CA1111617A

CA1111617A - Textile conditioning compositions containing polymeric cationic materials

Info

Publication number: CA1111617A
Application number: CA316,514A
Authority: CA
Inventors: Arthur L. Rudkin; John H. Clint; Kenneth Young
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 1977-11-21
Filing date: 1978-11-20
Publication date: 1981-11-03
Also published as: FR2409302B1; DE2849931A1; IT7829962A0; FR2409302A1; GB1604030A; JPS54106696A; BR7807644A

Abstract

TEXTILE CONDITIONING COMPOSITIONS
CONTAINING POLYMERIC CATIONIC MATERIALS

ABSTRACT OF THE DISCLOSURE

A textile conditioning composition intended for use in the final rinse after a washing operation comprises a cationic textile softening agent and a small amount of a polymeric cationic salt of specified type, and optionally a substantially water insoluble nonionic textile softening agent the weight ratio of nonionic textile softener to cationic components being in the ratio no greater than 10:1. Preferably, the compositions are in the form of an aqueous dispersion and contain a water-insoluble cationic surfactant in combination with a cationic polysaccharide.
Especially useful compositions are based on di-tallow quaternary ammonium or imidazolinium salts and cationic guar gums.

Description

l'7 BACKGROUND OF THE INVENTION
__ The invention relates to textile conditioning compositions employin~ cationic textile softening agents and containing certain polymeric substances which increase the effectiveness of the cationic textile agents employed.
Textile conditioning, especially softening, compositions in the form of aqueous dispersions are well known, and are primarily intended to be added to the last rinse liquor in a conventional clothes-washing process.
Most of such compositions currently on the market comprise a fairly low concentration, for instance about 3-10~, of a cationic textile softener or of a mixture of more than one, together with relatively minor amounts of emulsifiers, and with aesthetic additives such as colour and perfume. These compositions are used at quite low concentration in the treatment bath, for instance about 0.25~ by weight.
The rinse liquors, even the last, after a conven-tional bath using an anionic surfactant~based detergent composition normally contain traces of residual anionic surfactant carried through from the wash liquor. Typically 5-20 parts per million of anionic surfactant is present in the final rinse liquor. This anionic surfac~ant reacts with the cationic softener component of a softening compositions, thereby reducing its performance. The use of relatively water soluble cationic surfactants to scavenge anionic has been described in U.S. Patent No. 3,974,076, but these sub~
stances need to be used at considerable levels.
It has now been found that this scavencJing func-tion can be performed by very Low levels of certain polymeric cationic salts. Furthermore some of these salts ha~e been found to have softening properties in the presence of cationic - ~a.~ 7 softenexs even when employed in baths which contain no an-ionic surfactant, and they even replace several times their own weight of conventional cationic softener without overall loss of softening performance of the composition. This en-ables the cost of such compositions to be reduced.
German Offenlegungsschrift No. 2,724,816 describes textile softening and ironing assistants containlng cationic softeners or mix-tures -thereof with nonionic softeners and relatively high levels of cationic dextrin as agent providing the ironing assistant properties.
A paper by J.A. Faucher and E.D. Goddard in J.
Colloid and Interface Science 55 12) 313-319, 1976 describes a study of the effect of, inter alia, a cationic surfactant upon the sorption of cationic hydroxyalkyl cellulose on hair.

DESCRIPTION OF q~HE INVENTION

It is the object of the present invention to provide a textile conditioning composition which has good softening performance and improved resistance to carry-over of an-ionic surfactants into the last rinse.
It is a further object of the invention to provide a textile conditioning composition with enhanced fabric softening ability without a substantially increased concen-tration of cationic materials.
According to the present invention, a textile conditioning composition comprises:
(a) a cationic textile softening agent, as here-inafter defined, and (b) from 0.001 to 0.70% by weight of one or more polymeric cationic salts selected from the group consisting of (i) cationic polysaccharide gums, (ii) cationic starch and starch derivatives (iii) cationic polyvinyl pyrldien and poly~inyl pyridinium salts, and co-polymers therewith.

(iv) cationic polyvinyl alcohol, (v) cationic polyvinyl pyrollidone co-polymers, (vi) co polymer of dialkylaminoalkyl meth-acrylate, wherein each alkyl has 1-3 carbon atoms, with styrene, or a neutral acrylic ester, (vii) condensation co-polymers having the repeating unit R12 ~ R12 - - C - R13 - C - o wherein Rll is hydrogen or a Cl 6 alkyl group, or is R12OA, wherein A is hydrogen or a Cl_20 acyl group or a quaternary nitrogen-containing group, each R12 independently is a Cl 6 alkylene group and R13 is a Cl_6 alkylene, hydroxy alkylene or C2 6 alkenylene group or an arylene group said copolymer being rendered cationic either by the presence of said quaternary group in some or all of radicals A, or by rendering some or all of the nitrogen atoms in the back bone cationic or by both, (viii) condensation copolymers havi.ng the repeating unit rIL~. ~L D ~:il7 r H 117 1 ~
13 C N - R15 - N - R16 - N _ wherein R13 is a Cl_6 alkylene hydroxyalkylene or alkyl or an aryl group, R15 and R16 independently are a Cl 6 alkylene group, and R17 is hydrogen or a Cl 6 alkyl group, said copolymer being rendered cationic at some or all of the nitrogen atoms which are not adjacent to CO groups, (ix) condensation copolymers having the repeating unit r I ~ 8 O - CH2 ~ CH - CH2 O - C - R13 - C

wherein R13 is a Cl 6 alkylene, hydroxy alkylene or C2_6 alkenylene residue or an arylene group and some or all of radicals A are quaternary nitrogen-containing groups the remainder being hydroyen atoms, and (x) quaternised polyethylenimines having at least 10 ethylenimine residues in the molecule, and (c) optionally a substantially water-insoluble nonionic textile conditioning agent, in amount such that the weight ratio of component ~c) to components (a) and (b) together is not grea-ter than 1:10.

Preferably the textiles treated are at least parkly made from cellulosic e.g. cotton, fibres. The compositions of the invention may be solids, e.g. granules, or gels, pastes or liquids, or they may be absorbed in or adsorbed on a water-insoluble substrate. Usually they are in the form of more or less viscous liquid dispersion and preferably the disperse phase is liquid crystalline. Such liquid pro-ducts usually contain from about 1% to about 30% ,by weight of components (a), ~b) and (c) together, more usually from about 3~ to ]5%, especially from about ~% to 10%.
The carrier liquid when present is aqueous and com-prises water ~or the main part, optionally with some water miscible organic solvent, such as, in particular, methyl, ethyl or isopropyl alcohols.

Cationic Softener The cationic textile softening agents used in compositions of the invention contain in their molecule either one long chain alkyl or alkenyl group having at least 16 carbon atoms, or two alkyl or alkenyl groups, which may be the same or different, each containing 10 to 22 carbon atoms. Mixtures of two or more of these cationic softeners may be used.
Highly preferred cationic softeners for the present invention are substantially water-insoluble quaternary ammonium compounds, and C16 25 alkyl imidazolinium salts, conventionally used in fabric softening compositions.
Well-known species of substantially water-insoluble quaternary ammonium compounds have the ormula:-r ~ , N ~ X

wherein Rl and R2 represent hydrocarbyl groups of from about10 to 22 carbon atoms; R3 and R4 represent hydrocarbyl groups containing from 1 to about 4 carbon atoms X is any anion such as a halide, a C2 22 carboxylate, or an alkyl- or aryl-sulf(on)ate. Examples o~ preferred anions include bromide, chloride, methyl sulfate, toluene-, xylene-, cumene-, and benzene-sulfonate, dodecylbenzenesulfonate, benzoate, para-hydroxybenzoate, acetate, propionate and laurate. Represent-ative examples of quaternary softeners include ditallow dimethyl ammonium chloride, ditallow dimethyl ammonium methylsulfate; dihexadecyl dimethyl ammonium chloride; di(hydrogenated tallow) dimethyl ammonium chloride; dioc~adecyl dimethyl ammonium chloride; dieicosyl dimethyl ammonium chloride; ~didocosyl ammonium chloride;
di(hydrogenated tallow) dimethyl ammonium methyl sulfate;

dihexadecyldiethYl ammonium chloride; di(coconutalkyl) dimethyl ammonium chloride. Ditallow dimethyl ammonium chloride, di(hydrogenated tallow)dimethyl ammonium chloride and di(coconutalkyl) dimethyl ammonium chloride are preferred.
Also suitable are the single long chained quaternary ammonium compounds of the above formula wherein Rl is a C16 to C22 alkyl or alkenyl, preferably C16 to C20 alkyl, and R2, R3 and R~ are lower alkyl groups that is Cl to C~ alkyl groups especially methyl, or aryl yroups and X is as defined above. Optionally also two or all three of R2, R3 and R~

.

may together represent a heterocyclic ring. Some repre-sentative examples of such compounds are cetyl and stearyl trimethyl ammonium bromides, behenyl trimethyl ar~monium methosulfate, oleyl methyl diethyl ammonium chloride, cetyl, stearyl or oleyl pyridinium chloride, behenyl pyridinium bromide, stearyl methyl morpholinium chloride, stearyl or oleyl ethyl or propyl morpholinium chloride.
Another class of preferred cationic surfactants are the C10 25 alkylimidazolinium salts. Preferred salts are 10 those conforming to the formula:-~ H H +
I I
H - C C H O

N ~ _ C2~4 - N - C R~ X

wherein R6 is a Cl-C4 alkyl radical, R$ is hydrogen or a Cl-C4 alkyl radical, R8 is a C10-C25 alkyl radical and R7 is hydrogen or a C10-C25 alkyl radical. X is a charge balancing ion which has the same meaning as X defined in the quaternary ammonium surfactant above.
Preferred members of this class are sold under the Trade Marks Varisoft 455 (Ashland Chemical Co.) and Steinaquat (Rewo). Varisoft 455 is believed to be the com-pound of formula given above wherein R6 is Me, R7 and R8 aretallow alkyl, and R5 is hydrogen.
The above described water-insoluble cationic softeners are very highly preferred in compositions of the present invention and, preferably, comprise the only cationic surfac-tant present.

Other suitable cationi.c surEactants, which are water-soluble, are descxibed below; these can be used as the sole cationic surfactant in compositions of the invention, but more preferably are us~d in comblnation with the water-insoluble cationic surfactants~ in a ratio of water-insoluble to water soluble of 5:1 to 1:3, especially from 3:1 to 1:1.
Suitable water-soluble cationic surfactants include the substituted polyamine salts of general formula:-Rlo l ~ ICH2)n N ~ Rg, X( ) Rg ~ Rg wherein Rlo is an alkyl or alkenyl group having from about 16 to 24, preferably from 16 to 20, especially from 16 to 18 carbon atoms, the groups Rg which may be the same or different, each represent hydrogen, a (C2H4O)pH, or a (C3H6O)qH, or a Cl 3 alkyl groups where p and q may each be O or a number such that (p + q) does not exceed 25, n is an integer from 2 to 6, preferably 3, m is from about 1 to 9, preferably from 1 to 4, most preferably 1 or 2, and X( )represents o~e or more anions having total charge balancing that of the nitrogen atoms.
Preferred compounds of this class, are most pre-ferred, N-tallow-N,N'N',tri-ethanol-1,3-propylene diamine dichloride or di-methosulfate commercially available under the Trade Marks Lilamin 540EO3 (Lilachim), Dinoramax SH3, Inopol ODX3 (Pierrefitte Auby), and N-tallow-N,N,N',N',N'-pentamethyl-l, 3-propylene diamine dichloride, commercially available under the Trade Marks Stabiran MS-3 (Pierrefitte Auby); Duoquad (Armour ~ess); Adogen 477 (Ashland Co.).
Also suitable is the sub~tance sold as Dinorma ~(Pierrefitte _ g ~' Auby) or Duomac~ (Armour Hessl believed to have the formula:-1 wy 2 ( 2)3 3~ 2(OCOCH3) or the corresponding chloride. Herein Tallowyl~ representspredominantly C16 and C18 alkyl groups derived from tallow fatty acids.
Other suitable cationic surfactants are marketed under the following Trade Marks:-Sopa (Pierrefitte ~uby) Sopapa " "
Lilamin LS33 (Lilachim) Polaram L 200 (Pierrefitte Auby) Taflon - 320A (Diichi Xogyo Seiyaku Co.).
When the compositions of the invention are in the conventional form or dispersions of active components in an aqueous carrier medium, they usually contain from about 0~1 to 14% cationic surfactant, preferably from about 0.3 to 8%
and most preferably about 1% to 5%.

Polymeric Cationic Salts The polymeric cationic salts of the present in-vention can be amine salts or quaternary ammonium, phosphoniumor sulphonium salts. Preferred are quaternary ammonium salts.
They include cationic derivatives of natural polymers such as some polysaccharide, gums, s-tarch and certain cationic synthetic polymers such as polymers and co-polymers of cationic vinyl pyridine or vinyl pyridinium halides.
Preferably the polymeric salts are water soluble, ~or in stance to the extent of at least 0.5~ by weight at 20C.

Preferably they have molecular weight from 1,000 to abou-t 1,000,000, especially from 2,000 to 500,000. As a general ,~

rule, the lower the molecular weight -the higher the aegree of subsititution (D.S.) by cationic, usually quakernary groups, which is desirable, or, correspondingly, the lower the degree of substitution the higher the molecular weigh-t which is desirable, but no precise relationship appears to exist.
O~ the polysaccharide gums, guar and locust bea~
gums, which are galactomannam gums are available commercially, and are preferred. Thus guar gums are marketed under Trade 10 Mark CSAA M/200, CSA 200/50 by Messrs. Meyhall and Stein-Hall, and hydroxyalkylated guar gums are available from the same suppliers. Other polysaccharide gums commercially available include:

Xanthan Gum Ghatti Gum Tamarind Gum Gum Arabic Agar.
Cationic guar gums and methods for making them are 20 disclosed in BP 1,136,842 and USP 4,031,307. Preferably they have a D.S. of from 0.1 to about 0.5.
An effective cationic guar gum is Jaguar C-13S (Trade Mark - Mayhall), believed to be derived from guar gum of molecular weight about 220,000, and to have a degree of substitution about 0.13, wherein the cationic moiety has the formula:
- CH2cH(oH)cH2N Me3, Cl Very effective also is guar gum quaternised to a D.S. of about 0.2 to 0.5 with the quaternary grouping:-~CH2cH(oH)cH2N Me3~ Cl or -cH2cH=c~cH2N Me3' Cl Cationic guar gums are a highly preferred group of cationic polymers in compositions according to the invention and act both as scavengers for residual anionic surfactant and also add to the softening effect of cationic textile softeners even when used in baths containlng little or no residual anionic surfactant. The cationic guar gums are effective at levels from about 0.03 to 0.7 ~ by weight of the compositions preferably up to 0.4%
The other polysaccharide-based gums may be quater-nised similarly and act substantially in the same way with varying degrees of effectiveness.
Suitable starches and derivatives are the natural starches such as those obtained from maize, wheat, barley etc., and from roots such as potato, tapioca etc., and dextrins, particularly the pyrodextrins such as British gum and white dextrin.
In particular, cationic dextrins such as the above, which have molecular weights (as dextrins) in the range from about 1,000 to about 10,000, u~ually about 5,000, are effective scavengers for anionic surfactants. Preferably the D.S. is in the range from 0.1 upwards, especially from about 0.2 to 0.8. Also suitable are cationic starches, especially the linear fractions, amylose, quaternised in khe usual ways. Usually the D.S. is from 0.01 to 0.9, pre~
ferably from 0.2 to 0.7, thak is rather hiyher than in most conventional cationic starches.

The cationic dextrins usually are employed at levels in the range from about 0.05 to 0.7% o~ the cornposition, especially from about 0.1 to 0.5%.
Polyvinyl pyridine and co-polymers thereof with for instance styrene, methyl methacrylate, acrylamides, N~
vinyl pyrrolidone, quaternised at the pyridine nitrogens are very effective, and can be employed at even lower levels than the polysacchaxide derivatives discussed above, for instance at 0.01 to 0.2% by weight of the composition, 10 especially from 0.02 to 0.1%~ In some instances the per-formance seems to fall off when the content exceeds some optimum level such as about 0.05~ by weight for polyvinyl pyridinium chloride and its co-polymer with styrene.
Some very effective individual polymeric cationic salts are the following Polyvinyl pyridine, molecular weight about 40,000, with about 60% of the available pyridine nitrogens quater-nised.
Co-polymer of 70/30 molar proportions of vinyl 20 pyridine/styrene, molecular weight about 43,000, with about 45% of the available pyridine nitrogens ~uaternised as above.
Co-polymers of 60/40 molar proportions of vinyl pyridine/acrylamide, with about 35~ of the available pyridinenitrogens quaternised as above.
Co-polymers of 77/23 and 57/43 molar proportions of vinyl pyridine/methyl methacrylate, molecular weight abou-t 43,000, with about 97% of the available pyridine nitrogens quaternised as above.
These polymeric cationic salts are effective in the compositions at very low concentrations Eor instance from 0.01~ by weight to 0.2% especially from about 0.02%

.~

to 0.1~. In some insta~ces the effectiveness seems to alloff, when the content exceeds some optimum level, such as for polyvinyl pyridine and its styrene co-polymer about 0.05%.
Some other ef~ective polymeric cationic salts are:
Co-polymer of vinyl pyridine and N-vinyl pyrrolidone (63/37) with about 40% of the available pyridine nitrogens quaternised.
; Co-polymer of vinyl pyridine and acrylonitrile (60/40), quaternised as above.
Co-polymer of N,N-dimethyl amino ethyl methacrylate and styrene (55/45) quaternised as above at about 75% of the available amino nitrogens.
Eudraglt E (Trade Maxk of Rohm GmbH) quaternised as above at about 75% of the available amino nitrogens.
Eudragit E is believed to be co-polymer of N,N-dialkyl amino alkyl meth~crylate and a neutral acrylic acid ester, and to have molecular weight about 100,000 to 1,000,000.
Co-polymer of N-vinyl pyrrolidone and N,N-diethyl amino methyl methacrylate (40/50), quaternised at about 50~ of the available amino nitrogens.
These cationic polymers may be pared in a known manner by quaternising the basic polymers.
Yet other co-polymers are condensation polymers, formed by the condensation of two or more reactive monomers both of which are bifunctional. Two broad classes of these polymers may be formed which are than made cationic, viz (a) those having a nitrogen atom which may be cationic in the back bone, and (b~ those not containing a nitroyen which may ~e made cationic in the back bone but containing d reactive , ~j site which will facilitate introduction of a cationic group.
Compounds of class (a) may be prepared by condens-ing a tertiary or secondary amine of formula:

/ Rl 2 RllN\
R12~
wherein Rll is H or a Cl 6 alkyl group, preferably methyl, or R12OH and each R12 independently is a Cl 6 alkylene group, preferably ethylene, with a dibasic acid, the corresponding acyl halide or anhydride having formula XOOC ( 13) or CO
\
CO
wherein R13 is a Cl 6 alkylene, hydroxy alkylene or alkenyl group or an aryl group, and X is H, or a halide preferably chloride. Some suitable acids are succinic, malic, glutaric, adipic, pimelic, suberic, maleic, ortho-, meta-and tere-phthalic, and their mono and di-chlorides. Very suitable anhydrides include maleic and phthalic anhydrides.
The condensation leads to polymers having repeating units of structure . _ _ Rl 1 f - - R12 ~ N R12C R13 _ ~ _ Reactions of this sort are described in sritish Patent Specification No. 602,048.

~,..

These can be rendered cationic for instance by addition of an alkyl or alkoyl halide or a di-alkyl sulphate at the back bone nitrogen atoms or at some of them. When R11 is (R120H) this group can be esterified by reaction with a carboxylic acid, e.g. a Cl 20 saturated or unsaturated fatty acid or its chloride or anhydride. When long chain, about C10 and higher, fatty acids are employed these polymers may be described as "comb" polymers. Alternatively when Rll is (R12OH) the Rll groups may be reacted with-a cationic e.g. a quaternary ammonium group such as glycidyl trimethyl ammonium chloride or l-chloro-but-2-ene trimethyl ammonium chloride, and like agents mentioned hereinafter.
Some cationic polymers of this class can also be made by direct condensation of a dicarboxylic acid etc. with a difunctional quaternary ammonium compound having for instance the formula RllR14N (R12H)2 ' where R14 is an H or Cl 6 alkyl group, and Rll and R12 are as defined above, and Z is an anion.
Some non limiting typical examples of polymers of this class have repeating units as follows:
(a) r (CH2)2OH f 11 t (CH2)2 - N - (CH232 - O C - (CH2)4 - C - O

from triethanolamine and adipic acid or its acid di-chloride.

(b) r C~H3 t' 2)2 1CH2)2 - O - C - C6~I4 C - O

from methyl diethanolamine and ortho or tere phthalic acid or phthalic anhydride (C)~2) 3N ~CEI2)--30--C -- (Cl~2)--2 C - O ~
from dipropanolamine and succinic acid or anhydride (d) r (cH2 20H O O

2) 2 (CH2)-20-C - CH = CH - C - O
from triethanolamine and maleic anhydride.
Cationic derivatives of these polymers may be illustrated by the following, based on polymers of class (a).
(e) ~CH2)20H O

_ ( 2)2 Nl (CH2)2 - O - C ~ (CH2)4 ~ C - -CH3, Cl _ by quaternisation of the back bone nitrogen by methyl chloride.

(f ) + (CH2) 2- N (C~2) 2 - - g -- (CH2)4 -C - D t 18 37 ~ Cl by quaternisation of the back bone nitrogen by octadecyl chloride. ~ Cl CH2)20 CH2CH(OH)CH2N(CH3) 3 0 (CH2)2 ~ N - (CH2)2 ~ - C - (CH2)4 C - o by reaction of the ethanol branches with glycidyl trimethyl ammonium chloride.

(C 2) 2 1 (C~2) 2 ~ - C - (C~2)4 - C -by direct condensation polymerisat:iorl of dimethyl diethanol ammonium chloride with adipic acid.

Another class of copolymer with nitrogens which can be made catiQnic in the back bone c~n be prepared by re-action of a dicarboxylic acid, etc. as defined above with a dialkylene triamine, having structure H2N R15 N R16 NHz where R15 and R16 independently each represent a C2 6 alkyl-ene group, and R17 is hydrogen or a Cl_6 alkyl group. This leads to polymers having the repeating unit fi O H 117 7 L 13 C N - Rls - N ~ R16 ~ J

~herein the nitrogen not directly linked to a CO group i.e.
not an amide nitrogen, may be rendered cationic, as by re-action with an alkyl halide or dialkyl sulphate.
- Some non limiting typical examples of polymers of this class are as follows:

O - O H H H
(a) _ = ( 2)4 C N (CH2)2 N ~ (CH2) 2 - N -from diethylene triamine and adipic acid, leadingby reaction with e.g. excess (CH3)2 S04 to r ~ H3 ~ 7 1 L C - (CH2)4- - - (CH2) 2- N ~ (CH2) 2 CH3,CH3S04 O O H H H
( b ) - C - C6H4 - C-- N - (CH2)3 - N - (CH2)3- N - -from dipropylene triamine and phthalic acid or anhydride, leading by reaction with e.y. excess C12 H25 I to - 1~ -)7 11 H f 12 25 H
C - C6H4 - C - N - (CH2)3 - N - (C~2)3 - N - _ _ C12H25, I

Commercial examples of a condensation polymers believed to be of this class are sold under the Trade Mark Alcostat by Messrs. Allied COlloidsa Yet other cationic polymeric salts are quaternised polyethyleneimines. These have at least 10 repeating units, some or all being quaternised, that is having the formula:

R18' X
where R18 is Cl_20 alkyl, or benzyl, and X is an anion Commercial examples of polymers of this class are also sold under the generic Trade name IAlcostat by Messrs.
Allied Colloids.
It will be appreciated by those skilled in the art that these quaternisation and esterification reactions do not easily go to completion, and usually a degree of substitution up to about 60% of the available nitrogen is achieved and is quite effective. Thus it should be under-stood that usually only some of the units constituting the cationic polymers have the indicated structures.
Polymers of class (b), with no nitrogen in the back bone can be made by reacting a -triol or higher poly-hydric alcohol with a dicarboxylic acid etc. as described above. Employing glycerol, for example, thus lead~ to polymers having the repeating unit .

.~

r O _ CH2 - CH(OH) - CH2 - O - ~ - R13 - C

wherein R13 is as defined above. These polymers can be reacted with cationic groups at all the hydroxyls, or at some of them.
Of course, mixtures of any of the above described polymeric cationic salts may be employed, and the selection of individual polymers or of particular mixtures can be used to control the physical properties of the compositions such as their viscosity and the stability of the aqueous dispersions.
These cationic salts of condenstion polymers are usually ef~ective at levels of from about 0.01% or even lower to about 0.7% by weight of the compositions of the invention, especially up to about 0.5%.
Preferred above all other types of cationic poly-meric material are the cationic polysaccharides, especially cationic galactomannam gums (such as guar gum) and cationic derivatives. These materials are commercially available and relatively inexpensive. They have good compatibility with cationic surfactants and allow stable, highly effective softening compositions according to the invention to be prepared. Such polymeric materials are preferably used at a level of from 0.03% to 0.5% of the composition.

Nonionic Softener Component Compositions of the present invention can also in-clude low levels of nonionic textile conditioning agents.
These materials are generally esters of fatty acids or fatty alcohols, especially C8 C18 ~atty acid esters o~ apolyhydric alcohol containing from 2 to 8 carbon atoms.
Suitable materials are more fully described in German Offenlegungsschrift No. 2,631, 114. Preferred are glycerol and sorbitan partial esters with fatty acids, which may be saturated and unsaturated, having from about 10 to 26 carbon atoms, especially glycerol mono-palmitate, monostearate, mono-oleate, and corresponding sorbitan mono- and di-esters.
As generally obtained these mono- and di-esters contain appreciable proportions of the higher esters.
These nonionic components are optional, but if present they are at a level such that the ratio of nonionic softener to total cationic components (a) and (b) does not exceed 1:10.
The compositions may contain other compatible components such as bactericides and fungicides, whether to protect the products or fabrics treated therewith from attack, tarnish inhibitors, viscosity modifiers, emulsifying agents, other textile conditioning agents and components having aesthetic properties, such as perfumes and coloursO
In preparing the liquid products according to the invention any effective method of mixing the components may be used. In general it is usually desirable to make a pre mix by melting together the softener components (a), (b) and (c), often at a temperature of about 65C. Especially in cases where these components include appreciable amounts of free amines, an acid or acid anhydride is added in small amounts to protonate said amines. This pxemix is added with appropriate mixing, sometlmes high shear mixing being necessary, to a water mixture at a temperature above the ~ 21 ~
,.~

melting point of the premix containing the water for the composition together with mostly the water soluble com-ponents such as colour, bactericide and sometimes a small amount of an electrolyte such as calcium chloride. The mixture is allowed to cool usually with continued stirring.
The products are usually weakly acidic, partly to ensure that at least a substantial proportion of any amines present is protonated. The preferred pH of the produc-ts is from about 3 to 7, especially from about 4.5 to 5~5O
The invention also embraces a method of softening fabrics which comprises steeping them in an aqueous liquor comprising from 20 to 2,000, preferably about 200 parts per mlllion by weight of the combination of:
(a) a cationic surfactant having either one alkyl chain having 12 to 22 carbon atoms or two alkyl chains haviny 10 to 22 carbon atoms in - the molecule, and (b) a polymeric cationic salt as described here-inbefore, preferably at a level of 0.5 to 20 parts per million~ `
Preferably said combination is provided by a com-position comprising a s~bstantially water insoluble cationic textile softener agent as hereinbefore defined, and from 0~001 to 0.7~ by weight of the composition of said polymeric cationic salt.
Preferably the cationic surfactant is a cationic softener having one alkyl chain of 16 to 22 carbon atoms or two alkyl chains haviny 10 to 22 carbon atoms in the mole-cule.

3~ In general, very 'highly preferred composit,ions of ~' the invention, for reasons of performance and also of avail-ability and cost of components, comprise by weight from 3~
to 5~ ditallow dimethyl ammonium chloride, methosulphate or other salt, and either from 0.05 to 0.15% of cationic guar gum of D.S. from 0.2 to 0.5 or from 0.16 to 0.3% of cationic guar gum of D.S. from 0.05 to 0.19.
EX~MPLES
The following compositions were prepared, the bal-ance of the compositions consisting of water with minor amounts of perfume and colouring matter.

_ample No.
1. 4.0% DTDMAC 0. 2% polyvinyl alcohol quaternised with epoxypropyl trimethyl ammonium chloride, D.S.
about 0.06, PVA molecular weight about 14,000.
2. 4.0% DTDMAC 0.03~ Poly(vinyl pyridine)/(methyl methacrylate) 57/47 by weight mix.ture quaternised by methyl halide.
3. 4.0% DTDMAC 0. 2% GAFQUAT 755 (Trade mark~
believed to be high mole-cular weight co-polymer of . vinyl pyrrolidone, M.wt about 1,000,000.

. 4.0~ DTD~AC 0.1% Eudragit E ~uaternised with methyl halide at about 75%
of the available amino nitrogen atoms. Eudragit E
(Trade mark) is believed to be a co-polymer of N,N-dialkyl amino alkyl methacrylate with a neutral acrylic ester.

_ 4.0~ DTDMAC 0.2% JR12S (Trade Mark) believed -to be hydroxyethyl celluose of molecular weight about 250,000 quaternized to a D.S. of about 0.3.
6. 4.0~ DTDMAC 0.2% JR400 (Trade Mark) believed to be hydroxyethyl cellulose of molecular weight about 400,000 quaternized to a D.S. of about 0,3, 7. 4.0% DTDMAC 0.03% Poly (vinyl pyridine) / ~styrene) 70/30 by weight mixture quater-nized by methyl halide at about 45~ of the available pyridine nitrogen atoms.
8. 3.0% DTDMAC 0.2% Jaguar C-13S (Trade Mark) believed to be guar gum quaternized to a ~.S. of about 0.13.
9. 4.0% DTDMAC 0.1% Cationic guar gum. Guar gum quaternized to D.S. 0.25.
10. 4.0% DTDMAC n . 2% Modocoll (Trade Mark) quater-nized -to a D.S. of about 0.5 by epoxypropyl trimethyl am-monium chloride.
11. 4.0~ DTDMAC 0,.20% Cationic xanthan gum.
12. 4.0% DTDMAC 0.20% British gum quaternized to D.S.
0.4 with epoxypropyl trimethyl ammonium chloride.
13. 4.0% DTDMAC 0.1% Cationic guar gum as in Example 9, and 0.3% glycerol monostearate.

~' All these products provided substantiall~ the same softening performance as a composition comprising 5.8%
DTDMAC typical of prior art textile softening compositions.
Substantially similar per~ormance is obtained when the DTDMAC is replaced by an equal amount of ditallow di-methyl ammonium methosulphate, -toluene sulphonate, acetate, or benzoate, and also when the DTDMAC is replaced by an equal amount of Varisoft 455 (Trade Mark - a tallow-based imidazol-inium salt). Effective compositions are also obtained when the DTDMAC is replaced by C16 20 alkyl pyridinium halide.
Cl6 20 alkyl methyl morpholinium halides, N~tallow-N,NlNl-triethanol-1,3-propylene diamine dichloride.

14. A textile softening composition in the form of a paste and intended to be used in a rinse bath at lower than present conventional concentrations, e.g. at 0.05 - 0.1% by weight of the composition in the rinse liquor comprises:
8.5% DTDMAC

4.0% N-tallow-N,Nl, Nl-triethanol propylene diamine dichloride 0.2% Guar yum, quaternised to a D.S. of 0.3 with epoxypropyl trimethyl ammonium chloride.
Balance to 100 - water with minor amounts of perfume, colour, bactericide, etc.

15. A textile conditioning composition comprises:
3. OQo Varisoft 455 (Trade Mark for tallow imidazoline) 0.4% Cationic yuar gum as employed in Fxample 9.

~' .

Balance to 100 - water and minor components.

16. A wash using natural soiled fabrics is carried out in a ~omestic washing machine (Miele 422) using the "boil wash" cycle, with a conventional heavy duty anionic detergent-based detergent composition.
Desized terry towelling test pieces are included among the soiled fabrics. At the last rinse, 9Og of a textile softening composition to be tested are added to 30 litres of the rinse liquor. The test swatches are removed with the treated fabrics, and aried. Their softness is compared by a panel of judges with that of swatches treated similarly with different softener compositions, using a paired-comparison technique.
The results indicate that a composition comprising 3.8% DTDMAC was perceptibly less effec-tive than one contain-ing 5.8% DTDMAC, typical of prior art textile softeners. A
compositions comprising 4.0% DTDMAC
0.2% Jaguar C13-S
is at least as effective as that with 5.8% DTD~C.

17~18. Textile softening compositions having substantially equivalent softening effectiveness to that of a composition based upon 5.8% DTDMAC alone, had the composition;-DTDMAC 4.5 Imidazolinium softener (1) - 4.5 Cationic polymeric s~alt ~2) 0.2 0.2 Water to 100 (1) Varisoft 455 (Trade Mark Ashland Chemical Co.) or S-teinaquat (Trade Mark Rewo).
(2) Alcostat PB (Trade Mark Allied Colloids Ltd) be-lieved to be a cationic comb co-polymer of tri-ethanolamine and a dicarboxylic acid further ester-ified with, typically, stearic acid followed by quaternisation using dimethyl sulphate.

19-20. Textile softening compositions comprise:-DTDMAC 4.5 4.0 Alcostat C 0.2 0.4 Water to 100 Alcostat C (Trade Mark Allied Colloids Ltd) is believed tobe a quaternised polyethylene salt.

Claims

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A textile conditioning composition comprising:
(a) a cationic textile softening agent having either one alkyl or alkenyl group with at least 16 carbon atoms or two alkyl or alkenyl groups having from 10 to 22 carbon atoms, (b) from 0.001 to 0.70% by weight of a polymeric cationic salt or mixture of such salts selected from the group consisting of (i) cationic polysaccharide gums, (ii) cationic starch and starch derivatives (iii) polyvinyl pyridine and polyvinyl pyridinium salts and co-polymers therewith, (iv) cationic polyvinyl alcohol, (v) cationic polyvinyl polyvinyl pyrrolidone co polymers (vi) co-polymer of dialkylaminoalkyl methacrylate, wherein each alkyl has 1 - 3 carbon atoms, with styrene, or a neutral acrylic ester, (vii) condensation co-polymers having the repeating unit wherein R11 is hydrogen or a C1-6 alkyl group, or is R12OA, wherein A is a hydrogen or a C1-20 acyl group or a quaternary nitrogen-containing group, each R12 independently is a C1-6 alkylene group, and R13 is a C1-6 alkylene, hydroxy alkylene or C2-6 alkenylene group or an arylene group said co-polymer being rendered cationic either by the presence of said quaternary group in some or all of radicals A, or by rendering some or all of the nitrogen atoms in the back bone cationic, or by both, (viii) condensation co-polymers having the repeating unit wherein R13 is a C1-6 alkylene, hydroxyalkylene or C2-6 alkenylene group or an arylene group, R15 and R16 independently are a C1-6 alkylene group, and R17 is hydrogen or a C1-6 alkyl group, said co-polymer being rendered cationic at some or all of the nitrogen atoms which are not adjacent to CO groups, (ix) condensation co-polymers having the repeating unit wherein R13 is a C1-6 alkylene, alkylene or C2-6 alkenylene residue or an arylene group and some or all of radicals A are quaternary nitrogen-containing groups the remainder being hydrogen atoms, and (x) quaternized polyethyleneimines having at least 10 ethyleneimine residues in the molecule, and (c) optionally a substantially water-insoluble nonionic textile conditioning agent, in amount such that the weight ratio of component (c), if present, to components (a) and (b) together is not greater than 1:10.

2. The composition of Claim 1 wherein said polymeric cationic salt has more than 10 monomeric units in the molecule.

3. The composition of Claim 2 in the form of an aqueous dispersion and containing from 1% to 30% by weight of com-ponents (a), (b) and (c) together.

4. A textile conditioning composition in the form of an aqueous dispersion, consisting essentially of:-(a) from 0.1% to 14% by weight of a cationic textile softening agent having either one alkyl or alkenyl group with at least 16 carbon atoms or two alkyl or alkenyl groups having from 10 to 22 carbon atoms, and (b) from 0.03% to 0.5% by weight of a cationic poly-saccharide having more than 10 monomeric units in the molecule, the balance of the composition being water.

5. The composition of Claim 4, wherein the cationic softener is selected from the group consisting of:
(a) non-cyclic quaternary ammonium salts having two C10-22 alkyl chains, (b) C16-25 alkyl imidazolinium salts, and (c) mixture thereof.

6. The composition of Claim 4, wherein the cationic softener is present in an amount of from 0.3% to 8%.

7. The composition of Claim 5, wherein the cationic polysaccharide is a cationic guar or locust bean gum of degree of substitution from 0.1 to 0.5.

8. The composition of Claim 5, wherein the cationic polysaccharide is a cationic dextrin having a molecular weight, of dextrin from 1,000 to 10,000 and D.S. from 0.2 to 0.8.

9. The composition of Claim 7, wherein the cationic groupings on the anhydro sugar residues of the guar gum have a formula selected from:

(a) CH2CH=CHCH2N+Me3, C1- and (b) CH2cH(OH)CH2N+Me3, C1-.

10. The composition of Claim 7, which comprises by weight from 3% to 5% of ditallow dimethyl ammonium chloride or methosulphate and from 0.05% to 0.15% of cationic guar gum with a degree of substitution from 0.2 to 0.5.

11. The composition of Claim 7, which comprises by weight from 3% to 5% of ditallow dimethyl ammonium chloride or methosulphate and from 0.16% to 0.3% of cationic guar gum with a degree of substitution from 0.05 to 0.19.