-tallowalkyl amidoethyl 2-tallowalkyl Par Oil 940, 5.71% “Synperonic' A3 (Registered Trade
3-methyl imidazolinium methosulphate) was mixed O Mark) Surfactant, and 19.02% isopropyl alcohol. The
with (a) Texaco 522 oil, (b) "Synprol', (c) Tung oil in concentrate was a clear mobile liquid at temperatures
ratios of 9:1 and 1:9 by weight. All mixtures were liquid down to 5 C.
at 23 C. The viscosity of a 7% dispersion/emulsion in water at
20 C. was compared with that of a 7% dispersion
EXAMPLE 7 15 /emulsion of a concentrate containing no Actisoft TE
A fabric softener concentrate was prepared by mix and consisting of 30.28% Kemamine QSML/2, 42.25%
ing Kemamine QSML/2 (4 pts) and non-ionic surfac Gulf Par Oil 940, 6.34% “Symperonic' A3 surfactant
tant "Symperonic' A3 (1 pt) with coconut oil (6 pts) at and 21.13% isopropanol. The viscosities (at 20° C. using
23 C. A clear mobile liquid was obtained. No 4 Ford Cup) were respectively 16 seconds and 11
NOTE: Kemamine QSML/2 is a quaternary ammo 20 seconds, thus indicating that the composition containing
nium product which is based on approximately both Actisoft TE and Kemamine QSML/2 had a rather
70% dimethyldihydrogenated tallow ammonium more commercially acceptable viscosity than that con
chloride and approximately 30% methanol. taining Kemamine QSML/2 alone.
EXAMPLE 8 25 EXAMPLE 3
A mixture of 4 pts "Synprolam' and 6 pts "Synprol" A series of tests were carried out on a number of
was diluted in water to give a dispersion containing fabric softening compositions to assess the softness of
2.33% quaternary salt wit/wt. This had a viscosity at 25 fabrics treated with them.
C. of ca 290 cS. A dispersion in water containing 2.33% The fabrics used in the tests were babies nappies
30 which were 50% cotton and 50% viscose. After desiz
quaternary salt and no "Synprol" had viscosity ca 2 cS.
The dispersion with "Synprol' was stable showing no ing by washing with a commercial washing powder
separation after seven days. ("Drive') and rinsing throughout, the nappies were put
through four wash-rinse-treat cycles as follows:
EXAMPLE 9 Wash cycle: tap water at 50° C. containing 1 g commer
35 cial washing powder (“Tide') per liter at a fabric:
A mixture of 4 pts Kemanine QSML/2 and 6 pts
Texaco 522 oil was diluted in water to give a dispersion water ratio of 1 kg: 30 l over 5 min.
containing 2.33% quaternary salt wit/wt. This had a Rinse cycle: Four washes in tap water at 25 C. at a
viscosity at 25 C. of 783 cS. A dispersion containing fabric: water ratio of 1 kg: 30 l.
2.33% quaternary salt and no oil had viscosity 59 cS. Treatment: Formulated fabric softener product was
The dispersion with oil was stable showing no separa applied at the rate of 10 g per 300 g fabric in 91 tap
tion after seven days. water at 25 C. over 2 min.
Drying: All nappies were dried separately in a tumble
EXAMPLE O dryer.
A fabric softener concentrate was prepared by mix 45
Two fabric softener formulations according to this in
ing 4.225 parts Gulf Par 940, 3.028 parts Kemamine vention were used with water being used as a control.
QSML/2 and 0.634 parts "Symperonic' A3 (Registered The formulations were:
Trade Mark) surfactant. A fabric softener composition 1. Kemamine QSML/2, 2.2% active wit/wt--Texaco
was prepared by dispersing the concentrate in water to Base Oil 522 6.67% wt/wt in water
form a composition containing 7.887% concentrate. 50 2. Kemamine QSML/2, 2.2% active wit/wt-Coconut
Two such compositions were prepared, the concen Oil 6.67%, wit/wt in water
trate temperature in each case being 25 C. The temper 3. Water only
ature of the water used was 25 C. in one case and 30 After 1 cycle and 4 cycles 24 judge paired compari
C. in the other and the viscosities (at 20 C. using No 4 son panel tests were carried out to evaluate softness.
The results of these tests are shown in Table 5:
Ford Cup) were respectively 25 seconds and 12 sec 55
onds. TABLE 5
It is clear, therefore, that it is advantageous to pre Panei Test for Softness : Votes awarded to each treatinent
pare fabric softener compositions according to the in (3 vote awarded where no decision)
vention by cold mixing of the concentrate and water. In Formulation No. 1 cycle 4 cycles
this way, it is possible to obtain compositions of com 60 30.5 39
mercially acceptable viscosity. Mixing at higher tem 2 30.5 33
3 11 O
peratures produces less viscous, unacceptable composi
tions.
EXAMPLE 11 NOTE: For a 3 object paired comparison test with 24
65 judges a difference of votes is significant at the
A liquid fabric softener concentrate was prepared by 95% level.
mixing 50 wit% of Alkaquat T (a 75% active 1-methyl These tests indicate the excellent qualities possessed
tallowanidioethyl 2-tallow imidazolinium methosul by formulations 1 and 2 which, coupled with their ease
 4,923,622
7 8
of manufacture, give them advantages over other simi The times were as follows:
lar formulations prepared in the past without the use of One immersion at 5% conditioner concentration
an oil or oily/fatty compound. Besides the good soften 10% composition of the invention: 20 seconds
ing properties shown, the results suggest that different 5% active DMDHT: 33 seconds
oils may give different degrees of fabric softening. 5 Five immersions at 1% concentration
10% composition of the invention: 21 seconds
EXAMPLE 14 5% active DMDHT: 63 seconds
Wetting tests were carried out by a modified Draves The water temperature was 12 C.
test comparing a 10% dilution of a fabric softener con It would appear that fabric conditioners according to
position according to this invention to a proprietary O this invention are superior in re-wetting and that there is
brand containing 5% active dimethyl di-hydrogenated virtually no build up of product on the cotton pieces.
tallow ammonium chloride (DMDHT). (The fabric We claim:
softener composition according to this invention con 1. A substantially water-free softener liquid concen
sisted of (all parts by wt) 30.28% Kemamine QSML/2, trate consisting essentially of a non-heterocyclic fatty
42.25% Gulf Par Oil 940, 6.34% "Symperonic' A3 sur 15 quaternary ammonium salt which contains at least one
factant, and 21.13% isopropanol.) long chain alkyl group of 8 to 30 carbon atoms and an
Cotton tapes of one inch width and 20 cm length oil or water-insoluble compound having oily/fatty
were soaked and dried five times in the two products properties and selected from the group consisting of a
using 3 pieces of tape in 250 cc solution containing 1% mineral oil, a half-refined white oil, rape seed oil, Sun
of the fabric conditioner. The experiment was repeated 20 flower oil, tung oil and long chain C8 to C24 fatty alco
by soaking and drying once only in a 5% solution of hols, said concentrate having a viscosity in the range of
conditioners. The wetting test was carried out using a about 15 to 40 seconds, measured at 20 C. in No. 4 Ford
20gm weight attached by means of a cotton thread to a Cup, and said concentrate capable of being dispersed
metal hook weighing approx. gm. The hook is at /emulsified in cold water at a temperature of 5 to 30
tached to the treated cotton pieces and dropped into a 25 C.
500 cc measuring cylinder full of water. The time is 2. A concentrate as in claim 1 wherein the quaternary
measured for the hook attached to the fabric to sink to ammonium salt is a tetraalkyl
k k :
ammonium
k
salt.
the bottom.

35

45

50

60

65