CA1102511A - Textile treating composition - Google Patents

Abstract

TEXTILE TREATING COMPOSITION
Ronald Edward ATKINSON, Frederick Edward HARDY, Richard John DUMBRELL.
ABSTRACT OF THE DISCLOSURE
A textile treating composition in the form of an aqueous dispersion comprises a fabric substantive quarternary ammonium compound and a silicone of cationic character. The quarternary ammonium compound can have two C12 - C20 alkyl groups or one C18 - C24 alkyl group or be an imidazolinium textile softener.
The silicone is preferably a polysiloxane substituted with amine groups, optionally quaternised. A weight ratio of sili-cone : quaternary ammonium compound of from 2:1 to 1:10 is especially useful.

Description

5~1 This invention relates to fabric treatment compositions and to a method for treating fabrics in an aqueous bath such as the final rinse after a washing process in order to improve various properties of the fabric. In particular this invention relates to compositions of the type disclosed in our pending Canadian Patent Application Serial No. 257,084 filed on July 15, 1976.

It has been known for some years that fabrics can be made to feel softer by treatment in a dilute solution or dispersion of certain cationic quaternary ammonium derivatives and rinse-additive compositions have been marketed for this purpose. The invention disclosed in Canadian Application Serial No. 257,084 of July 15, 1976 provides substantial additional benefits by a combination of fabric conditioning agents. These benefits may include some or all of: easier ironing, anti-static properties, pleasanter feel of the fabrics, soil release properties. It appears that recog-nition of improved "ease of ironing" can arise from a com-bination of at least three factors, namely fewer wrinkles to be removed, wrinkles more easily removed (e.g. with less weight upon the iron), or more completely removed, and less effort required to slide the iron along the fabric.
"Pleasanter" feel can be consistently observed by experienced judges, although it is not easy to define in words the sen-sation or combination of sensations they like. Anti-static and soil release properties improve the achieving and maintaining of soil-free fabrics.

The combination of fabric conditioning agents referred to above requires the presence of both a cationic quaternary ammonium (or imidazolinium) derivative and a silicone.

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The silicone is defined as predominantly linear polymers ie.
poly dialkyl- or alkylaryl siloxanes. The alkyl groups have l to 5 carbon atoms and are preferably methyl and may be wholly or partially fluorinated. A limited degree of cross- ;~
linking is permissible and up to about 10 ~ by weight of mono-alkyl or mono-aryl siloxanes may be present in the silicones. Preferred silicones are polydimethyl siloxanes having a viscosity at 25C in the range from 1000 to 200000 centistokes preferably 10000 - 120000 centistokes. Other lQ preferred silicones are fluorinated silicones having a viscosity at 25C of at least 100 centistokes.

As recited in the above discussed Canadian Application Serial No. 257,084 the combination of a fabric substantive quaternary ammonium textile softening compound and silicone of the above type materially improves the substantivity of the latter. It i6 postulated that this enhanced substantiv-ity arised from a 'carrier' effect by means of which the positively charged fabric softener molecules associate with the silicone molecules and cause them to migrate to the fabric surface. However, experiments have shown that the distribution of this combination on the fabric is less than optimum ie. some areas of fabric receive a high concentra-tion of silicone while others receive very little if any silicone.

It has now been found that the basic charge characteristics of the silicone as used in the combination are important in determining both the extent of deposition and the evenness of distribution of the silicone and hence the properties of a fabric treated therewith.

- 2 -~11325~L3 This is illustrated in the following table in which the adsorption of various silicone polymers on to cotton fabrics from a 0.2% by weight aqueous solution of the silicone is measured as a function of time.
wt. ~ adsorbed after:
2 10 15 30 minutes Polydimethyl siloxane nonionic emulsified n = 1, OOOcs 10 10 10 lo Polydimethyl siloxane cationic emulsified n = 28, OOOcs 65 85 86 88 n = 62,500cs 80 100 100 100 ~ dipyridinium polydimethyl siloxane ;

(High viscosity liquid `
M.wt. ~ 3000) 86 100 100 100 Amino functional silicone (DC 929 supplied by Dow Corning as a high 100 100 100 100 viscosity liquid and comprising polydimethyl silicone containing primary and ~econdary amino groups of d.s. 0. 008 ) It can be seen that silicones having cationic character show an enhanced tendency to deposit.
As mentioned above, silicones found to be of value in provid-ing fabric feel benefits have a predominantly linear charac-ter and are preferably polydialkyl siloxanes in which the alkyl group is most commonly methyl. Such silicone polymers are frequently manufactured commercially by emulsion poly-merisation using a strong acid or strong alkali catalyst in ~ the presence of a nonionic or mixed nonionic-anionic emul-; sifier system.

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5~1 In combination with the cationic fabric softening agent, anionic- or nonionic emulsified silicone polymers tend to aggregate in dilute aqueous solution due to the attraction between the negatively or non-charged emulsifier and the positively charged fabric softening agent. However, the provision of a silicone emulsion having a like charge to that of the fabric softening agent would tend to reduce this effect and a further reduction might be expected from the tendency of the charged silicone droplets to repel each other.
Accordingly, the present invention provides a textile treating composition which is an aqueous dispersion com-prising:
(a) a fabric substantive quaternary ammonium textile softening compound having in its molecular structure either two alkyl groups each having 12 to 20 carbon atoms or one alkyl chain having 18 to 24 carbon atoms or a fabric substantive quaternary imidazolinium textile softening compound and (b) a silicone component of cationic character as hereinafter defined, the weight ratio of the polysiloxane portion of component (b) to the fabric substantive quaternary textile softening com-pound of component (a) being in the range of 20:1 to 1:100.
Preferably the weight ratio of polysiloxane to the quaternary textile softening compound is from about 2:1 to to 1:10 especially from about 1:1 to 1:3.
For the purpose of the present application a silicone component of cationic character is defined as being one of:
(a) a predominantly linear di Cl-C5 alkyl or Cl-C5 alkyl, aryl siloxane having a viscosity at 25~C

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of at least 100 centistokes, prepared by emulsion polymerisation using a cationic surfactant as emulsifier.
(b) an ~ di quaternised di Cl C5 alkyl or Cl-C5 alkyl, aryl siloxane polymer or (c) an amino-functional di Cl-C5 alkyl or alkyl aryl siloxane polymer in which the amino group may be substituted and may be quaternised and in which the degree of substitution (d.s.) lies in the range 0.001 to 0.1, preferably .01 - 0.075.
a) Cationlc_emulsion polymerised siloxanes Cationic emulsion polymerised siloxanes are known in the art and can be prepared by strong alkali or acid catalysis of siloxane monomer(s) in the presence of a cationic emulsifying agent. Hyde and Wehryl U.S. Patent No. 2,891,920 describes general procedures for such polymerisations and Examples 1 -6 of the patent provide specific teaching of the required reaction conditions. The siloxane monomer can be any di lower alkyl siloxane such as dimethyl, diethyl dipropyl, or ethyl butyl siloxane or alkyl, aryl siloxane such as methyl, phenyl siloxane or ethyl phenyl siloxane. However, the preferred starting material for emulsion polymerisation is normally a cylic trimer or tetramer of the desired siloxane.
The emulsifying agent can be any one of a wide range of cationic surfactants such as:
Aliphatic fatty amines and their derivatives such as dodecylamine acetate, octadecylamine acetate and acetates of the amines of tallow fatty acids; homologues of aromatic amines having fatty chains such as dodecylaniline; fatty amides derived from aliphatic diamines such as undecylimidazoline;
fatty amines derived from disubstituted amines such as .

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oleylaminodiethylamine; derivatives of ethylene diamine;quaternary ammonium compounds such as dioctadecyldimethyl ammonium chloride, didodecyldimethyl ammonium chloride and dihexadecyldimethyl ammonium chloride; amide derivatives of amino alcohols such as ~-hydroxyethylstearyl-amide; amine salts of long chain fatty acids; quaternary ammonium bases derived from fatty amides of di-substituted diamines such as oleylbenzylaminoethylene diethylamine hydrochloride; quater-nary ammonium bases of the benzimidazolines such as methyl-heptadecyl benzimidazol hydrobromide; basic compounds ofpyridinium and its derivatives such as cetylpyridinium chloride;
sulfonium compounds such as octadecylsulfonium methyl sulfate;
quaternary ammonium compounds of betaine such as betaine compounds of diethylamino acetic acid and octadecylchloromethyl ether; urethanes of ethylene diamine such as the condensation products of stearic acid and diethylene triamine; polyethylene diamines; and polypropanolpolyethanol amines.
The emulsifier is conventionally employed at a level of 1% - 10% by weight of the siloxane, more preferably 2~ - 5% by weight.
The catalyst employed to polymerise the siloxane is preferably an alkaline catalyst such as an alkali metal hydroxide or a quaternary ammonium hydroxide of the formula (R)4N OH. In such ammonium hydroxides the R groups can be hydrogen or alkyl radicals such as methyl, ethyl, propyl, butyl, isobutyl, decyl or octadecyl or a~alkyl radicals such as benzyl or hydroxyalkyl radicals such as hydroxyethyl, hydroxypropyl and hydroxybutyl.
Most preferably the catalyst is a quaternary ammonium hydroxide having at least one radical of at least 12 carbon atoms in chain length, such a material also serving as an ~a :

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emulsification agent. Long chain length alkyl quaternary ammonium salts are also preferred as the emulsification agents, particularly di-long chain alkyl di-lower alkyl quaternaries, such as ditallowyl dimethyl ammonium chloride (DTDMAC), available commercially from Armour Chemical Company as Arquad 2HT (Arquad is a Registered Trade Mark) and imidazolinium derivatives such as methyl C18 alkyl amidoethyl, C18 alkyl imidazolinium methosulphate, available commercially from Ashland Chemical Company as Varisoft 275 (Varisoft is a Registered Trade Mark).
The level of catalyst usage is dependent on the catalyst type employed. Acid catalysts are conventionally used at high levels, e.g., at 15% or more by weight of the aqueous phase of the emulsion. Alkaline catalysts by contrast are used at lower levels, e.g., from 0.001% to 10~, preferably from 0.1%
to 5% by weight of the siloxane monomer.

Emulsion polymerisation of dimethyl siloxane using -DTDMAC as emulslfler In a typical preparation, dichloro dimethyl siloxane was first hydrolysed to form octamethyl cyclo tetra siloxane using the method of Patnode and Wilcock in JACS 68 1946 pp 358 - 363. 15 grs of this material was then added to a mix-ture of 131 grs of a 1% aqueous solution of ditallowyl dimethyl ammonium chloride and 3.75 grs of tetrabutyl ammonium hydroxide in the form of a 40% aqueous solution. The mixture was stirred during addition of the ingredients by means of a Silverson laboratory emulsifier mixer and, after addition was --complete, the reaction mixture was subjected to 15 minutes further agitation using an ultrasonic vibrator. After 18 hours at 80C the poly dimethyl siloxane oil was precipitated from the reaction mixture by addition of 500 mls of ethyl alcohol and was then dxied with further alcohol before being heated .~

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at 75C under a high vacuum to remove all volatile materials.The viscosity of the silicone was determined to be 22,000 centistokes by measurement of its rate of flow under gravity between two marks on a calibrated tube. The time taken for a given quantity to flow along the tube was converted to viscosity using a calibration curve established with commer-cial silicones of known viscosity.
Using the above-described polymerisation technique, stable 10% emulsions of polydimethyl siloxane were achieved and equivalent results were obtained when the procedure was repeated using cetyl trimethyl ammonium bromide and the imidazoline derivative Varisoft 475 respectively as the emulsifier.
b) a-~ quaternised polysiloxanes The preparation of ~,~ quaternised siloxane polymers can be conveniently carried out using the method disclosed in I.C.I. British Patent Specification No. 1,006,729. In this technique a polysiloxane end-stopped with alkyl halide groups in which the halogen atoms are separated from the nearest silicon atoms by at least three carbon atoms, is reacted with a tertiary amine to give an ~ quaternised siloxane polymer.
In order to provide the polysiloxane starting material a solution polymerisation is normally carried out to give a polymer of the appropriate molecular weight, and the poly-merisation reaction is terminated by reaction with a ~-halo alkyl dimethyl silanol.
As previously stated, the polysiloxane can be a poly di (Cl-C5 alkyl)- or (Cl-C5 alkyl, aryl) siloxane, preferably a polydimethyl siloxane and the tertiary amine can be any alkyl, aryl or mlxed alkyl and aryl material. Examples include trimethyl-amine, cetyl dimethyl-amine, pyridine, phenyl 8 - -~

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dimethyl-amine.
Preparation of a ~-~ dipyridinium polydimethyl siloxane A typical preparation of this class of silicone polymers -involved the polymerisation of 23.2 grs of octamethyl cyclo-tetra siloxane in the presence of 0.9 mls of concentrated sulphuric acid and 2.5 grs of 1,3-bis, 3-chloropropyl tetra-methyl disiloxane. The mixture was shaken in a sealed flask for 48 hours at room temperature, following which 5 mls of water were added and the flask shaken for a further hour.
The resulting emulsion was split by addition of 50 mls of diethyl ether and the organic layer was then washed twice with 30 ml aliquots of distilled water, dried over sodium bicarbonate and magnesium sulphate and filtered. Evaporation of the filtrate to remove the ether left 23 grs of a clear oil of viscosity 100 cs. NMR examination of the oil showed it to correspond to a polymer having 36 siloxane units.
10 grs. of the ~ bis (3 chloropropyl) silicone prepared above were then refluxed in 10 mls pyridine for 36 hours at 120C. Excess pyridine was distilled off under reduced pressure leaving a brown viscous oil. This was then dis-solved in toluene, washed with water and the toluene layer dried and evaporated to remove the toluene. NMR spectral analysis disclosed a level of proton activity corresponding to 70-80% of the theoretical uptake of pyridine.
10% aqueous emulsions of the silicone product were prepared by mechanical emulsification using an ethoxylated linear alcohol emulsifying agent (Dobanol 45E4, a Cl4-Cl5 linear alcohol tetra ethoxylate supplied by Shell Interna-tional Chemicals Limited) at a level of 20% by weight of the siloxane.
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c) Amino functional linear polysiloxanes Amino functional linear polysiloxanes can be prepared by the general method disclosed in sritish Patent Specification No. 1,339,906 at page 3 lines 78-108, page 4 lines 1-65 and page 3 lines 3-14. In this method, a hydrosiloxane is reacted with an alkenyl group-containing tertiary amine in the presence of a platinum catalyst in accordance with the equation H PtCl (Me3SiO)2 (SiMe20)x(SiMeHo)y + yCH2=CHR'NR2 2 6 (Me3SiO)2 (SiMe20)x(OSi(Me)R''NR2)y wherein x = 10 to 100, y = 1 to 20, R is a methyl, ethyl or phenyl group, R' is a direct linkage or a divalent organic group free of aliphatic unsaturation containing 1-16 carbon atoms and R" is a divalent organic group free of aliphatic unsaturation containing 2-18 carbon atoms.
The product of the above reaction can then be quaternised by further reaction with an alkyl halide or can be converted to the hydrochloride by acidification with hydrochloric acid.
Preparation of ~olydimethyl siloxane substituted with dimethylamlnopropyl groups In a typical preparation 50 grs of dimethyl-methyl hydro-gen siloxane copolymer containing approximately 76 dimethyl siloxane units and 6 hydromethyl siloxane units was dissolved in 50 mls toluene containing a trace of chlorplatinic acid.
The mixture was stirred under nitrogen at 80C, 5.18 grs of N,N-dimethyl allylamine in 10 mls of toluene was added drop-wise, holding the reaction temperature at 80-90C., and the reaction mixture was stirred for a further 2 hours and then cooled. Sodium carbonate was added to neutralise any remain-ing acid and the mixture was filtered and rotary evaporated to remove solvents, leaving a pale yellow fluid of low viscosity. NMR analysis showed the formation of poly dimethyl siloxane containing dimethylaminopropyl groups at a level corresponding to a reaction completeness of 80~+, and a degree of substitution (d.s.) of 0.06.
20 grs of the reaction product was stirred in lO0 mls of a 1:1 mixture of dichloromethane and isopropanol and 1.3 mls of concentrated HCl (11.21M) in 10 mls of the same solvent mixture was added slowly at room temperature. ~ollowing evaporation of the solvent a pale coloured solid was left and NMR analysis showed this material as having a proton ratio close to the expected value for the hydrochloride derivative with no detectable level of the starting material. The siloxane polymer was then made up into a 10% aqueous emulsion using 20% based on the siloxane weight of a nonionic emulsifi-cation agent (Dobanol* 45E4, a linear C14-C15 alcohol containing

4 moles of ethylene oxide supplied by Shell International Chemicals Limited).
A similar experimental technique to the above was employed to produce polydimethyl siloxanes having respectively approximately 40 siloxane units and a d.s. of 0.04 and 72 siloxane units with a d.s. of 0.015.
Cationic softening compounds ~_ , The cationic softening compounds suitable include those commonly used in rinse-added textile softening compositions.
These include quaternary ammonium salts of general formula ~ N - X (I) Rl R

wherein either (a) R2 and R3 (which may be the same or different) represent methyl, ethyl, propyl or benzyl, and either R and Rl each represent a straight or branched chain alkyl group having 12 to 20 carbon atoms, or R represents a *Dobanol is a Registered Trade Mark 51~ ~

straight or branched chain alkyl group having 18 to 24 carbon atoms and Rl represents methyl, ethyl, propyl or benzyl; or (b) R2 and R3 together with the nitrogen atom form a 5- or 6-membered heterocylic ring and R and Rl are as defined in (a); or (c) Rl, R2 and R3 together with the nitrogen atom form a 5-membered or 6-membered heterocylic ring and R
represents a straight or branched chain alkyl group having 18 to 24 carbon atoms; and X is an anion. The long chain alkyl groups may be derived from natural fats, e.g., coconut, or more preferably tallow, or from petroleum or synthetically.
In a preferred group of salts of formula (I), R and R
each represent an alkyl group having 16 to 18 carbon atoms, R2 and R3 each represent methyl, and X represents Cl , Br Other anions include nitrite, acetate and phosphate.
Specific examples of particularly preferred cationic softening agents include the following:
-tallowtrimethyl ammonium chloride, -tallowdimethyl (3-tallowalkoxypropyl) ammonium chloride, -ditallow dimethyl ammonium chloride, -ditallow dimethyl ammonium methyl sulphate, -eicosyltrimethyl ammonium chloride, and -dieicosyldimethyl ammonium chloride.
Examples of other suitable cationic softening agents suitable for use in the invention herein include the following:
-ditetradecyldimethyl ammonium chloride, ~ --dipentadecyldimethyl ammonium chloride, -didodecyldiethyl ammonium chloride, -didodecyldipropyl ammonium chloride, .. .. . .. . .. . .

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-ditetradecyldiethyl ammonium chloride, -ditetradecyldipropyl ammonium chloride, -ditallowdiethyl ammonium chloride, -ditallow dipropyl ammonium chloride, -tallowdimethyl benzyl ammonium chloride, -tallowdiethyl benzyl ammonium chloride, --didodecyldiethyl ammonium acetate, . --tallowtrimethyl ammonium acetate, -tallowdimethyl benzyl ammonium nitrite, and -ditallowdipropyl ammonium phosphate.
Other cationic softening agents of formula (1) are known and include variations wherein R and Rl can also represent a phenyl radical or a hydroxy-substituted alkyl of 1, 2 or 3 carbon atoms.
Many other cationic quaternary ammonium softening :
agents, which are useful herein, are known; for example, alkyl [C12 to C20]-pyridinium chlorides, alkyl ~C12 to C20]-alkyl [Cl to C3]-morpholinium chlorides, and quaternary derivatives of amino acids and amino esters.
Cation quaternary imidazolinium compounds are also suitable as softening agents in the compositions herein.
The most useful compounds generally conform to the formula ~ :' l 7 H-l Cl - H O ~ x Q (II) ~ :
C r \ 2 4 wherein R4 represents hydrogen or alkyl having 8 to 25, preferably at least 15, carbon atoms, R5 represents alkyl - 13 - :

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having 1 to 4, preferably 1 or 2, carbon atoms, R6 represents alkyl having 1 to 4 earbon atoms or hydrogen, R7 represents - alkyl having 8 to 25, preferably at least 15, carbon atoms and X is an anion, preferably methyl sulphate or chloride.
Other suitable anions include bromide, acetate, nitrite and phosphate. Particularly preferred are those compounds of formula (II~ in which both R4 and R7 represent alkyl having 16 to 25 (especially 16 to 18 or 20 to 22) carbon atoms.
The concentration of the aqueous dispersions (by which term is included solutions) which constitute the compositions of the invention is not critical and is controlled by practical considerations. Thus the dispersions should be concentrated enough not to be wasteful in transit costs, yet should be fluid enough to be poured and to disperse readily in a usage bath. Usually a content of from about 1% to 20%, especially -about 3-10%, by weight of components (a) and (b) together is convenient. As stated earlier, the ratio of the siloxane portion of component (b) to the quaternary softening agent of component (a) should be in the ratio of 20:1 to 1:100 by weight, preferably from 2:1 to 1:10 and most preferably from 1:1 to 1:5.
The aqueous dispersions may contain other components, such as emulsifying aids, for instance low levels of the order of about 1% by weight of nonionic surfactants to aid dispersion of the usually poorly soluble cationic softeners.
A wide range of nonionic emulsifiers can be used for this purpose such as those disclosed in German Patent Application OLS 2500111 published July 17th, 1975. It is found that use of emulsifiers is sometimes desirable to aid also the dispersion of the silicones in the compositions of the invention, especially when silicones of relatively high viscosity are employed.

5~1 Highly preferred optional ingredients also include non-ionic fabric treatment agents such as the fatty acid partial esters of polyhydric alcohols or anhydrides thereof having from 3 to about 8 carbon atoms in the alcohol and fatty acid esters of Cl - C8 monohydric alcohols. The fatty acid esters of the polyhydric alcohols should have at least 2 free (i.e., unesterified) hydroxyl groups and at least 1, more preferably at least 2, fatty acyl groups.
The polyhydric alcohol portion of the ester can be glycerol, diglycerol, xylitol, sucrose, erythritol, penta-erythritol, sorbitol or sorbitan; sorbitan esters are particularly preferred.

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The fatty acid portion of the ester normally comprises a fatty acid having from 12 to 20 carbon atoms, typical examples being lauric acid, myristic acid, palmitic acid, stearic acid and behenic acid.
Amongst these esters, the most preferred are the glyceryl esters of stearic acid, especially glyceryl monostearate, and the sorbitan fatty acid esters, which are esterified dehydration products of sorbitol.
These sorbitan fatty acid esters are disclosed in Canadian Patent 1,074,96~, issued April 8, 1980. Nonionic fabric condi-tioning materials of this type are commonly employed at levels of 1 - 5% preferably 2 - 4% by weight of the composition.
Other preferred ingredients include pyrodextrins such as British Gum and White dextrin and substituted dextrins such as dextrin phosphates, cationic dextrins and dextrin pyrollidone carboxylic acid, in which the degree of substitution is from 0.01 to 2.0 preferably 0.05 to 1.5. A preferred cationic dextrin is a white dextrin that has been reacted with glycidyl trimethyl ammonium chloride to provide a degree of substitution (d.s.) in the dextrin molecule of from about 0.1 to 1Ø The dextrins are used at levels of 0.5~ ~o 5~ by weight of the compositions, preferably at levels of 1% to 3~.
Non-aqueous, water miscible solvents may be present, and other viscosity controlling agents, such as low levels of electrolytes. Other optional components include appropriate optical brighteners, fungicides and germicides, colouring or opacifying agents, and perfumes.
In use the compositions of the invention are normally incorporated in an aqueous bath containing the ingredients of the compositions in the ratios defined hereinabove, at a con-centration such that there is present from about 20 to 1,000 parts per million by weight of components (a) and (b) together of which at least 10 ppm is component (b). Preferably the bath , 5~1 contains from about 50 to 200 ppm of components (a) and (b)together of which at least about 15 to 150 ppm is component (b)-The invention also embraces a method of treating textiles,and textiles when so treated, which method comprises steeping them in such a bath.
The textiles may be steeped in such a bath and then dried on any occasion, but it is envisaged that normally the treat-ment will constitute the final rinse after a washing process.
EXAMPLES
Test Procedures Clean test pieces of cotton or other fabric were treated in a domestic washing machine. Either a whole standard load was made up of test pieces or additional clean fabrics were used to make up the load. The machine cycle was set so that the load was subjected to gentle agitation (as for a wool wash cycle) for about 20 minutes in a solution of the test product in water, and was then spin-dried.
Wrinkling test Treated test pieces were compared with a standard set o 10 plastic simulated test pieces of different degrees of wrinkling (American Association of Textile Chemists and Colourists - Three dimensional durable press replicas for use with AATCC Test 124). Number 10 graded perfect, Number 1 worst. A grade 5-7 was deemed to represent about that degree of freedom from wrinkling at which a housewife might be expected to consider ironing unnecessary.
Ease of Ironing test This was judged by a panel of judges, employing a Scheffé analysis to provide gradings (panel score units -psu) and a "yardstick", i.e., least difference significant ~.

- ' '': ' ~25~1 at 95% probability.
End Result test A visual preference, graded as above in psu.
Softness test A tactile preference, graded as above in psu.
Drying of Fabrics The "spin-dried" test pieces were dried by hanging in the laboratory (static drying) or in a tumbler dryer.
Comparison of silicone types The performance of a conventional nonionic emulsion polymerised silicone A* was compared to that of two cationic silicone polymers B** and C*** by applying each to cotton pieces in a rinse bath at 0.2% concentration. The cotton pieces were dried and then graded for Ease of Ironing, Ironed end result and Softness. The results are expressed below in panel score units relative to the figures for silicone A. -~
*A was a polydimethyl siloxane of viscosity 60,000 centistokes prepared by emulsion polymerisation using a mixture of nonionic and anionic emulsifiers.
**B was an amino functional silicone of molecular weight ~6500 containing ~75 dimethyl siloxane units and approximately six siloxane units in which a methyl group was substituted by a H2cH2NH3cl grouping-***C was an ~,~-di pyridinium silicone of molecular weight ~3000.
B vs A C vs A Yardstick Ease of ironiny+ 0.8 + 1.75 1.1 Ironed end result + 1.5 + 1.03 0.79 30 Softness + 0.7 + 0.35 0.78 . ~

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This test took place in the absence of a cationic softener and demonstrates the advantages of the enhanced deposition of the two cationic polymers.

Comparison of cationic softeners + silicones of different emulsion type A number of aqueous softening compositions were made up as follows (percentages are by weight):
I 6% DTDMAC + 3% of silicone A
II 6% DTDMAC + 3% of silicone B
III 6% DTDMAC + 3% of a polydimethyl siloxane of viscosity 40,000 centistokes prepared by emulsion polymerisation with a cationic emulsifier (DTMAC) present at a level of 10% of the silicone.
Each composition was employed at 0.2% concentration in a rinse step to treat terry cotton cloths, which were then dried and graded for softness impression. The results in panel score units (psu) are expressed below in terms of the advantages for compositions II and III relative to composition I.
II III
+ 0.4 + 0.8 + 0.1 + 0.8 The yardstick for the tests, at the 95% conidence level, was 0.8 psu so that Composition III can be seen to provide a significant softness benefit relative to Composition I.
Comparison of silicones having different viscosities The effect of silicone viscosity on the wrinkle grade, ease-of-ironing grade and ironed-end-result grade of cotton tea towels treated with compositions of the invention was examined for a range of polydimethyl siloxanes prepared by emulsion polymerisation using a cationic emulsifier.

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Seven aqueous compositions were made up, each containing6% DTDMAC and 3% of a silicone emulsion polymerised in the presence of 1% DTDMAC on a silicone basis. The siloxane polymers varied in viscosity from 1000 to 170,000 centi-stokes. The compositions were applied at 0.2% concentration to the fabrics simulating a final rinse treatment in a conven-tional washing cycle and the treated fabrics were then air dried and graded by a panel of judges. In such panel testing a difference between fabrics of approximately 0.5 panel score units (psu) in wrinkle grade is normally detectable by the housewife, while for ease of ironing and ironing end result a panel score unit difference of between 0.75 - 1.0 between fabrics is generally necessary in order for a difference to be noticeable.
The results are shown below, indexed to the grades obtained with a cationic-emulsified silicone of viscosity 170,000 centistokes Wrinkle Ease of Ironed Grade Ironing end result 20170,000 0 o 0 100,000 + 0.2 0 + 0.5 40,000 + 0.3 + 0.1 - 0.2 20,000 + 0.4 + 0.8 + 1.2 8,000 + 0.6 + 0.7 + 1.7 3,700 + 0.6 + 1.1 + 2.1 1,000 + 0.5 + 0.8 + 1.3 It can be seen that performance for these parameters improves with a reduction in viscosity from 170,000 cs to a value in the range 3,000 - 20,000 cs with the optimum appear-ing to lie in the range 3,000 - 8,000 cs.

Claims (17)

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

1. A textile treating composition which is an aqueous dispersion comprising:
(a) a fabric substantive quaternary ammonium textile softening compound having in its molecular structure either two alkyl groups each having 12 to 20 carbon atoms or one alkyl chain having 18 to 24 carbon atoms or a fabric substantive quaternary imidazolinium textile softening compound and (b) a silicone component selected from:
(i) a predominantly linear di(C1-C5) alkyl or (C1-C5) alkylaryl siloxane having a viscosity at 25°C of at least 100 centistokes, prepared by emulsion polymerization using a cationc surfactant as emulsifier;
(ii) an .alpha., .omega.-diquaternized di(C1-C5) alkyl or (C1-C5) alkylaryl siloxane polymer; and (iii) a linear di(C1-C5) alkyl siloxane polymer in which from 0.001% to 0.1% of the siloxane units contain an amino substituent group, the weight ratio of the polysiloxane portion of components (b) to the fabric substantive quaternary textile softening compound of component (a) being in the range of 20:1 to 1:100.

2. A composition as claimed in claim 1 wherein the weight ratio of the siloxane of component (b) to the quaternary softening compound of component (a) is in the range from 2:1 to 1:10.

3. A composition as claimed in either one of claims 1 and 2 wherein the weight ratio of the siloxane of component (b) to the quaternary softening compound of component (a) is in the range from 1:1 to 1:3.

4. A composition as claimed in claim 1 wherein the silicone component is a predominantly linear di C1-C5 alkyl or C1-C5 alkyl, aryl siloxane prepared by emulsion polymerisation in the presence of a cationic emulsifier.

5. A composition as claimed in claim 4 wherein the cationic emulsifier is a quaternary ammonium compound.

6. A composition as claimed in claim 5 wherein the quaternary ammonium compound is a fabric softening compound.

7. A composition as claimed in claim 6 wherein the quaternary ammonium compound is a di C16-C18 alkyl dimethyl ammonium compound (in which the anion is a hydroxyl, halide or sulphate group) or an imidazolinium compound containing two C16-C18 alkyl groups.

8. A composition as claimed in claim 4 wherein the cationic emulsifier is present at a level of from 0.1%
to 10% by weight of the siloxane.

9. A composition as claimed in claim 8 wherein the cationic emulsifier is present at a level of from 0.5% to 5% by weight of the siloxane.

10. A composition as claimed in claim 1 wherein the silicone component is an .alpha.,.omega.-diquaternized di C1-C5 alkyl siloxane polymer.

11. A composition as claimed in claim 10 wherein the quaternising group comprises an aromatic molecule.

12. A composition as claimed in claim 11 wherein the quaternising group is pyridine.

13. A composition as claimed in claim 1 wherein the silicone component comprises a linear di C1-C5 alkyl siloxane polymer in which from 0.001% to 0.1% of the siloxane units contain an amino substituent group.

14. A composition as claimed in claim 13 wherein the degree of substitution (d.s.) lies in the range from 0.01 to 0.075%.

15. A composition as claimed in claim 13 wherein the amino group is a tertiary amine or the hydrochloride thereof.

16. A composition as claimed in claim 13, 14 or 15 wherein the amino group is a dimethyl aminopropyl group.

17. A composition as claimed in claim 13 or 14 wherein the amino group is a quaternary amino group.