GB2024873A - Cosmetic compositions containing certain quaternary ammonium polymers - Google Patents

Abstract

Cosmetic compositions in the form of a dyeing or bleaching carrier, a permanent-waving composition or a pre-perm or after-perm lotion are described which contain at least one polymer containing units of the formula: <IMAGE> in which each R1, each R2, each R3 and each R4, which are identical or different, represents a saturated or unsaturated, substituted or unsubstituted, aliphatic radical, a saturated or unsaturated, substituted or unsubstituted, alicyclic radical, or a substituted or unsubstituted arylaliphatic radical, or R1 and R2 and/or R3 and R4, form together with the nitrogen atom to which they are attached, a ring which can contain a second hetero-atom other than nitrogen, A represents a linear or branched, substituted or unsubstituted, alkylene or alkenylene group optionally containing, in the chain or as a substituent or both, one or more hetero-atoms or one or more arylene groups, X< theta > is an anion of an inorganic or organic acid and m is 2 or 3.

Description

SPECIFICATION Cosmetic compositions containing certain quaternary ammonium polymers The present invention relates to the use of certain quaternised polymers as cosmetic agents in certain types of cosmetic composition.

The present invention provides cosmetic compositions for hair which comprise at least one polymer of which the macrochain contains units of the formula:

in which R1 R2, R3 and R4, which are identical or different, represent a saturated or unsaturated, substituted or unsubstituted, aliphatic radical, a saturated or unsaturated, substituted or unsubstituted, alicyclic radical, or a substituted or unsubstituted arylaliphatic radical, or two radicals R1 and R2 and/or R3 and R4, form, together with the nitrogen atom to which they are attached, a ring with can contain a second hetero-atom other than nitrogen.A represents a linear or branched, substituted or unsubstituted, alkylene or alkenylene group optionally containing, in the chain or as a substituent or both, one or more hetero-atoms or one or more arylene groups, X is an anion of an inorganic or organic acid and m is 2 or 3, and also the ingredients which make it possible to present them in the form of a dyeing or bleaching carrier or in the form of a permanent-waving composition or a pre-perm or after-perm lotion.

Amongst the polymers which correspond to this definition, there may be mentioned, in particular, those in which R1, R2, R3 and R4, which are identical or different, represent an alkyl or hydroxyalkyl group 'containing from 1 to 20 carbon atoms, a (cycloalkyl)-alkyl radical having less than 20 carbon atoms, a cycloalkyl radical with 5 or 6 ring members, or an aralkyl radical, such as a phenylalkyl radical, in which the alkyl group preferably contains from 1 to 3 carbon atoms, or alternatively two radicals R1 and R2 (or R3 and R4), which are attached to one and the same nitrogen atom, together represent a polymethylene radical having from 2 to 6 carbon atoms, so as to form, with the said nitrogen atom, a ring which can contain a second hetero-atom, for example an oxygen or sulphur hetero atom, A represents a linear or branched alkylene or alkyl group which is optionally substituted by one or more groups, such as -OH or =O, is optionally interrupted by one or more oxygen, sulphur or nitrogen hetero-atoms and/or by one or more phenylene groups, and has from 2 to 18 carbon atoms, it being possible, in particular, for A to represent an ortho-, meta- or para xylylene radical or a radical of the formula::--(CH2)n--S--(CH2)n--,--CH2--CO--CH2--, --(CH2)n--O--(CH2)n--,--CH2--C8H4--C6H4--CH2--,--(CH2)n--S--S--(CH2)n--, -CH2-C6H4--O--C6H4--CH2--,--(CH2)n--SO--(CH2)n--,--CH2--C6H4--SO2--C6H4--CH2--, --(CH2)n--SO2--(CH2)n--,--C6H4--CH2--C6H4--,--CH2--CHOH--CH2--, --C6H4--C(CH3)2--C6H4--,--C6H4--CO--C6H4--,--C6H4--CHOH--C6H4--, -alkylene-N(R5)-alkylene or -arylene-N(R5)-arylene, n being an integer equal to 2 or 3, R5 representing alkyl, cycloalkyl or aralkyl having up to 20 carbon atoms, the alkylene and arylene having up to 20 carbon atoms, and X- is a halide ion, in general a bromide, chloride or iodide ion, or an anion derived from other inorganic acids, such as phosphoric acid or sulphuric acid, or an anion derived from an organic sulphonic acid, in particular para-toluenesulphonic acid, or from an organic carboxylic acid.

It should be noted thatthe invention extends to the use of the polymersin which the groups A and the pairs (R1, R2) or (R3, R4) have several different meanings in one and the same polymer.

Although the invention is not restricted to the use of polymers having a fixed degree of polymerisation, the polymers used according to the invention generally have a molecular weight of 1,500 to 50,000.

Amongst the polymers possessing quaternised nitrogen atoms, as defined aboe, there may be mentioned, in particular, the polymers of which all the units correspond to the formula I above, and, in particular, those in which R,=R7=R3=RX,=ÇH3 or C2H and those in which A represents:: (CH2)nO(CH2)n, n being defined as above,--CH2--C6H4--CH2--,--CH2--CHOH--CH2--, (CH2)p, p being an integer from 2 to 18, and --(CH2)n1--CH=CH--(CH2)n2--,n1 nr and 2 being O or integers, the sum of n1 and n2 being at most equal to 16. 1 (CH2)n2- n and n Amongst the preferred polymers, those which correspond to the formula I in which R,=R2=R3=R4=CH3, m = 3, X = Cí and A = -CH2CH2-O-CH2CH2- (polymer P1), A = -CH2-CHOH-CH2- (polymer P2), A = -CH2-C6H4-CH2- (polymer P3), A = -CH2-CH=CH-CH2- (polymer P4) or A=-(CH2)6-(polymer P5), and also those of the formula 1 in which R1=R2=R3=R4=C2H5, m=3, X=Cl and A=-(CH2)6-(polymer P6), A=-CH2-C HOH-CH2-(polymer P7) or A=-CH2H=CH-CH2-(polymer P8), may be mentioned in particular.

The polymers used according to the present invention can also be copolymers which additionally contain units of the formula:

in which R'1, R'2, R'3 and R'4 are as defined for R1, R2, R3 and R4, A' is a substituted or unsubstituted linear or branched, alkylene group or a substituted or unsubstituted arylene group, which can contain up to 20 carbon atoms, and A is defined as above.

Amongst these copolymers, polymers P9 to P14, the composition of which is indicated below, may be mentioned in particular.

The polymers mentioned above can be prepared, in particular, by processes analogous to those which are described in British Specification No. 1,513,672.

The compositions of the present application contain the ingredients and adjuvants which make it possible to present them in the form of dyeing or bleaching carriers or compositions or in the form of permanent-waving compositions (or pre-perm or after-perm lotions).

It is known that, currently, for dyeing or bleaching hair, dyeing or bleaching carriers are used which make it possible to present the composition either in the form of a cream or in the form of a gel, or a liquid which can be gel led upon dilution.

In general, the creams are obtained either from soaps of C12 to C20 fatty acids, of from fatty alcohols in the presence of anionic or non-ionic emulsifiers.

The soaps can be formed from natural or synthetic fatty acids having from 12 to 20 carbon atoms such as: lauric acid, myrlstic acid, palmitic acid, oleic acid, stearic acid, hydroxystearic acid, arachidic acid, ricinoleic acid, lanolinic acid, phenylstearic acid and linoleic acid, generally at concentrations of 1 to 60% and preferably 5 to 30% by weight (before dilution).

The alkalising agents used to form the soaps are, in particular, sodium hydroxide, potassium hydroxide, ammonia, monoethanolamine, diethanolamine, triethanolamine, mono- and diisopropanolamine, N-ethylmorpholine, 2-aminobutan-1 -'ol, 2-arniflo-2-methyiprop,an-1 -ol and mixtures thereof.

The creams can also be formulated from natural or synthetic alcohols having from, say, 12 to 20 carbon atoms, in a mixture with one or more emulsifiers. Amongst these fatty alcohols, there may be mentioned, in particular, alcohols derived from copra fatty acids, myristyl alcohol, cetyl alcohol, stearyl alcohol, arachidyl alcohol, isostearyl alcohol, hydroxystearyl alcohol, oleyl alcohol and ricinoleyl alcohol; they are generally used at concentrations from 1% to 60% and preferably from 5% to 30% by weight.

The emulsifiers which can be used in the compositions in the form of a cream include oxyethyleneated or polyglycerolated natural or synthetic C10C20 fatty alcohols such as polyoxyethyleneated oleyl alcohol containing from 10 to 30 mols of ethylene oxide (per mol of alcohol), oxyethyleneated cetyl alcohol containing from 6 to 10 mols of ethylene oxide, oxyethyleneated cetyl/stearyl alcohol containing 10 mols of ethylene oxide, oleyl/cetyl alcohol containing 30 mols of ethylene oxide, stearyl alcohol containing 10, 1 or 20 mols of ethylene oxide, polyglycerolated oleyl alcohol containing 4 mols of glycerol, and synthetic fatty alcohols which contain from 9 to 20 carbon atoms and are polyoxyethyleneated with 5 to 30 mols of ethylene oxide.

These non-ionic emulsifiers are generally present at concentrations from 1% to 60%, and preferably from 5% to 30%, by weight.

Other emulsifiers include alkyl-sulphates which may or may not be oxyethyleneated, such as sodium lauryl-sulphate, ammonium lauryl-sulphate, sodium cetyl-/stearyl-sulphate, triethanolamine cetyl-/steraryl-sulphate, monoethanolamine lauryl-sulphate or triethanolamine lauryl-sulphate, the sodium salt of the sulphate half-ester of oxyethyleneated lauryl alcohol containing, for example, 2.2 mols of ethylene oxide, and the monoethanolamine salt of the sulphate half-ester of oxyethyleneated lauryl alcohol containing, for example, 2.2 mols of ethylene oxide. These constituents are generally present at concentrations from 1% to 60%, and preferably from 3% to 15%, by weight.

These creams can additionally contain various customary adjuvants such as fatty amides, especially mono- or di-ethanolamides of acids derived from copra, of lauric acid or of oleic add, generally used at concentrations up to 15% by weight.

The creams can also contain sequestering agents, such as ethylenediaminetetraacetic acid and its salts, thickeners and perfumes.

In general, the gellable liquids are obtained either from oxyethyleneated or polyglycerolated nonionic compounds and from solvents, or from soaps of liquid fatty acids, such as soaps of oleic acid, linoleic acid, ricinoleic acid or isostearic acid, and from solvents.

The alkalising agents used to form the soaps can be, for example, an alkali metal base or an gamine.

in particular sodium hydroxide, potassium hydroxide, ammonia, monoethanolamine, diethanolamine, triethanolamine, mono- and di-isopropanolamine, N-ethylmorpholine, 2-aminobutan-1 -ol, 2-amino-2 methyl-propan- 1 -ol or a mixture thereof.

Amongst the oxyethyleneated non-ionic compounds, there may be mentioned natural or synthetic liquid fatty alcohols, such as oleyl alcohol, containing 4 and 10 mols of ethylene oxide, synthetic C10-C12 fatty alcohol containing 4 or 6 mols of ethylene oxide, and synthetic C9-C15 fatty alcohols containing 2, 6 or 9 mols of ethylene oxide.

Amongst the oxyethyleneated non-ionic compounds', there may be mentioned, in particular, nonylphenol polyether containing 4 or 9 mols of ethylene oxide. These constituents are generally present at concentrations from 5 to 60% by weight and preferably from 5% to 40% by weight.

Amongst the polyglycerolated non-ionic compounds, there may be mentioned, in particular, oleyl alcohol containing 2 mols of glycerol and glycerolated oleyl alcohol containing 4 mols of glycerol. These constituents are generally present at concentrations from 5% to 60% by weight and preferably from 5% to 40% by weight.

The solvents which can be used include lower aliphatic alcohols, such as ethyl alcohol and propyl or isopropyl alcohol, glycols, such as propylene glycol, methylglycol, ethylglycol and butylglycol, diethylene glycol, dipropylene glycol and hexylene glycol, and diethylene glycol monoethyl ether.

These solvents, or mixtures thereof, are generally used at concentrations (before dilution) of 2 to '20%, and preferably 5 to 15%, by weight.

The gellable composition can additionally contain various customary adjuvants, such as fatty amides, natural or synthetic fatty alcohols, alkali metal alkyl-sulphates which may or may not be oxyethyleneated, preservatives, sequestering agents and perfumes.

Amongst the fatty amides, oleyl or lauryl diethanolamide and copra mono- or di-ethanolamide may be mentioned in particular. These amides are generally used at concentrations (before dilution) of 0.5 to 15% and preferably 1 to 10%, by weight Amongst the natural or synthetic fatty alcohols, oleyl, lauryl, octyldodecyl, hexyldodecyl, isostearyl, ricinoleyl and linoleyl alcohols may be mentioned in particular. These alcohols are generally used at concentrations (before dilution) of 1 to 25%, and preferably 5 to 15%, by weight.

Amongst the alkali metal alkyl-sulphates which may or may not be oxyethyleneated, there may be mentioned, in particular, sodium lauryl-sulphate, ammonium ortriethanolamine lauryl-sulphate, monethanolamine lauryl-sulphate, the sodium salt of the sulphate half-ester of oxyethyleneated lauryl alcohol containing, for example, 2.2 mols of ethylene oxide, and the monoethanolamine salt of the sulphate half-ester of oxyethyleneated lauryl alcohol containing, for example, 2.2 mols of ethylene oxide. These sulphates are generally used at concentrations (before dilution) of 0.5 to 15%, and preferably 1 to 10%, by weight.

On mixing with hydrogen peroxide, in the dilution ratios which are most frequently used (from 1 to 3 times), in order to provide sufficient amounts of hydrogen peroxide and ammonia to obtain a lightening effect, the dyeing or bleaching carriers in the form of a cream give a cream and the carriers in the form of gellable liquids give a gel.

This invention includes dyeing compositions which contain the dyeing carrier of the invention in admixture with direct or oxidative dyestuffs.

This invention also includes dyeing or bleaching compositions which are presented in two parts to be mixed at the time of use, the first part consisting of the carrier, optionally containing an oxidative dyestuff, and the second part consisting of an oxidising agent, such as hydrogen peroxide, these two parts being combined in a package containing the directions for their use.

Oxidative dyestuffs are generally aromatic compounds of the diamine, aminophenol or phenol type. They are not generally dyestuffs in themselves, but are converted to dyestuffs by condensation in the presence of an oxidising medium, generally hydrogen peroxide. Amongst these oxidative dyestuffs, a distinction is made between, on the one hand bases which are para- or ortho-derivatives, in particular ortho or para diamines or aminophenols, and, on the other hand, compounds referred to as modifiers or couplers, which are meta-derivatives, in particular meta-diamines, m-aminophenols and polyphenols.

Other dyestuffs which can be used are direct dyestuffs such as nitro dyestuffs, anthraquinone, triphenylmethane, azo, metalliferous, xanthene and acridine derivatives.

In general, the dyeing carriers of the invention contain from 0.5 to 10% by weight, and preferably from 1 to 3% by weight, of quaternised polymers as defined above.

The pH of the carriers of the invention is generally from 6 to 11 (and preferably 8 to 11); this can be achieved by the addition, if necessary, of a suitable basic agent, or of an acidic agent such as tartaric acid, citric acid, acetic acid, hydrochloric acid or phosphoric acid.

Preferably, the compositions of this invention are free from anionic polymer.

The present invention also provides a process for dyeing or bleaching hair, in which a dyeing or bleaching carrier of this invention, which optionally contains dyestuffs and is optionally mixed with an oxidising agent such as hydrogen peroxide, is applied to the hair, the applied composition is left to act for a sufficient time to achieve the desired dyeing or bleaching effect, and the hair is then rinsed.

In general, the composition is left to act for 5 to 45 minutes and preferably for 1 5 to 30 minutes.

The amounts of dyeing or bleaching composition applied to the head of hair are generally from 10 to 100g.

The compositions of the present application can also be presented in the form of permanentwaving compositions.

The conventional technique for permanently waving hair consists, in a first stage, of opening the S-S bonds in the keratin of the hair using a composition containing a reducing agent, and then, in a second stage, preferably after having rinsed the head of hair, of re-forming the said S-S bonds by applying an oxidising composition to the hair, while it is in a deformed state, for example by stretching it so as to impart the desired shape to the hair.

The formulation of the said reducing and oxidising compositions is known and described in the works on cosmetology, in particular by E. SIDI and C. ZVIAK, Problemes Capillaires ("Hair Problems"), Paris, 1 966 (Gauthier-Villard).

The permanent-waving compositions of the present invention are preferably reducing compositions for the first stage of the permanent-waving operation.

In addition to the reducing agent, these compositions contain adjuvants which make it possible to present them in the form of lotions or in the form of a powder to be diluted with water.

The reducing agent is most frequently a mercaptan, such as thioglycerol, or thioglycolic acid or a derivative thereof.

Most frequently the compositions are based on thioglycolic acid or its derivatives, in particular its salts such as its ammonium, morpholine or ethylamine salts, its esters such as its glycol ester or glycerol ester, its hydrazide or its amide.

The concentration of the reducing agent is the concentration required to achieve the reduction of a sufficient number of S-S bonds, as is known in the art. For example, in the case of thioglycolic acid, the concentration is generally from 1 to 11% by weight.

The pH of these compositions for the first stage of a permanent-waving operation is generally from 7to 10.

The reducing compositions generally contain from 0.1 to i 0%, and preferably from 0.25 to 5%, by weight of the polymer of formula I.

These lotions for the first stage of the permanent-waving operation are most frequently aqueous solutions which can additionally contain pH modifiers, for example ammonium carbonate or bicarbonate, auxiliary reducing agents, such as sulphites, for example sodium sulphite or potassium sulphite, solvents, such as ethanol or isopropanol, non-ionic or cationic surface-active agents, perfumes and/or dyestuffs.

The polymers of formula I are compatible with the usual ingredients and adjuvants used in the permanent-waving (or dyeing) compositions.

This invention also provides a process for permanently waving hair, in which a sufficient amount of a reducing composition of this invention is applied to the hair, the composition is left to act for, say 5 to 20 minutes, the hair is rinsed and an oxidising composition is applied to the hair, while the hair is in a constrained state, for example while stretching on curlers, in a sufficient amount to re-form the S-S bonds in the keratin of the hair.

The oxidizing agent is, in particular, hydrogen peroxide (H2O2), a per-salt, such as sodium perborate or persulphate, a bromate (sodium bromate, calcium bromate or magnesium bromate) or sodium iodate.

The hair is generally stretched by rolling onto curlers, this preferably being carried out before applying the reducing composition.

After the oxidising composition has been applied for a sufficient time, the curlers are removed and the hair is then rinsed. it is then possible to finish with a wavesetting operation.

The compositions of the present invention can also be lotions to be applied before or after a permanent-waving operation. In addition to water, these lotions can contain, for example, solvents, for example ethanol, or isopropanol, non-ionic or cationic surface-active agents, pH modifiers, perfumes and/or dyestuffs. They generally contain from 0.1 to 10%, and preferably from 0.25 to 5%, by weight of the polymer of formula (I). The present invention also provides a process for treating hair, which- consists in applying a sufficient amount of such a pre-perm or after-perm lotion to the hair, before or after, respectively, a permanent-waving operation.

In the compositions of this invention, the polymers of formula I protect the hair against the wellknown degradation effects produced by dyeing, bleaching or permanent-waving operations.

When applied in the form of the compositions of this invention, the polymers of formula I make the hair easier to comb out when wet and when dry. They impart springiness properties, a glossy appearance and a soft feel to the hair. Furthermore, they prevent or reduce the development of static electricity on the hair.

The invention also provides certain polymers of the formula I which are new products, in particular polymers P2to Per4.

The following Examples further illustrate the present invention.

EXAMPLE 1 DYEING COMPOSITION The dyeing carrier has the formula: Cetyl/stearyl alcohol 22 g EXAMPLE 1 DYEING COMPOSITION Oleyl diethanolamine 5g Sodium cetyl-stearyl sulphate 4g Polymer P1 220 B6 strength ammonia solution 12 ml.

In order to obtain the dyeing composition, the following oxidative dyestuffs and adjuvants are added to this carrier: m-Diaminoanisole sulphate 0.048 g Resorcinol 0.420 g m-Aminophenol 0.150g Nitro-p-phenylenediamine 0.085 g.

p-Toluylenediamine 0.004 g Trilon B (ethylenediaminetetraacetic acid) 1.000 g Sodium bisulphate solution d = 1.32 1.200 g Water q.s.p. 100 g 30 g of this formulation are mixed with 45 g of hydrogen peroxide of 20 volumes strength; this gives a smooth consistent cream which is pleasant to apply and adheres weli to the hair.

After an application time of 30 minutes, the hair is rinsed and dried.

The hair is easy to comb out when wet and when dry.

The hair is glossy and has body (volume) and the feel is pleasant and silky.

A blond shade is obtained on 100% white hair.

EXAMPLE 2 DYEING COMPOSITION The dyeing carrier has the formulation: Stearyl alcohol 20 g Coconut monoethanolamide 5g Ammonium lauryl-sulphate (containing 20% of fatty alcohols) lOg.

Polymer P2 6g 220 B6 strength ammonia solution 10 ml In ordr to obtain the dyeing composition, the following oxidative dyestuffs and adjuvants are added to this carrier: m-Diaminoanisole sulphate 0.048 g Resorcinol 0.420 g m-Aminophenol O.15Og Nitro-p-phenylenediamine 0.085 g p-Toluylenediamine 0.004 g Trilon B (ethylenediaminetetraacetic acid) 1.000 g EXAMPLE 1 DYEING COMPOSITION Sodium bisulphate solution d = 1.32 1.200 g Water q.s.p. 100 g 30 g of this formulatin are mixed with 45 g of hydrogen peroxide of 20 volumes strength; this gives a smooth consistent cream which is pleasant to apply and adheres well to the hair.

After an application time of 30 minutes, the hair is rinsed and dried.

The hair is easy to comb out when wet and when dry.

The hair is glossy and has body (volume) and the feel is pleasant and silky.

A blond shade is obtained on 100% white hair.

Comparable results were obtained on replacing polymer P2 by an equivalent amount of polymer P3 or P4 or of a mixture of P3 and P4.

EXAMPLE 3 DYEING COMPOSITION The dyeing carrier has the formulation: Triethanolamine lauryl-sulphate (40% of active ingredient) 3 g 2-Octyidodecanol marketed under the name EUTANOL G by the Société Henkel 8g Oleyl diethanolamide 6g Oleyl/cetyl alcohol containing 30 mols of E.O., marketed under the name MERGITAL OC 30 by the Socio'to Henkel 3 g Oleic acid 19 g Polymer P4 Butylcellosolve 7g 96% strength ethyl alcohol 8.S g Propylene glycol 6 g 220 Bé strength ammonia solution 20 ml In order to obtain the dyeing composition, the following oxidative dyestuffs and adjuvants are added to this carrier:: p-Aminophenol 0.22 g m-Diaminoanisole sulphate 0.044 g Resorcinol 0.12 g m-Aminophenol 0.075 g Nitro-p-phenylenediamine 0.030 g p-Toluylenediamine 0.16 g Trilon B 3 g Sodium bisulphite solution d = 1.32 1.2 g Water q.s.p. 100 g 30 g of this formulation are mixed in a bowl with 30 g of hydrogen peroxide of 20 volumes strength. This gives a gel. It is applied using a paintbrush. It is left on the hair for 30 to 40 minutes and the hair is rinsed.

The hair is easy to comb out. The feel is silky.

The hair is set in waves and dried.

The hair is glossy and springy; it has body (volume); the feel is silky and the hair is easy to comb out.

A coppery light blond shade is obtained on 100% white hair.

E.O. denotes ethylene oxide.

Comparable results were obtained on replacing polymer P4 by an equivalent amount of polymer P2 or P5 or by an equivalent amount of a mixture of polymers P2 and P3 or of a mixture of P12 and P14.

EXAMPLE 4 DYEING COMPOSITION The dyeing carrier has the formulation: EUTANOL G 12 g Oleyl diethanolamide 99 MERGITAL OC 30 2g Oleic acid 20 g Polymer P2 3g Butylcellosolve 6g 96% strength ethyl alcohol lOg Propylene glycol 5g 220 B6 strength ammonia solution 18 ml In order to obtain to obtain the dyeing composition, the following oxidative dyestuffs and adjuvants are added to this carrier:: p-Aminophenol 0.08 g m-Diaminoanisole sulphate 0.04 g Resorcinol 0.248g m-Aminophenol 0.07 g Nitro-p-phenylenediamine 0.002 g p-Toluylenediamine 0.3 g TRILON B 3 g Sodium bisulphite solution d = 1.32 1.2 g Water q.s.p. 100 g 30 g of this formulation are mixed in a bowl with 30 g of hydrogen peroxide of 20 volumes strength. This gives a gel.

It s applied using a paintbrush. It is left on the hair for 30 to 40 minutes and the hair is rinsed.

The hair is easy to comb out. The feel is silky.

The hair is set in waves and dried.

The hair is glossy and springy and has body (volume); the feel is silky and the hair is easy to comb out.

An ashen blond shade is obtained on 100% white hair.

Comparable results were obtained in replacing polymer P2 by an equivalent amount of polymer P4, P5, P7 or P8.

EXAMPLE 5 DYEING COMPOSITION The dyeing carrier has the formulation: EUTANOL G 12 g Oleyl diethanolamide 9g MERGITAL OC 30 2g Oleic acid 20 g Polymer P3 3g Butylcel losolve 6g 96% strength ethyl alcohol lOg Propylene glycol 5g 22 Bé strength ammonia solution 18:ml In order to obtain the dyeing composition, the following oxidative dyestuffs and adjuvants are added to this carrier:: 4-(P-Methoxyethylamino)-aniline dihydrocchloride 0.4 g p-Aminophenol 0.2-5 g Resorcinol 0.07 g m-Aminophenol 0.04 g 5-N-(P-Hydroxyethyl)-amino-2-methylpheno 0.12 g 2,4-Diaminophenoxyethanol dihydrochloride 0.03 g Hydroquinone 0.1 g Trilon B 0.24 g Sodium bisuphite solution d = 1.32 1 ml Water q.s.p. 100 g 30 g of this formulation are mixed in a bowl with 30 g of hydrogen peroxide of 20 volumes strength. This gives a gel.

It is applied using a paintbrush. It is left on the hair for 30 to 40 minutes and the hair is rinsed.

The hair is easy to comb out and has a silky feel. It is set in waves and dried. The hair is glossy and springy and has body. In the dry state, the feel is still silky and the hair is easy to comb out.

A light blond shade is obtained on 100% white hair.

Comparable results were obtained on replacing polymer P3 by an equivalent amount of polymer P2, P4, P11 or P13.

EXAMPLE 6 BLEACHING COMPOSITION This composition has the formulation: Oleic acid 20 g Monoethanolamine 7g Oleyl alcohol 12 g EXAMPLE 1 DYEING COMPOSITION Triethanolamine lauryl-sulphate containing 40% of active ingredient 3g MERGITAL OC 30 3g Lauryl diethanolamide 12 g Polymer P5 3g Butylglycol 5g Ethyl glycol 8.5 g Propylene glycol 6 g Trilon B 0.2 g 220 B6 strength ammonia solution 18 ml Water q.s.p. 100 g Before use, 60 g of this formulation are mixed in a bowl with 120 g of hydrogen peroxide of 20 volumes strength. This gives a gelled liquid which is pleasant to apply and adheres well to the hair when applied using a paintbrush.It is left on the hair for 30 to 45 minutes and the hair is rinsed.

The hair is easy to comb out when wet and the feel is silky.

After drying, the hair is glossy and springy; it has body (volume); the feel is silky and the hair is easy to comb out.

The hair is in very much better condition than after bleaching with the same formulation which does not contain the cationic polymer.

After bleaching, a deep blond shade is obtained on deep chestnut hair.

Comparable results were obtained on replacing polymer P5 by an equivalent amount of one of polymers P2, P3, P4, P6, P8, P8 or P10.

The method of preparation of the cationic polymers used in the embodiments of compositions is given below.

PREPARATION NO. 1: Preparation of polymer P8 having units of the formula:

46 g (0.2 mol) of N,N'-bis-(3-dimethylaminopropyl)-urea, 31 g (0.2 mol) of 1,6-dichlorohexane and 50 g of water are heated under reflux for 3 hours, whilst stirring vigorously. The mixture is left to cool and 140 g of water are then added to the viscous solution thus obtained. About 150g of water are distilled in order to remove traces of residual 1,6-dichlorohexane and the concentration of the resulting polymer in the solution is then adjusted to 50%.

Analysis on 50% strength solution: calculated Clue: 9.22% found Clue: 8^.68% PREPARATION NO. 2: Preparation of polymer P2 having units of the formula:

The procedure followed is the same as for preparation no. 1, using N,N'-bis-(3 dimethylaminopropyl)-urea and 1,3-dichloropropan-2-ol as the starting materials.

Analysis on 59% strength solution: calculated Clue: 9.89% found Clue: 8.78% Appearance: viscous, clear, colourless solution.

PREPARATION NO. 3 Preparation of polymer P4 having units of the formula:

This compound is obtained in accordance with the same procedure as polymer P5, using N,N'-bis (3-dimethylaminopropyl)-urea and trans-1 -dibromobut-2-ene as the starting materials.

Analysis on 50% strength solution: calculated Bre: 18% found Bre: 17.32% Appearance: viscous, slightly yellow, clear solution.

PREPARATION NO. 4: Preparation of polymer P3 having units of the formula:

46 g (0.2 mol) of N,N'-bis-(3-dimethylaminopropyl)-urea, 52.8 g (0.2 mol) of 1,4-bis (bromomethyl)-benzene and 216 g of methanol are heated under reflux for 3 hours in a 500 cm3 Erlenmeyer flask, whilst stirring vigorously. The mixture is left to cool and the methanol is then distilled under reduced pressure. 200 cm3 of water are added and the aqueous phase is washed with three times 100 cm3 of chloroform.

1 50 cm3 of water are distilled under reduced pressure and the concentration of active ingredient in the resulting solution is adjusted to 50% by diluting with water.

Analysis on 50% strength solution: calculated Bre: 16.2% found Bre: 14.7% Appearance: viscous, clear, colourless solution.

PREPARATION NO. 5: Preparation of polymer P1 having units of the formula:

46 g (0.2 mol) of N,N'-bis-(3-dimethylami nopropyl)-urea and 50 g of water are mixed. The mixture is heated to about 50-600C, 28.6 g (0.2 mol) of dichloroethyl ether are introduced and the resulting mixture heated under reflux for 11 hours. 140 cm3 of water are then added. The water is distilled until a solution containing 50% of active ingredient is obtained.

Analysis on 50% strength solution: calculated C: 9.5% found Cl-: 9.19% EXAMPLE 7 PERMANENT-WAVING COMPOSITION a) Reducing composition (1st stage) Thioglycolic acid 8g Ammonia q.s.p. pH 7 Ammonium bicarbonate 6.4 g Dimethyldistearylammonium chloride 0.2 g EXAMPLE 7 PERMANENT-WAVING COMPOSITION Polymer P1 3g Oxyethyleneated oleyl alcohol containing 20 mols of ethylene oxide 1g Perfume q.s.

Water q.s.p. 100 g b) Neutraliser (2nd stage) Dimethylstearylammonium chloride 0.3 g Phenacetine 0.1 g Citric acid 0.3 g Oxyethyleneated nonylphenol containing 9 mols of ethylene oxide 1 g H202, q.s.p. 8 volumes strength Dyestuff q.s.

Perfume q.s.

Water q.s.p. 100 g The reducing composition is applied to the hair wound on curlers and is left to act for 5 to 1 5 minutes. The hair is rinsed carefully and the neutraliser is then applied and left to act for 10 minutes.

The hair is rinsed and finally set in waves.

The hair is easy to comb out when wet. It has a silky feel. After drying, the hair is glossy and springy, has a silky feel and is easy to comb out. The hair does not develop any static electricity.

Comparable results were obtained on replacing polymer P1 by an equivalent amount of a mixture of polymers P6 and P7, or P9and P11, or P10 and P,3.

It is recalled that a solution of H202 of 8 volumes strength is a solution which is capable of liberating 8 times its volume of oxygen by decomposition in accordance with the reaction H202 e H20 + 1/2 9r PREPARATIONS By following an analogous procedure to that described in the above preparation examples, the following polymers, the formulae of which have been given above, were prepared.

Polymer P6: chlorine content: 98% of theory Polymer P7: chlorine content: 98% of theory Polymer P8: chlorine content: 91% of theory Moreover, by reacting mixtures of dihalides and diamines (equimolecular proportions of dihalides and diamines) in accordance with the same procedure, and by using the following dihalides and' diamines:

D3 : ClCH2-CHpdH2-CH2Cl D4: Cl(CH2)6Cl the following copolymers were prepared:

Chlorine content Polymer Quaternary polymers prepared from (mols) (% of theory) P9 (3/4)D1+(1/4)D2+(3/4)D3+(1/4)D4 99% P, (1/2)D1+(1/2)D2+(1/2)D+(1/2)D4 100% P11 (114)Dl+(3/4)D2+(1/4)D3+(3/4)D4 95% P,2 (3/4)D & (1+4)D2+(1)Da 100% Pl, (1/2)D,+(1/2)D2+(1)D3 100% P14 (1/4)D1+(3I4)D2+(1)D3 99%

Claims (26)

1. A composition suitable for application to the hair which comprises at least one polymer containing units of the formula:

in which each R1, each R2 each R3 and each R4, which are identical or different, represents a saturated or unsaturated, substituted or unsubstituted, aliphatic radical, a saturated or unsaturated, substituted or unsubstituted, alicyclic radical, or a substituted or unsubstituted arylaliphatic radicai, or R, and R2and/or R3 and R41, form, together with the nitrogen atom to which they are attached, a ring which can contain a second hetero-atom other than nitrogen.A represents a linear or branched, substituted or unsubstituted, alkylene or alkenylene group optionally containing, in the chain or as a substituent or both, one or more hetero-atoms or one or more arylene groups, Xo is an anion of an inorganic or organic acid and m is 2 or 3, and also one or more ingredients such that the composition is in the form of a 1 dyeing or bleaching carrier, a permanent-waving composition or a pre-perm or after-perm lotion.

2. A composition according to claim 1, in which R1, R2, R3 and R4 which are identical or different, represent an alkyl or hydroxyalkyl group containing from 1 to 20 carbon atoms, a (cycloalkyl)-alkyl radical having less than 20 carbon atoms, a 5 or 6-membered cycloalkyl radical, or a phenylalkyl radical, in which the alkyl group contains from 1 to 3 carbon atoms, or Ri and R2 and/or R3 and R4 together represent a polymethylene radical having from 2 to 6 carbon atoms, A represents a linear or branched alkylene or alkenylene group which is optionally substituted by one or more -OH or =0 groups, and/or is optionally interrupted by one or more oxygen, sulphur or nitrogen hetero-atoms and/or by one or more phenylene groups, and has from 2 to 18 carbon atoms, and Xe is a halide ion or an anion derived from phosphoric acid or sulphuric acid, or an organic sulphonic acid or an organic carboxylic acid.

3. A composition according to claim 2 in which A represents an ortho-, meta- or para-xylylene radical or a radical of the formula: (CH2)n--S(CH2)n--CH2-CO-CH2--, (CH2) nO( CH 2) --CH,,-C,H,C,H,CHH,-, --(CH2)n--S--S--(CH2)n-- -(CH2) SS(CH2), --CH2--C6H4--O--C8H4--CH2--,--(CH2)n--SO--(CH2)n--CH2--C6H4--SO2--C6H4--CH2--, (CH2)n--SO2(CH2)n--,--C6H4--CH2--C6H4--,--CH2--CHOH--CH2--, -C6H4--C(CH3)2--C6H4--,--C6H4--CO-C6H4--,--C6H4--CHOH--C6H4,-alkylene-N(R5)-alkylene or -arylene-N(R5)-arylene, n being 2 or 3, R6 representing alkyl, cycloalkyl or aralkyl having up to 20 carbon atoms, and the alkylene and arylene having up to 20 carbon atoms.

4. A composition according to any one of claims 1 to 3, in which A represents: (CH2)nO(CH2)n, n being 2 or3;-CH2-C6H4CH2-; -CH 2-CKOH-CH2-;-(CH2)-, p being an integer from 2 to 18, or --(CH,)n1--CH=CH--(CH2)n2--, n1 and n2 being 0 or an integer, such that the sum of n1 and n2 is at most 16. 2

5. A composition according to any one of the preceding claims, in which the polymer has a molecular weight of 1,500 to 50,000.

6. A composition according to any one of the preceding claims, which is in the form of a dyeing or bleaching carrier cream.

7. A composition according to claim 6 which contains a soap of a C12-C20 fatty acid, or a mixture of a natural or synthetic C12-C20 alcohol and an anionic or non-ionic emulsifier, and optionally a fatty amide, sequestering agent, thickener and/or perfume.

8. A composition according to any one of claims 1 to 5, which is in the form of a gellable liquid which is capable of giving a dyeing or bleaching carrier gel on adding hydrogen peroxide.

9. A composition according to claim 8, which contains an oxyethyleneated or polyglycerolated non-ionic compound, or a soap of a liquid fatty acid, and a solvent and, optionally, a fatty amide, natural or synthetic fatty alcohol, alkali metal alkyl-sulphate, preservative, sequestering agent and/or perfume.

1 0. A composition according to any one of claims 6 to 9, which contains from 0.5 to 10% by weight of the quaternised polymer.

1 A composition according to claim 10 which contains from 1 to 3% by weight of the quaternised polymer.

12. A composition suitable for dyeing hair, which comprises a dyeing carrier as claimed in any one of claims 6 to 11 and a direct or oxidative dyestuff.

1 3. A composition suitable for dyeing or bleaching hair, which is in the form of a two part pack, the first part comprising a carrier as claimed in any one of claims 6 to 11 and, optionally, an oxidative dyestuff, and the second part comprising an oxidising agent.

14. Process for dyeing or bleaching hair, which comprises applying thereto a dyeing or bleaching carrier, as claimed in any one of claims 6 to 11, and, if the carrier does not contain one, a dyestuff or an oxidising agent allowing the composition to act on the hair, and then rinsing the hair.

1 5. A composition according to any one of claims 1 to 5, which is in the form of a permanentwaving composition.

16. A composition according to claim 15, which contains from 0.1 to 10% by weight of the polymer.

17. A composition according to claim 15 or 16, which contains a reducing agent and constitutes a composition for the first stage of a permanent-waving operation.

1 8. A composition according to any one of claims 1 5 to 17, which also contains at least one of a pH modifier, auxiliary reducing agent, solvent, non-ionic or cationic surface-active agent, perfume and/or dyestuff.

1 9. Process for permanently waving hair, which comprises applying thereto a reducing composition, allowing the composition to act for 5 to 20 minutes, rinsing the hair and applying an oxidising composition thereto while the hair is constrained in a deformed state, either or both of the said compositions being as claimed in claim 1 6 or 1 7.

20. Process according to claim 19 in which the reducing composition is one claimed in claim 1 7.

21. A composition according to any one of claims 1 to 5 which is in the form of a lotion to be applied before or after a permanent-waving operation.

22. Process for permanently waving hair, in which before the reducing composition on after the oxidising composition is applied, a composition as claimed in claim 21 is applied.

23. A composition according to any one of claims 1 to 13, 15 to 18 and 21 which is free from anionic polymer.

24. Process according to any one of claims 14, 19, 20 and 22 in which the said composition as claimed is free from anionic polymer.

25. A composition according to claim 1 substantially as described in any one of Examples 1 to 7.

26. Process according to claims 14 or 1 9 substantially as described in any one of Examples 1 to 7.