GB1604475A - Polyamino-polyamide polymers - Google Patents

Description

PATENT SPECIFICATION ( 1) 1 604 475

&O ( 21) Application No 24085/80 ( 22) Filed 1 March 1978 ( 62) Divided out of No1604473 ( 1 ( 31) Convention Application No 7706031 ( 32) Filed 2 March 1977 in ( 33) France (FR) ( 44) Complete Specification published 9 Dec 1981 " O ( 51) INT CL 3 C 08 G 69/48 A 61 K 7/06 C 08 G 81/00 ( 52) Index at acceptance C 3 R 22 C 22 D 1 A 2 22 DIAX 22 D 2 A 1 22 D 2 A 2 22 D 2 AX 22 M 7 22 N 1 A 22 N 1 B 22 T 2 C 12 C 13 P C 16 J L 2 A L 2 B L 2 X C 3 Y B 101 B 230 E 180 F 210 F 540 ( 72) Inventors GUY VANLERBERGHE HENRI SEBAG JEAN-FRANCOIS GROLLIER and ALEXANDRE ZYSMAN ( 54) POLYAMINO-POLYAMIDE POLYMERS ( 71) We, L'OREAL, a French body corporate of 14 rue Royale Paris, 75008 France, 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:-

In our Application No 8149/78 Serial No ( 1694473) we describe and claim a 5 process for conditioning human hair which comprises applying thereto a composition comprising a polyamino-polyamide polymer prepared by crosslinking a polyamino-polyamide obtained by the polycondensation of one or more acid compounds, selected from:

(i) an organic dicarboxylic acid, (ii) an ethylenically unsaturated aliphatic 10 mono or di-carboxylic acid, (iii) an ester of an acid as defined under (i) or (ii), (iv) a mixture of two or more compounds defined under (i), (ii) or (iii) or (v) the product of reaction of a bis-primary amine or a bis-secondary diamine with (i), (ii), (iii) or (iv), with one or more polyamines selected from a bis-primary, mono or disecondary polyalkylene-polyamine up to 50 mol%/ of this polyamine optionally 15 being replaced by a bis-primary amine or bis-secondary diamine with the proviso that the maximum percentage is 20 mol % when the amine is hexamethylene diamine, the crosslinking agent being:

(I) a simple bifunctional compound which is either ( 1) a bishalogenohydrin resulting from the reaction of an epihalogenohydrin with a primary amine, a bis 20 secondary diamine, a bis-phenol or a bis-mercaptan, ( 2) a bisazetidinium compound, ( 3) a bis-halogenoacyldiamine, or ( 4) a compound represented by the general formula:

CH 3 CH 3 X (CH 2)x (Z)m N-A 1 N (CH 2)x X (F 1) { I CH 3 CH 3 n in which X denotes Cl or Br, Z denotes 25 CH-CH c/ / >'C, x is l \ CH c OH / x is 1 to 3, m is O or I, and N is O or I, such that m and N cannot simultaneously be I and when m is 1, x is 1; and A, denotes either a divalent saturated C 2, C 3, C 4 or C O hydrocarbon radical or a 2-hydroxypropylene radical; (II) an oligomer obtained by reacting a compound (a), which is a compound as defined under ( 1), ( 2), ( 3) or ( 4) above, or ( 5) an epihalogenohydrin, ( 6) a bisepoxide or ( 7) a his-unsaturated compound, with a compound (b) which is a primary amine, a bis-secondary diamine, a bis-mercaptan or a bis-phenol, the molar ratio of (b):(a) being from 0 1:1 to 0 9:1; 5 (II bis) an oligomer obtained by reacting a compound (al), which is a compound as defined under ( 1), ( 3), ( 4) or ( 6) above, with a bistertiary diamine (b), the molar ratio of (bh):(a) being from 0 1:1 to 0 9:1, and (III) the product resulting from the quaternisation of a compound (a 2), which is either ( 1 ') a bis-halogenohydrin resulting from the reaction of an 10 epihalogenohydrin with piperazine, a bis-phenol or a bis-mercaptan, ( 2) a bisazetidinium compound, ( 3) a bis-halogenoacyldiamine, ( 4) a bis-(alkyl halide) of formula (F), ( 6) a his-epoxide, ( 7) a his-unsaturated compound, ( 8) an oligomer (II) obtained by reacting a compound (a 3), which is a compound as defined under ( 1), ( 2), ( 3), ( 4), ( 6) or ( 7) above, with a compound (b 3) which is a primary amine, a bis 15 secondary diamine, a bis-mercaptan or a bis-phenol, the molar ratio of (b 3):(a 3) being from 0 1:1 to 0 9:1, ( 9) an oligomer obtained by reacting an epihalogenohydrin (compound a,) with a bifunctional compound (b 4) which is piperazine, a bis-mercaptan, a bis-phenol or a piperazine bisepoxide, the molar ratio of compound (b 4): epihalogenohydrin being from 0 1:1 to 0 9:1, and ( 10) an 20 oligomer obtained by reacting a compound (a), which is either (P') a bishalogenohydrin resulting from the reaction of an epihalogenohydrin with piperazine, a bis-phenol or a bis-mercaptan, ( 2) a bishalogenoacyldiamine, ( 3) a is-(alkyl halide) of formula (F,), or ( 4) a bis-epoxide, with a bistertiary diamine (b 5), said compound (a 2) containing tertiary amine groups which can be alkylated 25 with an alkylating agent (c) which is methyl or ethyl chloride, bromide, iodide, sulphate, mesylate or tosylate, benzyl chloride or bromide, ethylene oxide, propylene oxide and glycidol, the molar ratio (b 5):(a 5) being from 0 1:1 to 0 9:1, said polyamino-polyamide possessing the following characteristics:

( 1) it is completely soluble in water to a concentration of 10 % without gel 30 formation; ( 2) the viscosity of a 10 % aqueous solution of the polymer at 25 C is at least 3 centipoises; and ( 3) it does not possess any reactive group and, in particular, it does not have any alkylating groups and is chemically stable, together with a compatible vehicle 35 Certain of these polymers are novel and these as well as compositions containing them which are suitable for application to the hair form the subject of the present invention.

These polymers have the advantage of ensuring that the hair is in a better cosmetic condition and, in particular, of imparting more body and elasticity to dry 40 hair and of improving the hold of the hairstyle, as compared with known polyamino-polyamides.

The polymers of the present invention are as defined above, the crosslinking agent containing one or more piperazino units and being:

(I) a simple bifunctional compound which is either (I) a bishalogenohydrin 45 resulting from the reaction of an epihalogenohydrin with piperazine, ( 2) a bisazetidinium compound containing a piperazino radical, or ( 3) a bishalogenoacyldiamine containing a piperazino radical; (II) an oligomer obtained by reacting a compound (a), which is a compound as defined under ( 2) or ( 3) above, with a compound (b) which is a primary amine, a 50 bis-secondary diamine, a bis-mercaptan or a bis-phenol, or a compound (a') which is ( 5) an epihalohydrin, ( 6) a bis-epoxide or ( 7) a bis-unsaturated compound, with a compound (b') which is piperazine, the molar ratio of (b):(a) and (b') :(a') being from 0 1:1 to 0 9:1; (II bis) an oligomer obtained by reacting a compound (a 1), which is a 55 compound as defined under (I) or ( 3) above or ( 6 A) a bis-epoxide containing a piperazino radical, with a bis-tertiary diamine (b,), the molar ratio of (b):(a 1) being from 0 1:1 to 0 9: 1, and (III) the product resulting from the quaternisation of a compound (a 2), which is either (I') a bis-halogenohydrin resulting from the reaction of an 60 epihalogenohydrin with piperazine, ( 2) a bis-azetidinium compound containing a piperazino radical, ( 3) a bis-halogenoacyldiamine containing a piperazino radical, ( 7) a bis-unsaturated compound containing a piperazino radical, ( 8), an oligomer (II) obtained by reacting a compound (a 3), which is a compound as defined under ( 1), ( 2), ( 3), ( 6 A) or ( 7) above, with a compound (b 3) which is a primary amine, a bis 65 1,604,475 secondary diamine, a bis-mercaptan or a bis-phenol, the molar ratio of (b 3):(a 3) being from 0 1:1 to 0 9:1, ( 9) an oligomer obtained by reacting an epihalogenohydrin (compound a 4) with a bifunctional compound (b 4) which is piperazine or a piperazine bis-epoxide, the molar ratio of compound (b 4) :

epihalogenohydrin being from 0 1:1 to 0 9:1, and ( 10) an oligomer obtained by 5 reacting a compound (as), which is either ( 1 ') a bis-halogenohydrin resulting from the reaction of an epihalogenohydrin with a piperazine ( 2) a bishalogenoacyldiamine containing a piperazino radical, or ( 4) a bisepoxide containing a piperazino radical, with a bis-tertiary diamine (b,) the molar ratio (b 5):(a 5) being from 0 1:1 to 0 9:1, said compound (a 2) containing tertiary amine 10 groups which can be alkylated, with an alkylating agent (c) which is methyl or ethyl chloride, bromide, iodide, sulphate, mesylate or tosylate, benzyl chloride or bromide, ethylene oxide, propylene oxide and glycidol, said polyaminopolyamide possessing the following characteristics:

i 5 ( 1) it is completely soluble in water to a concentration of 10 / without gel 15 formation; ( 2) the viscosity of a 10 % aqueous solution of the polymer at 25 C is at least 3 centipoises; and ( 3) it does not possess any reactive group and, in particular, it does not have any alkylating groups and is chemically stable, together with a compatible vehicle 20 The simple bifunctional compounds of group I are described in greater detail below.

(I) The bis-halogenohydrins obtained by reacting an epihalogenohydrin, such as epichlorohydrin or epibromohydrin, with piperazine constitute very valuable crosslinking agents 25 The bis-halogenohydrins can be direct intermediates in the preparation of bisepoxides but, conversely, they can be derived from the latter by opening the oxirane ring with a hydracid such as hydrochloric acid or hydrobromic acid.

In both cases, the halogen atom can be bonded to the last or penultimate carbon atom without its position being detrimental to the reactivity of the 30 crosslinking agent or to the properties of the final product.

The following bis-halogenohydrins may be mentioned by way of examples:

X CH 2 H CH 2 N CH 2 R N = 1 to 4 OH n CR 2CR O 1 CH R 2 C 2 N 0-L X X CH 2 C Ht OH c H 2 -2 N? ot 2 C Uo H c Bz N N C Ho H C-2 X 3 Bis-azetidinium compounds are derived from N,N dialkyl 35 halogenohydroxypropylamines by cyclisation.

Thus, for example:

X CH 2 CHO-l CH 2 CHOH CH 2 C 2 CO-C 2 X 2,/'C 124 i C Hnm I 2}I-CH 2-C Hon-CR 2 X n HO CRO-CH -N I' -C 2 2 \_ 9 X X denotes Cl or Br-.

However, the cyclisation can be difficult to carry out for certain sterically 40 hindered amines.

As the reactivity of azetidinium groups is not very different from that of epihalogenohydrin groups, it will be possible, for the purposes of the invention, to use those compounds which are derived from bis-halogenohydrins in which the halogenohydrin units are bonded to the remainder of the molecule by tertiary 45 nitrogen groups, and which contain two azetidinium groups or one azetidinium group and one halogenohydrin group.

The bis-halogenoacyldiamines which can be used as crosslinking agents can be represented by the following formula:

1.604 475 X (CH 2) CON NCO (CH 2)n,,,X X=CI or Br, N"' denotes a number from 1 to 10.

Bis-chloroacetyl-piperazine or bis-bromoundecanoyl-piperazine are particularly valuable for the purposes of the invention.

Oligomers which can be used within the spirit of the invention are statistical 5 mixtures of compounds obtained by reacting a compound (a), described in groups I and II, or a compound (a J), described in group II bis, or a compound (a 3), (a 4) or (as), described in group III, with a bifunctional compound (b), (b,), (b 3), (b 4) or (b 5) respectively, which is reactive towards the compounds (a), (a), (a 3), (a 4) or (a), that is to say, in general terms, primary amines, bis-secondary diamines such as 10 piperazine, bis-tertiary diamines such as N,N,N',N' tetramethyl ethylen-, -propylene-, -butylene or -hexamethylene-diamine, bis-mercaptans such as ethane 1,2 dithiol, or bis-phenols such as "Bis-phenol A" or 2,2 ' ( 4,4 ' dihydroxydiphenyl) propane.

1 5 The molar ratios of (b), (b 1), (b 3), (b 4) and (b 5), relative to (a), (a,), (a 3), (a 4) and 15 (as) respectively, are from 0 1:1 to 0 9:1.

The oligomerisation reactions are generally carried out at temperatures of 0 to C, and preferably from O to 50 C, in water or in a solvent such as isopropanol, t-butanol, acetone, benzene, toluene, dimethylformamide or chloroform.

The quaternisation reactions, which lead to a quaternisation product as 20 described above under III, are suitably carried out at 0 to 90 C in water or in a solvent such as methanol, ethanol, isopropanol, t-butanol, alkoxyethanols, acetone, benzene, toluene, dimethylformamide or chloroform.

The acids which can be used in the preparation of the polyaminopolyamides (A) areagenerally chosen from amongst saturated organic dicarboxylic acids having 25 from 6 to 10 carbon atoms, for example adipic, 2,2,4 trimethyl and 2,4,4 trimethyl adipic and terephthalic acids, and aliphatic mono and dicarboxylic acids containing an ethylenic double bond, for example acrylic, methacrylic and itaconic acids.

The preferred acids include adipic acid and the compounds resulting from the 30 addition of an alkylenediamine to unsaturated acids such as acrylic, methacrylic and itaconic acids.

Adipic acid is particularly preferred.

Esters of the abovementioned acids can also be used It is also possible to use mixtures of two or more carboxylic acids and of their esters 35 Polyamines which can be used in the preparation of the polyaminopolyamides (A) are chosen from amongst bis-primary, mono or di-secondary polyalkylenepolyamines, for example diethylenetriamine, dipropylenetriamine and triethylenetetramine and their mixtures.

Polycondensation is carried out by known processes, by mixing the reactants 40 and then heating them at say 80 to 250 C, and preferably 100 to 180 C, for I to 8 hours depending on the reactants used After heating under total reflux for + hour to I hour, the water or the alcohol formed during the polycondensation is removed, first at ordinary pressure and then under reduced pressure.

The reactions should take place under a stream of nitrogen in order to avoid 45 excessive colorations and to facilitate the removal of the volatile substances.

When carrying out the reaction, the amount of dicarboxylic acid and amines used is preferably such that they are in equimolar proportions.

According to a preferred method of preparation, the polycondensation of the polyalkylene-polyamine, which is preferably chosen from amongst 50 diethylenetriamine, triethylene-tetramine, dipropylenetriamine and their mixtures, is carried out either (i) with a dicarboxylic acid, preferably adipic acid or its dimethyl ester, or (ii) with the intermediate product resulting from the addition of one molecule of ethylenediamine to two molecules of the methyl ester of an ethylenically unsaturated acid, such as methyl acrylate, methacrylate or itaconate 55 The reactions involving the addition of ethylenediamine to unsaturated esters are carried out by mixing the reactants at say 5 to 80 C, and the polycondensation reactions are carried out by heating under reflux for 30 to 60 minutes, followed by removal of methyl alcohol at 120-150 C or of water at 140-175 C, first at ordinary pressure and then under a partial vacuum of 15 mm of mercury 60 The polyamino-polyamides (A) thus obtained have a viscosity, as a 10 strength solution in water and at 25 C, of less than 3 centipoises.

1,604,475 The structure of the preferred polyamino-polyamides (A) can be represented by the general formula (I) -l-OC-R-CO-Z-l (I) in which R represents a divalent radical which is derived from the acid used or from the product resulting from the addition of the addition of the acid to the bis 5 primary or bis-secondary amine.

Amongst the preferred meanings of R, the following may be mentioned:

\ = /, -(CH 2)4 -CH 2 CH 2 Nz H CH 2 CH 2 ' H CH 2 C -, o 10 CH CH 2 -H CH 2Ca 2 OC 1 c 2 _ a CH 3 CH 3 N C C 2 N C 12 -2 H O % 0 These radicals are derived respectively from terephthalic acid, from adipic acid and from the product resulting from the addition of ethylenediamine to acrylic, methacrylic and itaconic acids or their esters.

I 5 Z represents: 15 1) in proportions of 60 to 100 mol %, the radical -NH-l(CH 2)x-NH I (II) in which x= 2 and n= 2 or 3, or x= 3 and n= 2, this radical being derived from diethylenetriamine, triethylene-tetramine or dipropylenetriamine; 2) in proportions of O to 40 mol %, the above radical (II), in which x= 2 and 20 n=l, and which is derived from ethylenediamine, or the radical -N Nderived from piperazine; and 3) in proportions of O to 20 mol %, the radical -NH (CH 2),-NH-, derived from hexamethylenediamine 25 The polyamino-polyamides thus obtained are then cross-linked by adding a crosslinking agent chosen from amongst those described above.

The crosslinking reactions are generally carried out at 20 C to 90 C, starting from 20 to 30 % strength aqueous solutions of polyamino-polyamide, to which the crosslinking agent is added in very small portions until a large increase in the 30 viscosity is obtained, but without however reaching the stage of a gel which would no longer dissolve in water The concentration is then rapidly adjusted to 10 % by adding water, and the reaction mixture is cooled if necessary.

According to a preferred characteristic of the invention, from 0 025 to 0 35 mol of crosslinking agent per amine group of the polyamino-polyamide is employed 35 for crosslinking the polyamino-polyamide polymers A valuable category of these crosslinked polymers is obtained by using from 0 025 to about 0 2 mol of crosslinking agent per amine group of the polyamino-polyamide A further advantageous category of crosslinked polymers is obtained by using from 0 025 to about 0 1 mol of crosslinking agent per amine group of the polyaminopolyamide 40 The proportions of crosslinking agent to be used, which vary depending on the nature of the polyamino-polyamide and of the crosslinking agent, can be determined easily by adding the desired crosslinking agent to an aqueous solution 1.604475 of the polyamino-polyamide until the viscosity of a 10 %/ strength solution, at 250 C, is between 3 centipoises and the gel state, whilst retaining perfect solubility in water.

The crosslinked polymers according to the present invention can be stored satisfactorily and are compatible with anionic surface-active agents, whilst ensuring 5 that wet hair can be combed out easily This compatibility with anionic surfaceactive agents can be further improved by alkylating the secondary amine groups of the crosslinked polyamino-polyamides Alkylation increases the solubility in water of the crosslinked polyaminoamides, in the presence of anionic surfaceactive agents 10 The following can be used as the alkylating agent:

I) an epoxide, for example glycidol, ethylene oxide or propylene oxide; 2) a compound containing an ethylenic double bond, for example acrylamide or acrylic acid; 3) chloroacetic acid; or 15 4) an alkane sultone, for example propane sultone or butane sultone.

The alkylation of the crosslinked polyamino-amides is suitably carried out in aqueous solution, at a concentration of 10 to 30 % and at a temperature of between and 951 C.

The crosslinked polymers according to the invention can be used in various 20 cosmetic compositions for the hair, for the treatment of normal hair and more particularly of sensitised hair They can for example be used at concentrations of 0.1 to 5 %, preferably from 0 2 to 2 5 % and advantageously from 0 3 to 1 3 %, in cosmetic compositions for the hair and more particularly in shampoo compositions such as an anionic, cationic, non-ionic, amphoteric or zwitterionic shampoo, 25 colouring shampoo compositions, dyeing compositions, styling, gel compositions, styling lotion compositions, "brushing" lotion compositions, wavesetting lotion compositions, rinsed lotion (rinse) compositions and non-rinsed reinforcing wavesetting lotion compositions, in restructuring compositions and in more specific cosmetic compositions such as anti-dandruff, anti-seborrhoea and permanent 30 waving compositions.

The present invention therefore also provides a cosmetic composition for the hair which contains at least one water-soluble crosslinked polymer of the present invention which has been crosslinked to the extent of 0 025 to 0 35 mol, together with a diluent or carrier 35 The cosmetic composition is characterised in that the crosslinking is effected by means of 0 025 to 0 35, or 0 025 to about 0 2, or 0 025 to about 0 1 mol of crosslinking agent per amine group of the polyamino-amide.

The cosmetic compositions for the hair, which contain a crosslinked polymer according to the invention, generally have a p H of 2 to 11, and preferably 3 to 8 40 Those cosmetic compositions for the hair, according to the invention, which are to be applied to sensitised hair, advantageously contain an electrolyte The presence of the electrolyte in the composition reduces or eliminates the tendency of sensitised hair to retain the polymers for a long time Water-soluble alkali metal or alkaline earth metal salts of inorganic or organic acids, preferably the chlorides 45 and acetates of sodium, potassium, ammonium and calcium, are used as electrolytes The amount of electrolyte is not critical It is preferably from 0 01 to %, and advantageously from 0 4 to 3 %, of the total weight of the composition The ratio of electrolyte:polymer is suitably O I to 1 5:1.

The cosmetic compositions for the hair can be coloured and generally contain 50 from 0 001 to 0 5 % of colorants, relative to the total weight of the composition In addition, they usually contain a perfume in a proportion of 0 1 to 0 5 % of the total weight of the composition.

In the compositions of the present invention, the crosslinked polyaminoamides are usually present at the rate of 0 1 to 5 %, and preferably 0 1 to 3 %, by 55 weight, relative to the total weight of the composition.

The compositions for the hair which form the subject of the present application can be in the form of for example, aqueous or aqueousalcoholic solutions (the alcohol being a lower alkanol such as ethanol or isopropanol), or in the form of creams, gels, dispersions or emulsions 60 In addition to the crosslinked polyamino-polyamides, the cosmetic compositions generally comprise various adjuvants which are usually employed in cosmetic compositions for the hair The adjuvants which are generally present in these cosmetic compositions are, for example, perfumes, colorants, preservatives, sequestering agents, thickeners, emulsifiers, anionic, cationic, amphoteric, 65 1,604,475 zwitterionic or non-ionic surface-active agents, synergistic agents, softening agents and cosmetic polymers or resins, in particular non-ionic or cationic polymers or resins.

The cosmetic compositions for the hair, according to the invention, constitute, in particular, treatment creams to be applied before or after colouring or 5 bleaching, before or after shampooing, or before or after permanent waving, colouring products shampoos, rinsed lotions to be applied before or after shampooing, wavesetting lotions, brushing lotions and structuring lotions.

When the compositions of the invention constitute treatment creams to be applied before or after colouring or bleaching, before or after shampooing, or 10 before or after permanent waving, the formulation of these carriers is based on soaps or fatty alcohols, in the presence of emulsifiers They can additionally contain fatty amides, glycerol, polymers, perfumes and colorants.

The p H of these creams is generally 3 to 9, and preferably 5 to 9.

is The soaps can be formed from natural or synthetic C,2-C 18 fatty acids (such 15 as lauric acid, myristic acid, palmitic acid, oleic acid, ricinoleic acid, stearic acid and isostearic acid), at concentrations of, say, 10 to 30 % , and from alalng agents, (such as sodium hydroxide, potassium hydroxide, ammonia, monoethanolamine, diethanolamine and triethanolamine).

The fatty amides which can be used include the following compounds in 20 particular: the mono or di-ethanolamides of acids derived from copra, of lauric acid or of oleic acid, at concentrations of up to, say, 10 %.

Fatty alcohols which can be used include, in particular, oleyl, tetradecyl, cetyl, stearyl and isostearyl alcohols, at concentrations of up to, say, 10 %/.

The creams can also be formulated from natural or synthetic C,2,-C alcohols 25 mixed with emulsifiers Amongst the fatty alcohols, there may be mentioned in particular: the alcohol derived from copra fatty acids, tetradecyl alcohol, cetyl alcohol, stearyl alcohol and hydroxystearyl alcohol, at concentrations of between 5 and 25 %.

The emulsifiers can belong to the following classes: 30 Non-ionic surface-active agents such as oxyethyleneated or polyglycerolated fatty alcohols, such as, for example, polyoxyethyleneated oleyl alcohol containing mols of ethylene oxide, oxyethyleneated cetyl alcohol containing 6 to 10 mols of ethylene oxide, oxyethyleneated cetyl/stearyl alcohol containing 10 mols of ethylene oxide, stearyl alcohol containing 10-15 or 20 mols of ethylene oxide, 35 polyglycerolated oleyl alcohol containing 4 mols of glycerol, and polyoxyethyleneated synthetic C,-C 15 fatty alcohols containing 5 or 10 mols of ethylene oxide These "non-ionics" are suitably present at the rate of 5 to 25 % by weight.

Anionic surface-active agents such as alkyl-sulphates which may or may not be 40 oxyethyleneated, such as sodium lauryl-sulphate, ammonium lauryl-sulphate, sodium cetyl-/stearyl-sulphate, triethanolamine cetyl-/stearyl-sulphate, monoethanol-amine lauryl-sulphate, oxyethyleneated sodium lauryl-ethersulphate (containing, for example, 2 2 mols of ethylene oxide) and oxyethyleneated monoethanolamine lauryl-ether-sulphate (containing, for example, 2 2 mols of 45 ethylene oxide) These constituents are generally present at concentrations of 3 to % by weight.

Oleyl diethanolamide, copra mono or di-ethanolamide and stearyl monoethanolamine lauryl-ether-sulphate (containing for example, 2 2 mols of area used at concentrations of up to, say, 10 % 50 When the compositions of the invention constitute colouring creams, they comprise, in addition to the crosslinked polyamino-amide, various ingredients which make it possible to form creams as defined above, to which an alkalising agent and colorants are added.

The p H of these compositions is generally from 9 to 11 and it can be adjusted 55 by adding a suitable alkalising agent to the dyeing carrier, for example by adding ammonia, monoethanolamine, diethanolamine or triethanolamine.

The colorants are typically oxidation dyestuffs, to which direct dyestuffs, such as azo dyestuffs, anthraquinone dyestuffs, nitro-derivatives of the benzene series, indamines, indoanilines, indophenols, or other oxidation dyestuffs such as the 60 leuco-derivatives of these compounds, can be added.

When the compositions of-the invention constitute shampoos, they comprise, in addition to the crosslinked polyamino-amide polymer, at least one anionic, cationic, non-ionic or amphoteric detergent.

1.604 475 Amongst the anionic surface-active agents, the following compounds, as well as their mixtures, may be mentioned in particular:

the alkali metal salts, magnesium salts, ammonium salts, amine salts or aminoalcohol salts of the following compounds:

alkyl-sulphates, alkyl-ether-sulphates, of which the alkyl has a linear C 12 to C,8 5 chain, oxyethyleneated alkylamide-sulphates and ether-sulphates having linear C 12 to C, chains, alkylaryl-polyether-sulphates and monoglyceride-sulphates, alkylsulphonates, of which the alkyl has a linear C,2 to C,8 chain, alkylamidesulphonates, alkylarylsulphonates, and alpha-olefin-sulphonates having linear C 12 to C, chains, 10 alkylsulphosuccinates, alkyl-ether-sulphosuccinates, and alkylamidesulphosuccinates, of which the alkyl has a linear C,2-C, chain, alkylsulphosuccinamates, of which the alkyl has a linear C 12 to C,8 chain, alkylsulphoacetates, of which the alkyl has a C,2 to C 1, chain, alkyl-phosphates, and alkyl-ether-phosphates, of which the alkyl has a C, 2 to 15 C 18 chain, alkylsarcosinates, alkylpolypeptidates, alkylamido-polypeptidates, alkylisethionates, and alkyl-taurates, of which the alkyl has a C 12 to C 18 chain, and fatty acids such as oleic acid, ricinoleic acid, palmitic-acid, stearic acid, acids of copra oil or of hydrogenated copra oil, carboxylic acids, and carboxylic acids of 20 polyglycol ethers of the formulaAlk-(OCH 2-CH 2), OCH 2 CO 2 H, in which Alk is a C 12 to C 1, linear chain and N is an integer from 5 to 15.

Amongst the cationic surface-active agents which can be used by themselves or in mixtures, there may be mentioned in particular: fatty amine salts such as 25 alkylamine acetates, quaternary ammonium salts such as the chlorides and bromides of alkyldimethylbenzylammonium, alkyltrimethylammonium, alkylmethylhydroxyethylammonium and dimethyldistearylammonium, and alkylamidoethyltrimethylammonium methosulphates, alkylpyridinium salts and imidazoline derivatives 30 Amine oxides having a cationic character, such as alkyl-dimethylamine oxide or alkylaminoethyldimethylamine oxide, may also be mentioned.

Amongst the non-ionic surface-active agents which can optionally be used in mixtures with the abovementioned anionic surface-active agents, there may be mentioned: products resulting from the condensation of a monoalcohol, an a-diol, 35 an alkylphenol or an amide with glycidol, for example compounds of the formula R-CHOH-CH 2 O (CH 2-CHOH-CH 2-O-) H, in which R denotes an aliphatic, cycloaliphatic or arylaliphatic radical having from 7 to 21 carbon atoms, and their mixtures, it being possible for the aliphatic chains to contain ether, thioether and hydroxymethylene groups, and in which 1 <n< 10, and 40 compounds of the formula ROlC 2 H 3 O(CH 2 OH)l,H, in which R denotes an alkyl, alkenyl or alkylaryl radical having from 8 to 22 carbon atoms and N denotes a number between I and 10, polyoxy-ethyleneated or polyglycerolated alcohols, alkylphenols or fatty acids having a linear C, to C 1, fatty chain and most frequently containing from 2 to 15 mols of ethylene oxide, for example polyoxyethyleneated 45 lauryl alcohol containing 12 mols of ethylene oxide, ethylene oxide/propylene oxide copolymers, condensates of ethylene oxide and of propylene oxide with fatty alcohols, polyoxyethylenated fatty amides, polyoxyethyleneated fatty amines, ethanolamides, glycol fatty acid esters, sorbitol fatty acid esters and sucrose fatty acid esters 50 Amongst the amphoteric surface-active agents which can be used, there may be mentioned in particular: alkylamino-mono and di-propionates, betaines such as N-alkylbetaines, N alkyl sulphobetaines and N-alkylamidobetaines, and cycloimidinium compounds (alkylimidazolines).

All these detergents, as well as numerous other detergents which can be used 55 in the shampoos according to the present invention, are well known and are described in the literature.

The compositions in the form of shampoos can also contain variousadjuvants such as, for example, perfumes, colorants, preservatives, thickeners, foam stabilisers, softening agents and cosmetic resins 60 1.604 475 Amongst the foam stabilisers, there may be mentioned fatty amides and, in particular, copra mono or di-ethanolamides and lauryl mono or diethanolamides.

In these shampoos, the concentration of detergent is generally from 3 to 50 %, and preferably from 3 to 20 %, by weight, relative to the total weight of the composition, and the p H is generally from 3 to 9 5 When the compositions of the invention constitute lotions, they can be hairstyling lotions, shaping lotions (called "brushing lotions"), non-rinsed reinforcing wavesetting lotions or rinsed lotions (called "rinses"), for example.

The term shaping lotion or "brushing lotion" is to be understood as meaning a lotion which is applied after the shampoo and which assists the shaping of the head 10 of hair, this shaping process being carried out on wet hair, using a brush, at the same time as the hair is dried using a hand-held drier.

The term non-rinsed reinforcing wavesetting lotion is to be understood as meaning a lotion which is applied after shampooing and before wavesetting; this i lotion, which is not removed by rinsing, facilitates the subsequent wavesetting 15 process and lengthens the time for which the hair holds its set.

These lotions comprise, in aqueous, alcoholic or aqueous-alcoholic solution, at least one crosslinked polyamino-amide as defined above They can additionally contain: film-forming polymers such as polyvinylpyrrolidone, polyvinylpyrrolidone/vinyl acetate copolymers, and copolymers resulting from the 20 copolymerisation of vinyl acetate with a vinyl alkyl ether.

Amongst the preferred resins, there may be mentioned polyvinylpyrrolidone having a molecular weight of 10,000 to 70,000, polyvinylpyrrohlidone (PVP) /vinyl acetate(VA) copolymers having a molecular weight of 30,000 to 200,000, the ratio of PVP:VA being between 30:70 and 70:30, and methyl methacrylate ( 15 25 %)/stearyl methacrylate ( 18-28 %)/dimethylaminoethyl methacrylate ( 5262 %) terpolymers which may or may not be quaternised by methyl sulphate, quaternary polyvinylpyrrolidone copolymers such as, for example, the polymer having a molecular weight of the order of 1,000,000 and sold under the trademark "Gafquat 755 " by GAF Corporation, and the polymer having a 30 molecular weight of the order of 100,000 and sold under the trademark "Gafquat 734 " by GAF Corporation, cationic graft copolymers resulting from the copolymerisation of 3 to 95 % by weight of N vinyl pyrrolidone, 3 to 95 by weight of dimethylaminoethyl methacrylate and 2 to 50 % by weight of polyethyfene glycol, such as those described in French Patent No 76/15,948 of the Applicant 35 Company, cationic polymers resulting from the condensation of piperazine or of its derivatives (I) with bifunctional compounds such as alkyl or alkylaryl dihalides, bisepoxides, epihalogenohydrins or bis-unsaturated derivatives ( 2) with a primary amine, the two hydrogen atoms of which can be substituted and which behaves as a bifunctional compound, or ( 3) both with an epihalogenohydrin and with a 40 hydroxylated amine such as diglycolamine or 2 amino 2 methylpropane 1,3 diol, or with an aminoacid such as glycocoll, and quaternised celluloses such as "JR 400 " sold by Messrs Union Carbide.

In these lotions, the concentration of polymer is generally from 0 1 to 5 %, and preferably from 0 1 to 3 %, and the p H is generally from 3 to 9 45 The term rinsed lotion is to be understood as meaning a lotion which is applied before or after colouring or bleaching, before or after shampooing or between the two stages of shampooing, or before or after permanent waving, in order to obtain a hair conditioning effect, and which is rinsed out after remaining on the hair for a period of time 50 These compositions can be aqueous or aqueous-alcoholic solutions which may or may not comprise surface-active agents, or they can be emulsions or gels.

These compositions can be pressurised in the form of an aerosol Surfaceactive agents which can be used in the rinsed lotions are principally nonionic or cationic surface-active agents such as those described in the composition of the 55 shampoos, and more particularly: products resulting from the condensation of a monoalcohol, an alpha-diol, an alkylphenol or an amide with glycidol, for example compounds of the formula R-CHOH-CH 2-O (CH 2-CHOH-CH 2 O-)n-H, in which R denotes an aliphatic, cycloaliphatic or arylaliphatic radical having from 60 7 to 21 carbon atoms, and their mixtures, it being possible for the aliphatic chains to contain ether, thioether and hydroxymethylene groups, and in which lt<n 10, and compounds of the formula ROlC 2 H 3 O(CHOH)-l,-H, in which R denotes an 1.604 475 alkyl, alkenyl or alkylaryl radical having from 8 to 22 carbon atoms and N is between I and 10, and polyoxyethyleneated or polyglycerolated alcohols, alkylphenols or fatty acids having a linear C, to C 18 fatty chain and most frequently containing from 2 to 15 mols of ethylene oxide.

The concentration of surface-active agents in the rinsed lotions can generally 5 vary up to 7 %.

Anionic or amphoteric surface-active agents can also be added.

When the compositions are in the form of emulsions, they can be non-ionic or anionic The non-ionic emulsions comprise a mixture of oils and/or of waxes, fatty alcohols, and polyoxyethyleneated fatty alcohols such as polyoxyethyleneated 10 stearyl or cetyl/stearyl alcohols, for example, containing 10 mols of ethylene oxide.

Cationics such as, for example, those defined above can be added to these compositions.

The anionic emulsions are formed from soaps Thus, there may be mentioned the emulsion comprising self-emulsifying glycerol stearate sold under the 15 tradename IMWITOR 960 K by Messrs DYNAMIT NOBEL, and the emulsions comprising a combination of glycerol monostearate with citric acid esters, with fatty alcohols and lipopeptides or with alkali metal stearates, sold respectively under the tradenames LAMEFORM ZEM, PLM and NSM by Messrs GRUNAU.

When the compositions are in the form of gels, they contain thickeners which 20 may or may not be in the presence of solvents.

The thickeners can be sodium alginate, gum arabic, cellulose derivatives such as methylcellulose, hydroxymethyl-cellulose, hydroxyethylcellulose, hydroxypropylcellulose and carboxymethylcellulose, or carboxylic polymers such as the "Carbopols" (Registered Trade Mark) It is possible to obtain a thickener for 25 the lotions by mixing polyethylene glycols with polyethylene glycol stearates or distearates, or by mixing phosphoric esters with amines.

The concentration of thickener is generally from 0 5 to 30 %, and preferably from 0 5 to 15 % by weight.

The p H of the rinsed lotions generally varies from 2 to 9 5 30 When the compositions of the invention constitute restructuring lotions, they contain products which strengthen the keratin chain of hair.

Methylol-type derivatives, such as those described in French Patents Nos.

1,527,085 and 1,519,979, belong to this class of products.

The present invention is further illustrated by the following examples 35 Preparation Examples EXAMPLE A

Polycondensation of adipic acid with diethylenetriamine in equimolar amounts.

The structure of the polymer obtained can be characterised by the following 40 unit:

-l-OC-(CH 2), CONH (CH 2-CH 2-NH)2,-I876 g ( 6 mols) of adipic acid are added, whilst stirring and in a nitrogen atmosphere, to 619 g ( 6 mols) of diethylenetriamine, in the course of 15 minutes.

The reaction mixture is then heated to 145-150 C, at which temperature 45 condensation of water is observed Refluxing is maintained for 45 minutes and the water is then removed by distillation at ordinary pressure for 2 hours and then under reduced pressure ( 15 mm Hg) for 1 hour The heating temperature gradually increases to 170 C.

The product thus obtained is cast whilst hot After cooling, it is in the form of a 50 hard and brittle resin The resin is a transparent yellow-green colour and dissolves completely in water.

EXAMPLE Ia

Preparation of a bis-unsaturated oligomeric crosslinking agent which is obtained from piperazine bis-acrylamide and piperazine in the molar proportions 55 of 3/2 and which has the formula:

I,,-KH{ 20 / CH N-717 H -CH -CH -C N -OCH=CIS 2 -OC 2 CH 2 N N 22 -2 O 1,604,475 223 g of an aqueous solution containing 56 8 g ( 066 mol) of piperazine are added, in the course of one hour and at between 10 and 15 C, to 380 g of an aqueous solution containing 194 g of bisacrylamide ( 1 I mol) The reaction medium is then left for 24 hours at ambient temperature The solution becomes turbid and thickens It is clarified by heating and is then run dropwise into 5 litres of acetone 5 The crosslinking agent precipitates After filtration and drying, a white solid is collected, which has a solids content of 80 %.

EXAMPLE lb

Crosslinking, using the crosslinking agent prepared in Example Ia, of the I O polyamino-amide polymer obtained by condensing adipic acid with 10 diethylenetriamine.

g of the crosslinking agent prepared above are added, at ambient temperature, to 370 g of an aqueous solution containing 11 lg ( 0 649 equivalent of amine) of the polyamino-amide prepared according to Example A, and the I 5 temperature of the reaction medium is then brought to 90 C After 30 minutes, the 15 medium gels The solids content of the solution is rapidly brought back to 10 % by adding 1,050 g of water.

A clear yellow-green solution is obtained, which has a viscosity, measured at C, of 58 centipoises.

EXAMPLE Ha 20

Bis-halogenohydrin oligomeric crosslinking agent which is prepared from epichlorohydrin and piperazine in the molar proportions of 5/4 and which has the formula:

C 1 CH 2 CH OH CH 2 l NX CH 2 CH OH C 1 12 N = 4 92.5 g ( 1 mol) of epichlorohydrin are added, in the course of one hour and without exceeding 20 C, to 541 g of an aqueous solution containing 69 4 g ( 0 806 mol) of piperazine The reaction medium is stirred for a further one hour at 20 C and 60 g ( 0 6 mol) of a 40 % strength sodium hydroxide solution are then added at the same temperature in the course of one hour 30 EXAMPLE I Ib

Crosslinking, using the crosslinking agent prepared in Example Ila, of the polyamino-amide polymer obtained by condensing adipic acid with diethylenetriamine.

268 g of an aqueous solution containing 54 9 g of the crosslinking agent 35 prepared above are added, at ambient temperature, to 787 5 g of an aqueous solution containing 157 5 g ( 0 92 milliequivalent of amine) of the polyamino-amide prepared according to Example A The temperature of the reaction medium is kept at 90 C for 4 hours 50 minutes Gelling is then observed By rapidly adding 1,100 cc of water, a clear solution is obtained, which contains 9 85 % of active material and 40 has a viscosity, measured at 25 C, of 73 centipoises.

EXAMPLE II Ia

Preparation of the quaternised crosslinking agent of the formula:

CH, Cl CH 2-CHOH-CH 2 A c\ 2lf o H a CH 2 lC N 4 CH 35 04 _n 1,604,475 47.4 g ( 0 376 mol) of dimethyl sulphate are added, in the course of one hour and without exceeding 30 C, to 330 g of an aqueous solution containing 67 7 g ( 0.752 equivalent of amine) of the crosslinking agent prepared in Example I Ia The reaction medium is stirred for a further 2 hours at this temperature.

EXAMPLE II Ib 5 Crosslinking, using a crosslinking agent prepared in Example l Ila, of the polyamino-amide polymer obtained by condensing adipic acid with diethylenetriamine.

g of an aqueous solution containing 47 25 g of the crosslinking agent prepared above are added, at ambient temperature, to 327 7 g of an aqueous 10 solution containing 65 5 g ( 0 383 equivalent of amine) of the polyaminoamide prepared according to, Example A After heating at 85 C for 4 hours, the reaction medium gels.

By rapidly adding 645 g of water, a clear solution containing 10 % of active material is obtained The viscosity, measured at 25 C and at a rate of shear of 67 18 15 seconds-', is 0 47 Poise.

EXAMPLE I Va

Preparation of the bis-azetidinium crosslinking agent of the formula:

C 2 CHOH CH 2 f r OH 01 z Ci 1 43 5 g ( 0 47 mol) of epichlorohydrin are added, at between 0 and 5 C, to 50 g 20 ( 0.212 mol) of his 1,3 piperazine propan 2 ol, prepared by adding epichlorohydrin to piperazine in accordance with Example 15 of British Specification No 1,416,454 which are dissolved in 100 g of absolute alcohol The reaction medium is left for 24 hours at O C and the cross-linking agent is then precipitated from its solution with a large excess of ether A white solid having a 25 softening point of about 120 C is isolated.

EXAMPLE I Vb

Crosslinking, using a crosslinking agent prepared in Example I Va, of the polyamino-amide polymer obtained by condensing adipic acid with diethylenetriamine 30 15.4 g ( 0 036 mol) of the crosslinking agent prepared above are added, at ambient temperature, to 386 g of an aqueous solution containing 77 2 g ( 0 452 equivalent of amine) of the polyamino-amide of Example A After heating at 90 C for 2 hours 30 minutes, the medium gels By rapidly adding 525 g of water, a clear solution containing 10 % of active material is obtained The viscosity, measured at 35 C and at a rate of shear of 67 18 seconds-', is 0 7 Poise.

EXAMPLE Va

Preparation of the bis (chloroacetyl) piperazine crosslinking agent of the formula:

CCH 2 CO N/ N CO CH C 1 40 2 OM 2 4 This crosslinking agent is prepared by condensing 2 molecules of chloroacetyl chloride with one molecule of piperazine in the presence of sodium hydroxide.

EXAMPLE Vb

Crosslinking using the crosslinking agent prepared in Example Va, of the polyamino-amide polymer obtained by condensing adipic acid with 45 diethylenetriamine.

24 g ( O 1 mol) of his (chloroacetyl) piperazine are added, at ambient temperature, to 1,000 g of an aqueous solution containing 200 g ( 1 170 equivalents of amine) of the polyamino-amide of Example A, and the temperature of the reaction medium is then brought to 90 C After heating for 30 minutes, gelling of 50 the medium is observed.

1.604475 1,604,475 1,216 g of water are added rapidly and the heating is continued at 80 C for one hour A clear solution is obtained, which contains 10 % of active material and has a viscosity, measured at 25 C and at a rate of shear of 88 41 seconds-', of 0 29 Poise.

EXAMPLE V Ia

Preparation of the bis ( 1,1 bromoundecanoyl) piperazine cross-linking agent of the formula:

Br (CH 2)10 CO N N CO (CH 2)10 Br This crosslinking agent is prepared by condensing 2 molecules of bromoundecanoyl bromide with 1 molecule of piperazine in the presence of sodium hydroxide.

EXAMPLE V Il Ib Crosslinking, using the crosslinking agent prepared in Example V Ia, of the polyamino-amide polymer obtained by condensing adipic acid with diethylenetriamine.

60 g of an isopropanol solution containing 10 g ( 0 017 mol) of bis ( 1,1 bromoundecanoyl) piperazine are added, at ambient temperature, to 113 3 g of tn aqueous solution containing 56 7 g ( 0 33 equivalent of amine) of the polyaminoamide of Example A The reaction medium is heated at the reflux temperature of the solvent for 2 hours 30 minutes The isopropanol is then distilled, whilst adding water until a concentration of 10 % of active material in the aqueous solution of resin is obtained The solution is slightly opalescent and its viscosity, measured at C and at a rate of shear of 87 93 seconds-', is 0 052 Poise.

EXAMPLE V Ia

Preparation of an oligomeric crosslinking agent of the formula:

C 1 CH 2-CH OH-CH 2 N-CH 2-CH OH-CH 2 N/NC 2-C O C H 2 _ -Cl 3 from epichlorohydrin and piperazine in the molar proportions of 4/3.

246 7 g ( 2 66 mols) of epichlorohydrin are added, in the course of I hour, to 1,149 g of an aqueous solution containing 172 g ( 2 mols) of piperazine, whilst stirring the reaction medium at 20 C.

After stirring for a further one hour at 20 C, 133 g ( 1 33 mols) of a 40 % strength sodium hydroxide solution are added at the same temperature and in the space of one hour Precipitation is observed during the neutralisation 638 g of water are added and the mixture is heated for a few minutes at 50 C in order to obtain a clear solution.

EXAMPLE VI Ib

Crosslinking, using the crosslinking agent prepared in Example V Ila, of the polyamino-amide polymer obtained by condensing adipic acid with diethylenetriamine.

584 g of an aqueous solution containing 99 8 g of the crosslinking agent prepared in Example V Ila, are added to 2,000 g of an aqueous solution containing 400 g ( 2 34 equivalents of amine) of the polyamino-amide prepared according to Example A, and the reaction medium is then stirred at 90 C for 5 hours 2, 414 g of water are then added in order to obtain a clear solution, which contains 10 % of active material and has a viscosity, measured at 25 C, of 0 22 Poise.

EXAMPLE VI Ia

Preparation of an oligomeric crosslinking agent of the formula:

C 1 CH 2 N N-C-CH OH-CH 2 C 11 14 1604475 14 from epichlorohydrin and piperazine in the molar proportions of 3/2.

277 5 g ( 3 mols) of epichlorohydrin are added, in the course of 1 hour and at C, to 1,221 g of an aqueous solution containing 172 g ( 2 mols) of piperazine, whilst stirring the reaction medium at 20 C After stirring for a further one hour, 100 g ( 1 mol) of a 40 % strength solution of sodium hydroxide in water are added at a 5 temperature of 20 C.

By adding 727 5 g of water and after heating for a few minutes, a clear solution is obtained.

EXAMPLE V Il Ib Crosslinking, using the crosslinking agent prepared in Example V Illa, of the 10 polyamino-amide polymer obtaine by condensing adipic acid with diethylenetriamine.

472 g of an aqueous solution containing 83 8 g of the crosslinking agent prepared in Example VII Ia are added to 2,000 g of an aqueous solution containing 400 g ( 2 34 equivalents of amine) of the polyamino-amide prepared according to 15 Example A.

The reaction medium is stirred at 90 C and, after heating for 4 hours, gelling of the solution is observed.

The concentration of active material in the solution is rapidly brought back to 10 %/ by adding 2,326 g of water 20 A clear solution is obtained, which has a viscosity, at a rate of shear of 88 4 seconds-', of 0 64 Poise.

EXAMPLE la

The following rinse composition is prepared:

Compound of Example I Vb 0 5 g of 25 active material CH 3 CIH 3 _ N (CH 2)6 N O c 2 CH O H C-12 N l l CHH CH 0 5 g of active 3 3 material Bre Bre R-CHOH-CH 2-O-(CH 2-CHOH-CH 2 O-),-H 0 7 g R: C 9 to Co alkyl; n=mean statistical value of 3 5 30 Acid phosphate ester of oxyethyleneated oleyl alcohol, sold under the tradename "DIVALIN SO" by Messrs.

Zschimmer and Schwarz 0 4 g Water, q s p 100 cc The p H of this solution is 7-8.

This rinse composition is applied to hair which has been washed beforehand.

Hair treated in this way can be combed out very easily When dry, the hair is particularly bulky, glossy and easy to style.

EXAMPLE lb

The following rinse composition is prepared: 40 Polymer obtained by condensing adipic acid with diethylenetriamine in equimolar amounts and crosslinking with 0 11 mol of epichlorohydrin per amine group (according to Example I of British Specification No 1494915) 0 5 g of 45 active material Compound of Example V Ib 0 5 g of active so material 50 1.604 475 _ -R-CHOH-CH 2 O-(CH 2 CHOH CH 2-O-), H 0 7 g R: C 9 to C,0 alkyl; n=mean statistical value of 3 5 Acid phosphoric ester of oxyethyleneated oleyl alcohol, sold under the tradename "DIVALIN SO" by Messrs.

Zschimmer and Schwarz 0 4 g 5 Water, q s p 100 cc The p H of this solution is 7-8.

This rinse composition is applied to hair which has been washed beforehand.

Hair treated in this way can be combed out very easily When dry, the hair is particularly bulky, glossy and easy to style 10 EXAMPLE lc

An emulsion having the following composition is prepared:

Vaseline (Registered Trade Mark) oil 15 g Partially sulphated cetyl/stearyl alcohol, sold under the tradename "Lanette wax" 2 5 g 15 Polyoxyethyleneated cetyl/stearyl alcohol containing 10 mols of ethylene oxide, sold under the tradename "SIMULSOL 1951 RD" 2 5 g Compound of Example Vb 0 7 g Water, q s p 100 g 20 The p H of this solution is 9 5.

The application to the hair of this "rinse" in the form of an emulsion, followed by rinsing, makes it possible to comb the hair out more easily, imparts softness to the hair and renders the hairstyle very full of life.

EXAMPLE ld 25

An emulsion having the following composition is prepared:

Vaseline oil 15 g "Lanette wax" (partially sulphated cetylstearyl alcohol) 2 5 g Polyoxyethyleneated cetyl/stearyl alcohol containing 10 mols of ethylene oxide, sold under the tradename 30 "SIMULSOL 1951 RD" 2 5 g Compound of Example lb 0 5 g Water, q s p 100 g The p H of this solution is 9.

This "rinse" is applied to the hair, allowed to remain for a few minutes and then rinsed out The hair can be combed out more easily and has a harder feel, and the hairstyle is more full of life.

EXAMPLE 2 a

3 1 ' I N -(CH 2)6 N O CH 2-CHOH-CH 2 O 5 g of active 1126 material CH 3 CH 3 Br Br Compound of Example I Vb 0 5 g of 40 active material 1,604 A 475 1604475 Quaternary polyvinylpyrrolidone copolymer having a molecular weight of about 100,000 and marketed under the name "Gafquat 734 " by Messrs General Aniline 0 4 g of active material Perfume 0 2 g Colorants O 05 g Water, q s p 100 cc The p H is 7 3 10 When applied to hair which has been coloured, this wavesetting lotion makes the wet hair easier to comb out.

The dry hair is soft and easy to style This softness effect remains after several shampoo treatments.

s 15 EXAMPLE 2 b The following wavesetting lotion composition is prepared:

Compound of Example I Ib 0 3 g of active material Quaternary polyvinylpyrrolidone copolymer having a 20 molecular weight of about 100,000, marketed under the name "Gafquat 734 " by Messrs General Aniline 0 5 g Quaternised cellulose sold under the tradename "JR 400 " by Messrs Union Carbide 0 3 g 25 Ethyl alcohol, q s p 15 Perfume 0 1 g Water, q s p 100 cc The p H is adjusted to 8.

When applied to hair which has been washed, this wavesetting lotion makes 30 the hair easier to comb out After drying and wavesetting, the hair is soft, glossy and easy to style This effect remains after several shampoo treatments.

EXAMPLE 3 a

The following brushing lotion is prepared:

Compound of Example I Ib 0 6 g of 35 active material Ethanol, q s p 100 o Colorants 0 1 g Perfume 0 1 g 40 Water, q s p 100 g The p H of the solution is adjusted to 7.

EXAMPLE 3 b

The following brushing lotion is prepared:

Compound of Example lb 0 4 g of 45 active material Ethanol, q s p 10 Colorants 0 1 g Perfume O 1 g 50 Water, q s p 100 cc The p H of the solution is adjusted to 8.

1.604475 17 1,604,475 17 EXAMPLE 3 c

The following brushing lotion is prepared:

Compound of Example V Ib 0 5 g of active material 5 Ethanol, q s p 20 Colorants 0 2 g Perfume 0 1 g Water, q s p 100 cc The p H of the solution is adjusted to 6 10 EXAMPLE 3 d

The following brushing lotion is prepared:

Compound of Example Vb 0 6 g of active material 15 Colorants 0 05 g Perfume 0 15 g Water, q s p 100 cc The p H of the solution is adjusted to 6.

The brushing lotions to which Examples 3 a-3 d relate are applied to wet hair 20 which has been dried without heat after shampooing The head of hair is shaped, using a brush, whilst drying the hair using a hand-held drier.

It is found that the brush passes very easily through the hair and that the hairstyle holds for a long time It is also found that the hair is glossy and soft.

EXAMPLE 4 a 25 A shampoo having the following composition is prepared:

Triethanolamine C,2-C 14 alkyl sulphate 5 g R-CHOH-CH 2-O (CH 2 CHOH-CH 2 O-),-H 5 g R=Cg to C,2 alkyl; n=mean statistical value of 3 5 30 Lauryl diethanolamide 3 g Compound of Example I Vb I g Perfume 0 1 g Colorants 0 01 g _ Water, q s p 100 g 35 The p H is adjusted to 8 with triethanolamine.

This shampoo is in the form of a clear liquid It makes the wet hair easier to comb out and imparts manageability and body to the hair.

EXAMPLE 4 b

A shampoo having the following composition is prepared: 40 R-CHOH-CH 2-O (CH 2-CHOH-CH 2-O-)n-H 10 g R=C 9 to C,2 alkyl; n=mean statistical value of 3 5 Copra diethanolamide 3 g Colorant of Example Ib I g of active 45 material Water, q s p 100 g The initial p H of 8 7 is brought back to a p H of 6 with lactic acid.

This shampoo is in the form of a clear liquid and is applied to natural hair It makes the wet hair easier to comb out The dried hair is bulky and full of life 50 EXAMPLE 4 c

A shampoo having the following composition is prepared:

Ammonium lauryl-sulphate 25 g Diethanolamide of copra fatty acids 2 g Compound of Example V Ib I g of 5 active material Water, q s p 100 g The initial p H of 8 1 is brought back to a p H of 7 7 with lactic acid.

When applied to permed dyed hair, this slightly opalescent clear shampoo 10 ensures that the wet hair can be satisfactorily combed out After drying, the hair is bulky and full of life.

EXAMPLE 4 d

A shampoo having the following composition is prepared:

Alcohol (C 12-C,4) which is oxyethyleneated with 10 mols of 15ethylene oxide and is carboxymethylated, sold under the trademark AKYPO RLM 100 by Messrs.

CHEM Y 3 5 g Polyoxyethyleneated lauryl alcohol containing 12 mols of ethylene oxide 10 g 20 Compound of Example V Ib 0 5 g of active material Dimethyldiallylammonium chloride homopolymer having a molecular weight of about 100,000, sold under the 25 Trademark "Merquat 100 " by Messrs Merck 0 4 g of active material Water, q s p 100 g The spontaneous p H is 7 4 30 When applied to dyed hair, this liquid shampoo makes the wet hair easier to comb out The dried hair is manageable and glossy.

EXAMPLE 4 e

A shampoo having the following composition is prepared:

Hydroxypropylmethylcellulose 0 2 g 35 Diethanolamide of copra fatty acids 3 g Triethanolamine alkyl(C 12-C,4)-sulphate 10 g Compound of Example Vb 0 8 g of active material 40 Perfume 0 15 g Colorants 0 01 g Water, q s p 100 g The p H is adjusted to 7 8.

When applied to natural permed hair, this shampoo ensures that the wet hair is 45 easy to cornmb out and renders the dry hair full of life and bulky.

EXAMPLE 4 f

A shampoo having the following composition is prepared:

Polyoxyethyleneated lauryl alcohol containing 12 mols of ethylene oxide 7 g 50 R-CHOH-CH 2-O (CH 2-CHOH-CH 2-O-) H 7 g R=Cg to C,2 alkyl; n=mean statistical value of 3 5 Diethanolamide of copra fatty acids 1,604,475 2 g 55 Compound of Example l Ib 0,8 g of active material Perfume O 1 g Colorants O 01 g 5 Water, q s p 100 g The p H is adjusted to 7 2.

When applied to dyed hair, this shampoo ensures that the wet hair is easy to comb out and renders the dry hair full of life and bulky.

EXAMPLE 4 g 10 A shampoo having the following composition is prepared:

Alcohol (C,2-C 14) which is oxyethyleneated with 10 mols of ethylene oxide and is carboxymethylated, sold under the Trademark "AKYPO RLM 100 " by Messrs CHEM Y 3 g 15 Polyoxyethyleneated lauryl alcohol containing 12 mols of ethylene oxide 7 g Lauryl diethanolamide 3 g Compound of Example Ib 0 6 g of active 20 material CH CII 1 N ( 3 -(CH 2) N ( CH 2)6 O X 3 g of active 1 24 I 261 material CH 3 el 13 Cl H ca i C 1 C 1Water, q s p 100 g The initial p H of 4 5 is brought back to a p H of 7 2 with triethanolamine.

This shampoo is in the form of a clear liquid and is applied to dyed hair The 25 wet hair is easy to comb out When dry, the hair is well-cared for and glossy.

EXAMPLE 4 h

A shampoo having the following composition is prepared:

Triethanolamine C 12-C 14-alkyl-sulphate 10 g Lauryl diethanolamide 2 g 30 Hydroxypropylmethylcellulose 0 2 g Compound of Example II Ib 0 8 g Perfume 0 1 l g Colorants 0 01 g Water, q s p 100 g 35 The p H is adjusted to 8 with triethanolamine.

This clear liquid shampoo makes the wet hair easier to comb out It ensures good manageability and dried hair which is well-cared for.

EXAMPLE 4 i

A shampoo having the following composition is prepared: 40 Triethanolamine alkyl(C 12-C 14)-sulphate 15 g Hydroxypropylmethylcellulose 0 2 g Lauryl diethanolamide 3 g Compound of Example VI Ib I g Perfume 0 2 g 45 Colorants 0 01 g Water, q s p 100 g The spontaneous p H is 7 7.

1,604,475 1604475 7 ( 1 EXAMPLE 4 j

A shampoo having the following composition is prepared:

Triethanolamine alkyl(C,2-C,4)-sulphate 10 g Hydroxypropylmethylcellulose 0 3 g Compound of Example VII Ib I g 5 Perfume O 1 g Colorants O 015 g Water, q s p 100 g The spontaneous p H is 7 7.

EXAMPLE 5 a 10 Deep care cream after shampooing.

Cetyl alcohol 20 g Oxyethyleneated cetyl alcohol containing 10 mols of ethylene oxide, sold under the name "BRIJ 50 " (ATLAS) 12 g 15 3 15 N@ (CH 2)3 N( (CH 2)6 1 5 g of active X { material CH e C H Compound of Example Vb 0 5 g of active material Acid phosphoric ester of oxyethyleneated oleyl alcohol, sold 20 under the trademark "DIVALIN SO" by Messrs.

Zschimmer and Schwarz I g Water, q s p 100 g EXAMPLE Sb

Deep care cream after shampooing 25 Cetyl alcohol 22 g Oxyethyleneated cetyl alcohol containing 10 mols of ethylene oxide, sold under the trademark "BRIJ 56 " by MessrsATLAS 10 g Compound of Example lib 0 5 g of 30 active material Acid phosphoric ester of oxyethyleneated oleyl alcohol, sold under the trademark "DIVALIN SO" by Messrs Zschimmer and Schwarz 1 2 g 35 Water, q s p 100 g The care cream of Example Sa or Example Sb is applied to clean, damp hair, which has been dried without heat, in an amount ( 60 to 80 g) which is sufficient to thoroughly impregnate and cover the head of hair It is allowed to remain for 30 to 40 minutes and rinsed out The wet hair is very soft and easy to comb out It is set in 40 waves and dried under a drier The dried hair can be combed out easily and has a silky feel; it is glossy, full of life and has body and bulk.

EXAMPLE 5 c

Deep care cream before shampooing.

Stearic acid 12 g 45 Oxyethyleneated cetyl/stearyl alcohol containing 10 mols of ethylene oxide 4 g 1.604 475 2 r 1 O 47 2 Monoethanolamine Glycerol CH 3 NO I (CH 3)2 CH 3 13 Nt 1 CR,3 cl O (CH 2)6 Cl O Compound of Example V Ib Perfumes and colorants Water, q s p.

2 g 4 g 1.2 g of active material 0.5 g of active material $ g The p H is adjusted to 7.

EXAMPLE 5 d

Deep care cream before shampooing.

Stearic acid Oxyethyleneated cetyl/stearyl alcohol containing 10 mols of ethylene oxide IS Monoethanolamine Glycerol Compound of Example Ib Perfumes and colorants Water, q s p.

12 g 6 g 3 g 3 g 0.8 g of active material g The p H is adjusted to 7.

The care cream of Example 5 c or 5 d is applied at the rate of 60 grams to dirty, damp hair The head of hair is throughly impregnated by massaging The cream is allowed to remain for 30 minutes Shampooing is carried out The wet hair is very soft and easy to comb out After wavesetting and drying, the hair has a particularly soft feel It is glossy, full of life and has body This effect remains after several shampoo treatments.

EXAMPLE 6 a

Structuring lotion applied without rinsing The following composition is prepared:

Dimethylolethylenethiourea of the formula:

*CH 2 OH CH 2-N x C=S CH 2 -N \ 2, , CH 2 OH Quaternary polyvinylpyrrolidone copolymer having a molecular weight of about 1,000,000, marketed under the name "Gafquat 755 " by Messrs General Aniline Compound of Example I Ib O 5 g 0.5 g 0.4 g of active material I 5 1.604475 Polyvinylpyrrolidone/vinyl acetate copolymer ( 70:30) 0 8 g Phosphoric acid, q s p p H 3 Water, q s p 100 cc This lotion is applied to hair which has been washed and dried without heat after shampooing and before wavesetting It is found that, in the wet state, the hair 5 can be combed out easily and that it has a silky feel After wavesetting and drying, the hair is glossy and full of life.

EXAMPLE 7 a

Non-rinsed lotion suitable for use before permanent waving.

Trimethylcetylammonium bromide 0 1 g 10 Compound of Example I Ib 1 5 g Perfume 0 1 g Colorants 0 1 g Citric acid, q s p p H 5 Water, q s p 100 g 15 When applied to hair which has been washed, this non-rinsed product makes the hair easier to comb out and makes it possible for permanent waving to be carried out easily It protects the hair, and the curl is held for a longer time.

EXAMPLE 7 b

Non-rinsed lotion suitable for use before permanent waving 20 Trimethylcetylammonium bromide 0 15 g Compound of Example Vb 2 2 g Perfume 0 2 g Colorants 0 01 g Citric acid, q s p p H 4 25 Water, q s p 100 g When applied to hair which has been washed, this non-rinsed product makes the hair easier to comb out and makes it possible for permanent waving to be carried out easily It protects the hair, and the curl is held for a longer time.

EXAMPLE 8 a 30 Permant waving.

Reducing liquid:

Thioglycolic acid 3 g Thiolactic acid 2 g 22 B 6 strength ammonia solution 4 g 35 Triethanolamine 3 5 g Compound of Example IV 1 4 g Perfume 0 2 g Colorants 0 05 g Water, q s p 100 g 40 Fixing liquid:

Potassium bromate 9 5 g Cetylpyridinium chloride I g Tartaric acid, q s p p H 6 5 Perfume 0 1 g 45 Colorants O 05 g Water, q s p 100 g The reducing liquid is applied very easily to sensitised hair and penetrates deeply into the hair After rinsing and application of the fixing liquid, a very strong and very uniform curl is observed The hair is in a very attractive cosmetic 50 condition After drying, the hair is very soft and particularly glossy The hairstyle is held particularly well.

1.604 475 23 1,604,475 2 EXAMPLE 8 b

Reducing liquid:

Thioglycolic acid 3 5 g Thiolactic acid 2 g 22 B 6 strength ammonia solution 3 5 g 5 Triethanolamine 4 g Compound of Example V Ib 2 g Perfume 0 2 g Colorants 0 01 g Water, q s p 100 g 10 Fixing liquid:

Potassium bromate 8 g Cetylpyridinium chloride 0 8 g Tartaric acid, q s p p H 6 5 Perfume 0 2 g 15 Colorants 0 05 g Water, q s p 100 g The reducing liquid is applied very easily to sensitised hair and penetrates deeply into the hair After rinsing and application of the fixing liquid, a very strong and very uniform curl is observed The hair is in a very attractive cosmetic 20 condition After drying, the hair is very soft and particularly glossy The hairstyle is held particularly well.

Claims (1)

1. WHAT WE CLAIM IS:-

   1 A polyamino-polyamide polymer containing one or more piperazino units prepared by crosslinking a polyamino-polyamide obtained by the polycondensation 25 of one or more acid compounds selected from:

   (i) an organic dicarboxylic acid, (ii) an ethylenically unsaturated aliphatic mono or di-carboxylic acid, (iii) an ester of an acid as defined under (i) or (ii) , (iv) a mixture of two or more compounds defined under (i), (ii) or (iii), or (v) the product of reaction of a bis-primary amine or a bis-secondary diamine with (i), (ii), (iii) or (iv), 30 with one or more polyamines selected from a bis-primary, mono or disecondary polyalkylene-polyamine, up to 50 mol% of this polyamine optionally being replaced by a bis-primary amine or bis-secondary diamine with the proviso that the maximum percentage is 20 mol % when the amine is hexamethylene diamine, the crosslinking agent containing one or more piperazino units and being: 35 (I) a simple bifunctional compound which is either (I) a bishalogenohydrin resulting from the reaction of an epihalogenohydrin with piperazine, ( 2) a bisazetidinium compound containing a piperazino radical, or ( 3) a bishalogenoacyldiamine containing a piperazino radical; (II) an oligomer obtained by reacting a compound (a), which is a compound as 40 defined under ( 2) or ( 3) above, with a compound (b) which is a primary amine, a bis-secondary diamine, a bis-mercaptan or a bis-phenol, or a compound (a') which is ( 5) an epihalohydrin, ( 6) a bis-epoxide or ( 7) a bis-unsaturated compound, with a compound (b') which is piperazine, the molar ratio of (b):(a) and (b') :(a') being from 0 1:1 to 0 9:1; 45 (II bis) an oligomer obtained by reacting a compound (a), which is a compound as defined under (I) or ( 3) above or ( 6 A) a bis-epoxide containing a piperazino radical, with a bis-tertiary diamine (b 1), the molar ratio of (b,):(a 1) being from 0 1:1 to 0 9:1, and (III) the product resulting from the quaternisation of a compound (a 2), which is 50 either ( 1 ') a bis-halogenohydrin resulting from the reaction of an epihalogenohydrin with piperazine, ( 2) a bis-azetidinium compound containing a piperazino radical, ( 3) a bis-halogenoacyldiamine containing a piperazino radical, ( 7) a bis-unsaturated compound containing a piperazino radical, ( 8), an oligomer (II) obtained by reacting a compound (a 3), which is a compound as defined under 55 ( 1), ( 2), ( 3), ( 6 A) or ( 7) above, with a compound (b 3) which is a primary amine, a bissecondary diamine, a bis-mercaptan or a bis-phenol, the molar ratio of (b 3):(a 3) being from 0 1:1 to 0 9:1, ( 9) an oligomer obtained by reacting an epihalogenohydrin (compound a 4) with a bifunctional compound (b 4) which is piperazine or a piperazine bisepoxide, the molar ratio of compound (b 4): 60 1,604,475 24 1,604,475 24 epihalogenohydrin being from 0 1:1 to 0 9:1, and ( 10) an oligomer obtained by reacting a compound (a%), which is either (I') a bis-halogenohydrin resulting from the reaction of an epihalogenohydrin with a piperazine, ( 2) a bishalogenoacyldiamine containing a piperazino radical, or ( 4) a bisepoxide containing a piperazino radical, with a bis-tertiary diamine (b 5) the molar ratio 5 (b 5):(a%) being from 0 1:1 to 0 9:1, said compound (a 2) containing tertiary amine groups which can be alkylated, with an alkylating agent (c) which is methyl or ethyl chloride, bromide, iodide, sulphate, mesylate or tosylate, benzyl chloride or bromide, ethylene oxide, propylene oxide and glycidol, said polyaminopolyamide possessing the following characteristics: 10 (I) it is completely soluble in water to a concentration of 10 % without gel formation; ( 2) the viscosity of a 10 % aqueous solution of the polymer at 25 C is at least 3 centipoises; and I 15 ( 3) it does not possess any reactive group and, in particular, it does not have 15 any alkylating groups and is chemically stable, together with a compatible vehicle.

   2 A polymer according to claim 1, in which the acid compound is chosen from adipic acid, terephthalic acid, or an ester thereof, or the product resulting from the addition of ethylenediamine to acrylic, methacrylic or itaconic acids or an ester thereof 20 3 A polymer according to claim I or 2 in which the polyalkylene-polyamine is diethylenetriamine, dipropylenetriamine or triethylenetetramine, or a mixture thereof with ethylenediamine, hexamethylenediamine or piperazine.

   4 A polymer according to any one of claims I to 3, in which the polyaminopolyamide is obtained by condensing adipic acid with diethylenetriamine 25 A polymer according to any one of claims 1 to 4, which has been crosslinked to the extent of 0 025 to 0 35 mol of crosslinking agent per amine group of the polyamino-polyamide.

   6 A polymer according to claim 5 which has been crosslinked to the extent of 0 025 to 0 2 mol of crosslinking agent per amine group of the polyaminopolyamide 30 7 A polymer according to claim 5 which has been crosslinked to the extent of 0.025 to 0 1 mol of crosslinking agent per amine group of the polyaminopolyamide.

   8 A polymer according to any one of claims I to 7 in which the crosslinking agent is:

   a bis-halogenohydrin of the formulae: 35 ( 1) X-CH 2-CH-CH 2 N N CH 2-CH-CH 2 X I I OH OH n' in which n' is 1 to 4, ( 2) X-CH 2-CHOH-CH 2-N -N / N-CH 2-CHOH-CH 2 X, a bis-azetidinium compound of the formula:

   ( 8) HO X N- CH -CHOH-CH -N N OH 4 ( 8) HO <N NH_Hc 2 N N OH 40 + + C 1 l Cl a bis-halogenoacyldiamine of the formula:

   ( 9) x (CH 2)n, CON NCO (CH 2)n,,,X in which X=CI or Br, n"'=l to 10.

   9 A polymer according to any one of claims I to 8 in which compound (b) is a primary amine, a bis-secondary diamine or a bis-mercaptan 45 _ llIl -l 1,604,475 25 A polymer according to any one of claims I to 8 in which compound (b) is piperazine or ethane-l, 2-dithiol.

   11 A polymer according to any one of claims I to 8 in which compound(b) is a bis-phenol.

   12 A polymer according to claim 11 in which compound (b) is a bis-phenol A 5 or 2,2 ( 4,4 ' dihydroxydiphenyl) propane.

   13 A polymer according to any one of claims I to 7 in which the compound (b 1) is N,N,N'N' tetramethyl ethylene-, propylene-, butylene or hexamethylene-diamine.

   14 A polymer according to any one of claims I to 13 in which the alkylating 10 agent (c) is dimethyl sulphate.

   A polymer according to any one of claims I to 7 in which the crosslinking agent is a compound of the formula:

   ( 3) N-CO-CH 2-CH 2-N,_ CH 2-CH 2 -C 2 -N NCO-CCH 2 CO-CH=CH 2 ( 4) C 1 CH 2 CH OH CH N N CH 2N N CH 2 CH OHCH 2 j C 1 15 CH 3 ( 5) C 1 CH 2-CHOH-CH 2 12 DN -CH 2-CHOH-CH 2 C 1 c O CH 3504 34 ( 6) H "N 'N CH 2 -CHOH -CH 2 Nf N OH +'N J+ \ Cl cl ( 7) C 1 CH 2 CO N N CO CH 2 C 1 l 2 2 ( 8) Cl CH 2 CH oi -CH 2 flNQ CH 2-CHOH CH 23 C 1 l ( 9) Cl CH 2 CH OH CH 2 {N\ _N CH 2-CH OH CH 2} Cl, 20 or ( 10) Br (CH 2)10-CO N N CO (CH 2)10 Br 16 A polymer according to claim 1 specifically identified herein.

   17 A process for preparing a polymer as claimed in claim I which comprises polycondensing the acid compound with the polyamine and crosslinking the 25 product with the crosslinking agent.

   26 1,604,475 26 18 A process according to claim 17 substantially as hereinbefore described.

   19 A polymer as defined in claim I whenever prepared by a process as claimed in claim 17 or 18.

   A composition suitable for application to the hair, which contains at least one water-soluble crosslinked polymer as claimed in any one of claims I to 16 and 5 19 which has been crosslinked to the extent of 0 025 to 0 35 mol, together with a diluent or carrier.

   21 A composition according to claim 20 in which the polymer is one claimed in any one of claims 3 to 5, and 7 to 15.

   22 A composition according to claim 20 or 21 which is in the form of a 10 shampoo and contains a non-ionic, anionic, cationic, amphoteric or Zwitterionic surface-active agent.

   23 A composition according to claim 20 or 21 which contains a hair restructuring agent.

   24 A composition according to claim 20 or 21 which is in the form of a 15 treatment cream and contains a soap or fatty alcohol and an emulsifier.

   A composition according to claim 20 or 21 which is in the form of a colouring cream and contains an alkalising agent and a colorant.

   26 A composition according to claim 20 or 21 which is in the form of a brushing lotion or non-rinsed reinforcing wavesetting lotion 20 27 A composition according to claim 20 or 21 which is in the form of an emulsion.

   28 A composition according to claim 20 or 21 which is in the form of a reducing composition for permanent waving.

   29 A composition according to any one of claims 20 to 28 which has a p H of 2 25 to 11.

   A composition according to claim 29 which has a p H of 3 to 8.

   31 A composition according to any one of claims 20 to 30 which contains the crosslinked polymer in an amount from 0 1 to 5 % by weight based on the total weight of the composition 30 32 A composition according to any one of claims 20 to 31 which contains a water-soluble electrolyte.

   33 A composition according to claim 32 in which the electrolyte is a sodium, potassium, ammonium or calcium chloride or acetate.

   34 A composition according to claim 32 or 33 in which the electrolyte is 35 present in an amount from 0 01 to 5 % by weight based on the total weight of the composition.

   A composition according to any one of claims 20 to 34 which contains a cosmetic polymer.

   36 A composition according to any one of claims 20 to 35 which contains at 40 least one of a perfume, colorant, sequestering agent, thickener, anionic, cationic, amphoteric, Zwitterionic or non-ionic surface-active agent, synergistic agent, foam stabiliser or softening agent.

   37 A composition according to any one of claims 20 to 36 which is in the form of an aqueous or aqueous-alcoholic solution, a cream, a gel, a dispersion, an 45 emulsion or an aerosol.

   38 A composition according to claim 20 substantially as described in any one of Examples la to Sb.

   J A KEMP & CO, Chartered Patent Agents, 14, South Square, Gray's Inn, London WCIR 5 EU.

   Printed for Her Majesty's Stationery Office by the Courier Press, Leamington Spa, 1981 Published by The Patent Office, 25 Southampton Buildings, London, WC 2 A l AY, from which copies may be obtained.