GB1604030A

GB1604030A - Textile conditioning compositions

Info

Publication number: GB1604030A
Application number: GB48377/77A
Authority: GB
Original assignee: Procter and Gamble Ltd
Current assignee: Procter and Gamble Ltd
Priority date: 1977-11-21
Filing date: 1977-11-21
Publication date: 1981-12-02
Also published as: IT7829962A0; FR2409302A1; DE2849931A1; JPS54106696A; FR2409302B1; CA1111617A; BR7807644A

Description

(54) IMPROVED TEXTILE CONDITIONING COMPOSITIONS (71) We, PROCTER & GAMBLE LIMITED, a company organised under the laws of the United Kingdom, of Hedley House, Gosforth, Newcastle Upon Tyne, NE99 lEE, do hereby declare the invention for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- The invention relates to textile conditioning compositions employing 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 conventional 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 surfactant reacts with the cationic softener component of a softening composition, thereby reducing its performance. The use of relatively water soluble cationic surfactants to scavenge anionic has been described in our co-pending British Patent SPecification No. 1,487,432, but these substances need to be used at considerabielevels.

It has now been found that this scavenging function can be performed by very low levels of certain polymeric cationic salts. Furthermore some of these salts have been found to have softening properties in the presence of cationic softeners even when employed in baths which contain no anionic surfactant, and they even replace several times their own weight of conventional cationic softener without overall loss of softening performance of the composition. This enables the cost of such compositions to be reduced.

Our co-pending British Patent application 23170/76 Serial No. 1,576,325) describes textile softening and ironing assistants containing cationic softeners or mixtures 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 (2) 313319, 1976 describes a study of the effect of, inter alia, a cationic surfactant upon the sorption of cationic hydroxyalkyl cellulose on hair.

The present invention then provides a textile conditioning composition comprising: (a) a substantially water insoluble cationic textile softening agent, as hereinafter defined, (b) from 0.001 to 0.70% by weight of the composition of one or more polymeric cationic salts selected from the group consisting of (i) cationic polysaccharide gums, (ii) cationic starch and starch derivatives, (iii) polyvinyl pyridinium salts, and co-polymers therewith, (iv) cationic polyvinyl alcohol, (v) cationic polyvinyl pyrollidone co-polymers, (vi) cationic co-polymers of dialkylaminoalkyl methacrylate, wherein each alkyl has 1-3 carbon atoms, with styrene, or with a neutral acrylic ester, and (vii) quaternised polyethyleneimines having at least 10 ethylenimine residues in the molecule, and, optionally, (c) 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.

Preferably the textiles treated are at least partly made from cellulosic, eg.

cotton, fibres. The compositions of the invention may be solids, eg. granules, or gels, pasts or liquids, or they may be absorbed in or absorbed 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 products usually contain from 1% to 30 /O by weight of components (a), (b) and (c) together, more usually from 3% to 15% especially from 4/O to 10%.

The carrier liquid when present is aqueous and comprises water for the main part, optionally with some water miscible organic solvent such as, methyl, ethyl or isopropyl alcohol.

The substantially water-insoluble cationic textile softening agents used in the compositions of the invention contain in their molecule either one 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.

Among suitable cationic softeners may be named the conventional substantially water-insoluble quaternary ammonium compounds, and C16~25 alkyl imidazolinium salts.

Well-known species of substantially water-insoluble quaternary ammonium compounds have the formula:

wherein R1 and R2 represent alkyl or alkenyl groups of from 10 to 22carbon atoms; R3 and R4 represe alkyl or alkenyl groups containing from 1 to 4 carbon atomX is any anion such as a halide, a C2 22 carboxylate, or an alkyl-or arylsulf(on)ate.

Examples of preferred anions include bromide, chloride, methyl sulfate, toluene-, xylene-, cumene-, and benzene-sulfonate, dodecylbenzenesulfonate, benzoate, parahydroxybenzoate, acetate, propionate and laurate. Representative examples of quaternary softeners include ditallow dimethyl ammonium chloride, ditallow dimethyl ammonium methyl sulfate; dihexadecyl dimethyl ammonium chloride; di(hydrogenated tallow) dimethyl ammonium chloride; dioctadecyl dimethyl ammonium chloride; dieicosyl dimethyl ammonium chloride; didocosyl ammonium chloride; di(hydrogenated tallow) dimethyl ammonium methyl sulfate; dihexadecyl diethyl 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 R, is C16 to C22 alkyl or alkenyl, preferably C16 to C20 alkyl, and R2, R3 and R4 are lower alkyl groups that is Ct to C4 alkyl groups especially methyl, or aryl groups and X is as defined above. Optionally also two or all three of R2, R2 and R4 may together represent a heterocyclic ring.

Some representative examples of such compounds are cetyl and stearyl trimethyl ammonium bromides, behenyl trimethyl ammonium 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 suitable cationic surfactants are C, > 2s alkylimidazolinium salts. Preferred salts are those conforming to the formula:

wherein R6 is a C1-C4 alkyl radical, R5 is hydrogen or a C1-C4 alkyl radical, R9 is a C10-C25 alkyl radical and R7 is hydrogen or a C10C25 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 Trade Marks "Varisoft" 455 (Ashland Chemical Co.) and "Steinaquat" (Rewo). "Varisoft" 455 is believed to be the compound of formula given above wherein R8 is Me, R7 and RB are tallow alkyl, and R5 is hydrogen.

Among other suitable cationic surfactants may be mentioned N - tallow N,N',Nt,tri - ethanol - 1,3 - propylene diamine dichloride or di-methosulfate commercially available under the Trade Names Lilamin 540E03 (Lilachim), Dinoramex SH3, Inopol ODX3 (Pierrefitte-Auby), and N- tallow N,N,N',N',N' - pentamethyl - 1,3 - propylene diamine dichloride, commercially available under the Trade Names Stabiran MS-3 (Pierrefitte-Auby); "Duoquand" (Trade Mark(Armour Hess)); Adogen 477 (Ashland Co.). Also suitable is the substance sold as Dinormac (Pierrefitte-Auby) or "Duomac" (Trade Mark (Armour Hess)) believed to have the formula: Tallowyl-N+H2CH2)3-N+H3, 2(0COCH39 or the corresponding chloride.Herein Tallowyl represents predominantly C16 and C,8 alkyl groups derived from tallow fatty acids.

When the compositions of the invention are in the conventional form of dispersions of active components in an aqueous carrier medium, they usually contain from 0.1 to 14% cationic surfactant, preferably from 0.3 to 8% and most preferably 1% to 5%.

The polymeric cationic (i.e. polycationic) salts of the invention can be amine salts or quaternary ammonium, phosphonium or sulphonium salts. Preferred are quaternary ammonium salts. They include cationic derivatives of natural polymers such as some polysaccharide; gums, and starch, and certain cationic synthetic polymers such as polymers and co-polymers of cationic vinyl pyridinium halides.

Preferably the polymeric salts are water soluble to the extent of at least 0.5% by weight at 200 C. Preferably they have molecular weight from 1,000 to about 1,000,000, especially from 2,000 to 500,000. As a general rule, the lower the molecular weight the higher the degree of substitution (D.S.) by cationic, usually quaternary groups which is desirable, or, correspondingly, the lower the degree of substitution the higher the molecular weight which is desirable, but no precise relationship appears to exist.

Of the polysaccharide gums, guar and locust bean gums, which are galactomannam gums are available commercially, and are preferred. Thus guar gums are marketed under Trade Names 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 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(Meyhall)), 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+Me, Cl Very effective also is guar gum quaternised to a D.S. of about 0.2 to 0.5 with the quaternary grouping CH2CH=CHCH2N+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 containing 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 quaternised 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, usually 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 the usual ways.

Usually the D.S. is from 0.01 to 0.9, preferably from 0.2 to 0.7, that is rather higher than in most conventional cationic starches.

The cationic dextrins usually are employed at levels in the range from about 0.05 to 0.7% of the composition, 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 polysaccharide derivatives discussed above, for instance at 0.01 to 0.2% by weight of the composition, especially from 0.02 to 0.1%. In some instances the performance 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 4 of the available pyridine nitrogens quaternised.

Co-polymer of 70/30 molar proportions of vinyl pyridine/styrene, molecular weight about 43,000, with about 45% of the available pyridine nitrogens quaternised as above.

Co-polymers of 60/40 molar proportions of vinyl pyridine/acrylamide, with about 35% of the available pyridine nitrogens quaternised as above.

Co-polymers of 77/23 and 57/43 molar proportions of vinyl pyridine/methyl methacrylate, molecular weight about 43,000, with about 97% of the available pyridine nitrogens quaternised as above.

These polymeric cationic salts are effective in the compositions at the specified very low concentrations preferably from 0.01% by weight to 0.2or especially from about 0.02% to 0.1%. In some instances the effectiveness seems to fall off, when the content exceeds some optimum level, such as for polyvinyl pyridine and its styrene co-polymer about 0.05%.

Some other effective polymeric cationic salts are: Co-polymer of vinyl pyridine and N-vinyl pyrrolidone (63/37) with about 400/, 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.

"Eudragit" E (Trade Mark 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 methacrylate 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 made from the non-quaternised polymers as described in our co-pending British Patent application 48376/77) filed on the same day as the present application.

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:

where R,8 is C,~20 alkyl, or benzyl, and X is an anion.

Commercial examples of polymers of this class are sold under the generic Trade Mark" "Alcostat" 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 understood that usually only some of the units constituting the cationic polymers have the indicated structures.

Very highly preferred compositions of the invention, for reasons of performance and also of availability 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 to about double this amount, viz from 0.16 to 0.3% of cationic guar gum of D.S. from 0.05 to 0.19.

In other preferred compositions of the invention the cationic agar gum is wholly or partly replaced by a co-polymer believed to be of class (viii) viz Alcostat PB (Trade Name of AllieQColloids Ltd.).

Nonionic Softener Component Suitable softening agents and mixtures thereof are those described fully in our co-pending British Patent application 48376/77 filed on the same day as the present application. 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 monoand di-esters contain appreciable proportions of the higher esters.

As indicated above, these nonionic components are optional, and if present are at low levels such that the ratio of non ionic 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 colours.

In preparing the products according to the invention any effective method of mixing the components may be used. In general it is usually desirable to make a premix by melting together the softener components (a), (b) and (c), often at a temperature of about 65"C. 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 premix is added with appropriate mixing, sometimes high shear mixing being necessary, to a watery mixture at a temperature above the melting point of the premix containing the water for the composition together with mostly the water soluble components 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 products is from 3 to 7, especially from 4.5 to 5.5.

EXAMPLES Softening Test Treatment Samples of textile softening compositions as indicated below were prepared.

Treatment solutions, 3 gms in 2 litres of water were then prepared, the water containing various levels from 0 to 30 parts per million by weight of sodium dodecyl benzene sulphonate to simulate various degrees of anionic carry over in rinse liquors. Five previously desized Terry towelling swatches (5x25 grams) were treated in each test solution (2 litres) for 15 minutes in a Tergetometer at room temperature. The swatches were then rinsed spin dried and line dried. The swatches from different treatments were compared for softness of feel by a panel of judges using a paired comparison technique.

The following compositions were compared, the balance of the compositions consisting of water with minor amounts of perfume and colouring matter.

1. 4.0 /O DTDMAC 0.2% polyvinyl alcohol reacted with epoxypropyl trimethyl ammonium chloride, D.S. about 0.06, PVA molecular weight about 14,000.

2. 4.0 /O DTDMAC 0.03% Poly(vinyl pyridine)/(methyl meth acrylate) 57/47 by weight mixture quaternised by methyl halide.

3. 4.00/, DTDMAC 0.2% GAFQUAT 755 (Trade Name) a quaternised material believed to be high molecular weight co-polymer of vinyl pyrrolidone, m.wt. about 1,000,000.

4. 4.0 DTDMAC 0.1% Eudragit E quaternised with methyl halide at about 75% of the available amino nitrogen atoms. Eudragit E (Trade Name) is believed to be a co-polymer of N,N-dialkyl amino alkyl methacrylate with a neutral acrylic ester.

5. 4.00/, DTDMAC 0.03% Poly (vinyl pyridine)/(styrene) 70/30 by weight mixture quaternised by methyl halide at about 45% of the available pyridine nitrogen atoms.

6. 3.0 / DTDMAC 0.2% Jaguar C-l39 (Trade Name) believed to be guar gum quaternised to a D.S. of about 0.13.

7. 4.0 DTDMAC 0.1% Cationic guar gum quaternised to D.S.

0.25.

8. 4.0 /O DTDMAC 0.20% Cationic xanthan gum.

9. 4.0 /O DTDMAC 0.20% British gum quaternised to D.S. 0.4 with epoxypropyl trimethyl ammonium chloride.

10. 4.0 DTDMAC 0.1% Cationic guar gum as in example 7, and 0.3% glycerol monostearate.

All these products provided substantially the same softening performance as a composition comprising 5.8% DTDMAC typical of prior art textile softening compositions.

Substantially similar performance is obtained when the DTDMAC is replaced by an equal amount of ditallow dimethyl ammonium methosulphate, -toluene sulphonate, acetate, or benzoate.

Substantially similar performance is obtained also when the DTDMAC is replaced by an equal amount of Varisoft 455 (Trade Name-a tallow-based imidazolinium salt), C1 > 20 alkyl pyridinium halide. C1e~20 alkyl methyl morpholinium halides, N - tallow - N,N'N' - triethanol - 1,3 - propylene diamine dichloride.

11. 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, eg. at 0.050.1% by weight of the composition in the rinse liquor comprises 8.5% DTDMAC 4.0% N - tallow - N,N',N' - triethanol propylene diamine dichloride.

0.2% Guar gum, quaternised to a D.S. of 0.3 with epoxypropyl trimethyl ammonium chloride.

Balance to 100water with minor amount of perfume, colour, bactericide, etc.

12. A textile conditioning composition comprises 3.0% Varisoft 455 (Trade Name for tallow imidazoline) 0.4% Cationic guar gum as employed in example 7.

Balance to 100water and minor components.

13-14 Textile softening compositions comprise: 13 14 DTDMAC 4.5 4.0 Alcostat C 0.2 0.4 Water to 100 Alcostat C (Trade Name Allied Colloids Ltd) is believed to be a quaternised polyethyleneimine salt.

WHAT WE CLAIM IS: 1. A textile conditioning composition comprising (a) a substantially water-insoluble cationic textile softening agent, as hereinbefore defined, (b) from 0.001 to 0.70% by weight of the composition 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 pyridinium salts, and co-polymers therewith, (iv) cationic polyvinyl alcohol, (v) cationic polyvinyl pyrrolidone co-polymers, (vi) cationic co-polymers of dialkylaminoalkyl methacrylate, wherein each alkyl has 1--3 carbon atoms, with styrene, or a neutral acrylic ester, and (vii) Quaternised polyethyleneimines having at least 10 ethylenimine residues in the molecule, and, optionally, (c) 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. A composition according to claim I wherein the cationic salt has more than 10 monomeric units in the molecular.

3. A composition according to claim I or 2 in the form of an aqueous dispersion containing from 1% to 30 /O by weight of components (a), (b) and (c) together.

4. A composition according to any one of claims l to 3 wherein the polymeric cationic salt has a molecular weight of from 1,000 to 1,000,000.

5. A composition according to claim 4 wherein the cationic softening agent is selected from: (a) non-cyclic quaternary ammonium salts having two C,0 2s alkyl chains, and (b) C, , 25 alkyl imidazotinium salts, and (c) mixtures thereof.

**WARNING** end of DESC field may overlap start of CLMS **.

Claims

**WARNING** start of CLMS field may overlap end of DESC **. Substantially similar performance is obtained when the DTDMAC is replaced by an equal amount of ditallow dimethyl ammonium methosulphate, -toluene sulphonate, acetate, or benzoate. Substantially similar performance is obtained also when the DTDMAC is replaced by an equal amount of Varisoft 455 (Trade Name-a tallow-based imidazolinium salt), C1 > 20 alkyl pyridinium halide. C1e~20 alkyl methyl morpholinium halides, N - tallow - N,N'N' - triethanol - 1,3 - propylene diamine dichloride. 11. 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, eg. at 0.050.1% by weight of the composition in the rinse liquor comprises 8.5% DTDMAC 4.0% N - tallow - N,N',N' - triethanol propylene diamine dichloride. 0.2% Guar gum, quaternised to a D.S. of 0.3 with epoxypropyl trimethyl ammonium chloride. Balance to 100water with minor amount of perfume, colour, bactericide, etc. 12. A textile conditioning composition comprises 3.0% Varisoft 455 (Trade Name for tallow imidazoline) 0.4% Cationic guar gum as employed in example 7. Balance to 100water and minor components. 13-14 Textile softening compositions comprise: 13 14 DTDMAC 4.5 4.0 Alcostat C 0.2 0.4 Water to 100 Alcostat C (Trade Name Allied Colloids Ltd) is believed to be a quaternised polyethyleneimine salt. WHAT WE CLAIM IS:

1. A textile conditioning composition comprising (a) a substantially water-insoluble cationic textile softening agent, as hereinbefore defined, (b) from 0.001 to 0.70% by weight of the composition 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 pyridinium salts, and co-polymers therewith, (iv) cationic polyvinyl alcohol, (v) cationic polyvinyl pyrrolidone co-polymers, (vi) cationic co-polymers of dialkylaminoalkyl methacrylate, wherein each alkyl has 1--3 carbon atoms, with styrene, or a neutral acrylic ester, and (vii) Quaternised polyethyleneimines having at least 10 ethylenimine residues in the molecule, and, optionally, (c) 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.

6. A composition according to claim 5 which contains from 0.3 " to 8 , of said

cationic softening agent.

7. A composition according to any one of claims 4 to 6 wherein the cationic polysaccharide is a cationic guar or locust bean gum of degree of substitution from 0.1 to 0.5.

8. A composition according to any one of claims 4 to 6 wherein the cationic polysaccharide is a cationic dextrin having molecular weight, of dextrin, from 1,000 to 10,000 and D.S. from 0.2 to 0.8.

9. A composition according to claim 7 or claim 8 wherein the cationic groupings on the anhydro sugar residues have formula -CH2CH=CHCH2N+Me, Cl- or -CH2CH(OH)CH2N+Me3, Cl

10. A composition according to claim 1 substantially as hereinbefore described with reference to any one of the Examples.