GB1604474A - Composition for conditioning the head of hair - Google Patents

Description

PATENT SPECIFICATION () 1 604 474

( 21) Application No 24084/80 ( 22) Filed I March 1978 ( 61) Patent of addition to No 1494916 dated 29 Nov 1974 () ( 62) Divided out of No 1604473 ( 31) Convention Application No 7706031 ( 32) Filed 2 March 1977 in ( 33) France (FR) ( 44) Complete Specification published 9 Dec 1981 ( 51) INT CL 3 C 08 L 77/00 A 61 K 7/06 ( 52) Index at acceptance C 3 R 22 C 22 DIA 2 22 DIAX 22 D 1 B 2 22 D 2 A 1 22 D 2 A 2 22 D 2 AX 22 D 2 B 3 22 M 7 22 NIA 22 NIB 22 T 2 C 10 Cl 1 C 12 C 13 P C 13 S C 14 B C 16 C 21 C 25 C 29 C 2 A C 6 X C 7 C 8 P C 8 R C 8 T C 9 A C 9 N J L 2 X L 5 C L 6 H V W 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) COMPOSITION FOR CONDITIONING THE HEAD OF HAIR ( 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 Specification No 1,494,915 we have described and claimed a method of 5 conditioning human hair which comprises applying thereto a composition comprising a compatible aqueous or aqueous alcoholic medium and at least one water-soluble crosslinked polymer which is either (I) a polymer produced by crosslinking a polyamino-polyamide prepared by polycondensation of an acid compound which is either: (i) an organic dicarboxylic acid, (ii) an ethylenically 10 unsaturated aliphatic mono or dicarboxylic acid, (iii) an ester of an acid as defined under (i) or (ii), (iv) a mixture of two or more compounds as defined under (i), (ii) and (iii), or (v) the product of reaction of a bis-primary amine or a bissecondary amine with (i), (ii), (iii), or (iv), with a polyamine which is a bisprimary, mono or di-secondary polyalkylene-polyamine, up to 50 mol % of this polyamine optionally 15 being replaced by a bis-primary amine or a bis-secondary amine, with the proviso that the maximum percentage is 20 mol % when the amine is hexamethylene diamine, the polymer being crosslinked by an epihalohydrin, diepoxide, dianhydride or bis-unsaturated compound, the crosslinking agent being used in an amount from 0 025 to 0 35 mol per amine group of the polyamine-polyamide, or (II) 20 a crosslinked polymer as defined under (I) which has been alkylated (as hereinbefore defined) by an epoxide, ethylenically unsaturated compound, chloroacetic acid, propanesultone or butane sultone, the cross-linked polymer in the composition possessing the following characteristics:

(i) it does not possess any alkylating groups and is chemically stable, 25 (ii) it is completely soluble in water at a concentration of 10 /%o by weight, without gel formation, and (iii) the apparent viscosity at a shear rate of 26 3 secs-' of a 10 %/ by weight solution of it in water at 25 C is at least 3 centipoises.

The viscosity of a 10 % strength solution in water at 25 C is greater than 3 c P 30 and usually between 3 and 200 c P.

The cosmetic compositions for the hair constitute "hair conditioners", which are compatible with anionic shampoos whilst ensuring that wet hair can be combed out satisfactorily and that dry hair possesses good elasticity in order to ensure that the hairstyle holds well 35 We have discovered further cross-linking agents which make it possible to prepare new crosslinked polymers from the polyamino-polyamide (A).

Relative to the polymers and the compositions for the hair which are described in Specification No 1,494,915, the new polymers and the new compositions in which these polymers are present have the advantage of ensuring that the hair is generally in a better cosmetic condition and, in particular, of imparting more body and elasticity to dry hair and of improving the hold of the hairstyle.

This advantage is more important in the case of damaged hair which has been subjected to repeated bleaching and/or permanent waving treatments 5 The new crosslinking agents can be classed in the following three groups:

I Simple bifunctional compounds chosen from the group comprising bishalogenohydrins, bis-azetidinium compounds, bis-halogenoacyldiamines and bis-(alkyl halides); II oligomers obtained by reacting a compound (a), chosen from the groups 10 comprising the bifunctional compounds described in group I above and the bifunctional crosslinking agents described in Specification No.

1,494,915, namely epihalogenohydrins, bis-epoxides and bis-unsaturated derivatives, especially epichlorohydrin, N,N'-bis-epoxypropylpiperazine, diglycidyl ether, divinyl sulphone and methylene-bis-acrylamide, with a 15 compound (b) which is a bifunctional compound and reactive towards the compounds (a); and III the product resulting from the quaternisation of a compound which is chosen from the group comprising the compounds (a) (described in the preceding paragraph) and the oligomers described under (II), and which contains 20 one or more tertiary amine groups which can be totally or partially alkylated, with a known alkylating agent and, in particular, with an alkylating agent chosen from the group comprising methyl or ethyl chlorides, bromides, iodides, sulphates, mesylates and tosylates, benzyl chloride or bromide, ethylene oxide, propylene oxide and glycidol 25 In our Application No 8149/78, Serial No 1,604,473, we describe and claim a 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 30 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), with one or more polyamines selected from a bisprimary, mono or di-secondary polyalkylene-polyamine up to 50 mol % of this 35 polyamine optionally being replaced by a bis-primary amine or bissecondary diamine with the proviso that the maximum percentage is 20 mol % when the amine is hexamethylene diamine, the crosslinking agent being:

(I) Simple bifunctional compounds chosen from the group comprising (I) bishalogenohydrins resulting from the reaction of an epihalogenohydrin with 40 a primary amine, a bis-secondary diamine, a bis-phenol or a bismercaptan, ( 2) bis-azetidinium compounds, ( 3) bis-halogenoacyldiamines and ( 4) compounds represented by the general formula:

CH 3 CH 3 X (c 2)X (z)m N X (F) x m I 1 2 x in which X=CI or Br, Z denotes 45 e CH -C Ha CH CH 3 x=l to 3, m= 0 or 1, and n= 0 or 1, it not being possible for m and N to simultaneously denote n; furthermore, when m=l, x=l; A, denotes either a divalent saturated C 2, C 3, C 4 or Ce hydrocarbon radical or the 2hydroxypropylene radical; 50 (II) the oligomers obtained by reacting a compound (a), chosen from the group comprising the compounds ( 1), ( 2), ( 3) and ( 4) above, ( 5) epihalogenohydrins, ( 6) bis-epoxides and ( 7) bis-unsaturated derivatives, with a compound (b) which is a bifunctional compound, reactive towards the compound (a) and chosen from the group comprising primary amines, 55 1,604,474 bis-secondary diamines, bis-mercaptans and bis-phenols, the molar ratio of (b):(a) being from 0 1:1 to 0 9:1; (II bis) the oligomers obtained by reacting a compound (a 1), chosen from the group comprising the compounds ( 1), ( 3), ( 4) and ( 6) above, with a bis-tertiary diamine (b, ) which is a bifunctional compound and reactive towards the compound 5 (a,), the molar ratio of (b 1):(a,) being from 0 1:1 to 0 9:1; and (III) the product resulting from the quaternisation of a compound (a 2), chosen from the group comprising (I) bis-halogenohydrins resulting from the reaction of an epihalogenohydrin with piperazine, a bis-phenol or a bis-mercaptan, ( 2) bis-azetidinium compounds, ( 3) bis-halogenoacyldiamines, ( 4) 10 compounds of the formula F 1, ( 6) bis-epoxides, ( 7) bis-unsaturated derivatives, ( 8) the oligomers II obtained by reacting a compound (a 3), chosen from the group comprising the compounds ( 1), ( 2), ( 3), ( 4), ( 6) and ( 7) above, with a compound (b 3) which is a bifunctional compound, reactive towards the compound (a 3) and chosen from the group IS comprising primary amines, bis-secondary diamines bis-mercaptans and bis-phenols, the molar ratio of (b 3):(a 3) being from 0 1:1 to 0 9:1 ( 9) the oligomers obtained by reacting an epihalogenohydrin (compound a 4) with a bifunctional compound (b 4), chosen from amongst piperazine, bismercaptans, bis-phenols and piperazine bis-epoxides, the molar ratio of 20 compound (b 4): epihalogenohydrin being from 0 1:1 to 0 9:1 and ( 10) the oligomers obtained by reacting a compound (a 5), chosen from the, group comprising ( 1) bis-halogenohydrins resulting from the reaction of an epihalogenohydrin with piperazine, a bis-phenol or a bis-mercaptan, ( 2) bis-halogenoacyldiamines, ( 3) compounds of the formula F,, and ( 4) bis 25 epoxides, with a compound (b 5), chosen from the group of the bistertiary diamines, the molar ratio of (b 5):(a 5) 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) chosen from the group comprising methyl or ethyl chlorides, bromides, iodides, sulphates, mesylates and tosylates, 30 benzyl chloride or bromine, ethylene oxide, propylene oxide and glycidol.

The simple bifunctional compounds of group I are described in greater detail below.

( 1) The bis-halogenohydrins obtained by reacting an epihalogenohydrin, such as epichlorohydrin or epibromohydrin, with bifunction compounds, such as bis 35 secondary diamines, primary amines, diols, bis-phenols or bis-mercaptans, constitute very valuable crosslinking agents.

The bis-halogenohydrins resulting from the reaction of epichlorohydrin with piperazine are particularly valuable.

The bis-halogenohydrins can be direct intermediates in the preparation of bis 40 epoxides 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 crosslinking agent or to the properties of the final product 45 The following bis-halogenohydrins may be mentioned by way of examples:

X C 2 CH 2 CH X n= 1 to 4 OH X CO C-H C 011 C -LX 2 2 2 CR( H X-CH 2-CHOH-CH 2 N (C Hn,-N-CH 2-CHOH-CH 2 X n= 2 to 6, I I CH, CH 3 X-CH 2-CHOH-CH 2-N-CH 2-CHOH-CH 2 X 50 R R=Cn H 2 n+ 1 or also -(CH 2-CH 2-O)m H, n=l to 18, and m=l or 2, 25, X-CH 2-CHOH-CH 2-O-lCH 2-CH 2 Olp CH 2-CHOH-CH 2 X p= O to 1,604,474 X CH 2-Ci H c H 2 o -CH 2-CHOH-CH 2 X cl.

and X-CH 2-CHOH-CH 2-S (CH 2)q CH CHOH-CH 2 X q= 2 to 6.

X denotes Cl or Br in the above formulae.

Bis-azetidinium compounds are derived from N,N 5 dialkylhalogenohydroxypropylamines by cyclisation.

Thus, for example:

X-CH 2-CHOH-C 2-N\ N-CH 2-CHOH-CH 2-K N-CH 2-CHOH-CH 2 X, / CH 2 X denotes Cl or Br 10 However, the cyclisation can be difficult to carry out for certain stericallyhindered amines.

As the reactivity 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 15 halogenohydrin units are bonded to the remainder of the molecule by tertiary 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: 20 X (CH 2),,-CON-A-NCO (CH 2),X l l R, R 2 X=CI or Br, A-CH 2 CH 2-, -CH 2-CH 2-CH 2 or -C-, II n'" denotes a number from I to 10, and R 1 =R 2 =H, or R 1 and R 2 can be bonded to one another, and together denote the ethylene radical; when 25 A= CII or -CH 2 CH 2-CH 2-, R 1 =R 2 =H, the group -N-A-Nl l R R 2 denoting the radical 30 derived from piperazine.

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

Piperazine bis-epoxides may be mentioned amongst the particularly valuable bis-epoxides 35 Oligomers which can be used include statistical mixtures of compounds 1,604,474 obtained by reacting a compound (a), described in groups I and II, or a compound (a,), described in group II bis, or a compound (a 3), (a 4) or (as), described in group III, with a bifunctional compound (b), (b 1), (b 3), (b 4) or (b 5) respectively, which is reactive towards the compounds (a), (a 1), (a 3), (a 4) or (as) that is to say, in general S terms, primary amines, bis-secondary diamines such as piperazine, bistertiary 5 diamines such as N,N,N',N'-tetramethyl-ethylene-, -propylene-, -butylene or hexamethylene-diamine, bis-mercaptans such as ethane-1,2-dithiol, or bisphenols such as "Bis-phenol A" or 2,2 ' ( 4,4 ' dihydroxydiphenyl) propane.

The molar ratios of (b), (b 1), (b 3), (b 4) and (b 5), relative to (a), (a), (a 3), (a 4) and (a 5) respectively, are from 0 1:1 to 0 9:1 10 The oligomerisation reactions are generally carried out at temperatures of 0 to C, and preferably from 0 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 described above under III, are generally carried out at between 0 to 90 C in water 15 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) are chosen from amongst saturated organic dicarboxylic acids having from 6 to 10 carbon atoms, for example adipic, 2,2,4-trimethyl and 2,4,4-trimethyladipic 20 and terephthalic acids, and aliphatic mono and di-carboxylic 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 addition of an alkylenediamine to unsaturated acids such as acrylic, methacrylic and itaconic acids 25 Adipic acid is particularly preferred.

Esters of the above mentioned acids can also be used It is also possible to use mixtures of two or more carboxylic acids and of their esters.

Polyamines which can be used in the preparation of the polyaminopolyamides (A) are chosen from amongst bis-primary, mono or di-secondary polyalkylene 30 polyamines, for example diethylenetriamine, dipropylenetriamine and triethylenetetramine and their mixtures.

Polycondensation is carried out by known processes, by mixing the reactants 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 35 to 1 hour, the water or the alcohol formed during the polycondensation is removed, first at ordinary pressure and then under reduced pressure.

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

When carrying out the reaction, the amount of dicarboxylic acid and amines 40 used is preferably such that they are in equimolecular proportions.

According to a preferred method of preparation, the polycondensation of the polyalkylene-polyamine, which is preferably chosen from amongst diethylenetriamine, triethylenetetramine, dipropylenetriamine and their mixtures, is carried out either (i) with a dicarboxylic acid, preferably adipic acid or its 45 dimethyl ester, or (ii) with the intermediate product resulting from the addition of one molecule of ethylene diamine to two moles of the methyl ester of an ethylenically unsaturated acid, such as methyl acrylate, methacrylate or itaconate.

The reactions involving the addition of ethylenediamine to unsaturated esters are suitably carried out by mixing the reactants at 5 to 80 C, and the 50 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 C, first at ordinary pressure and then under a partial vacuum of 15 mm of mercury.

The polyamino-polyamides (A) thus obtained have a viscosity, as a 10 % 55 strength solution in water and at 25 C, of less than 3 centipoises.

The structure of the preferred polyamino-polyamides (A) can be represented by the general formula (I) -l-OC-R-CO-Z-1 l (I) in which R represents a divalent radical which is derived from the acid used or from 60 the product resulting from the addition of the acid to the bis-primary of bissecondary amine.

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

1,604,474 6 1,604,474 6 -(CH 2)4-, CHN o H 2 H 2 CH 2 CH 2 CH 2 c H 2 a, CH 2 H C 2 22 -NE H _and CE 3 CH 3 CH2 e lj H 2 \ / 2 I X CH 2 CH I N 11 CH 2 A C C O 2 0 O These radicals are derived respectively from terephthalic acid, from adipic 5 acid and from the product resulting from the addition of ethylenediamine to acrylic, methacrylic and itaconic acids or their esters.

Z represents:

1) in proportions of 60 to 100 mol %, the radical -NH-l(CH 2) NH-1 I (II) 10 in which x= 2 and n= 2 or 3, or x= 3 and n= 2, this radical being derived from diethylenetriamine, triethylenetetramine or dipropylenetriamine; 2) in proportions of 0 to 40 mol %, the above radical (II), in which x= 2 and n=l, and which is derived from ethylenediamine, or the radical C 15 derived from piperazine; and 3) in proportions of 0 to 20 mol %, the radical -NH (CH 2) NH-, derived from the hexamethylenediamine.

The polyamino-polyamides thus obtained are then crosslinked by adding a crosslinking agent chosen from amongst those described above 20 The crosslinking reactions are generally carried out at 20 C to 90 C, starting from 20 to 30 %/ strength aqueous solutions of polyamine-polyamide, to which the crosslinking agent is added in very small portions until a large increase in the 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 25 adding water, and the reaction mixture is cooled if necessary.

According to a preferred characteristic from 0 025 to 0 35 mol of crosslinking agent per amine group of the polyamino-polyamide is employed 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 30 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 polyamino-polyamide.

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 35 determined easily by adding the desired crosslinking agent to an aqueous solution of the polyamino-polyamide until the viscosity of a 10 % strength solution, at 25 C, is between 3 centipoises and the gel state, whilst retaining perfect solubility in water.

In fact the crosslinked polymer possesses all the following characteristics: 40 (I) it is perfectly soluble in water to a concentration of 10 % without gel formation; ( 2) the viscosity of a 10 % strength solution of the polymer in water at 25 C is at least 3 centipoises; and ( 3) it does not possess any reacting group and, in particular, it does not have 45 any alkylating property and is chemically stable.

7 1,6034,4747 The crosslinked polymers used can be stored satisfactorily and are compatible with anionic surface-active agents, whilst ensuring that wet hair can be combed out easily This compatibility with anionic surface-active agents can be further improved by alkylating the secondary amine groups of the crosslinked polyaminopolyamides Alkylation increases the solubility in water of the crosslinked 5 polyamino-amides, in the presence of anionic surface-active agents.

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 IQ or acrylic acid; 10 3) chloroacetic acid; or 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 10 and 950 C 15 The crosslinked polymers used can be used in various cosmetic compositions for the hair, for the treatment of normal hair and more particularly of sensitised hair They can also 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 26 and more particularly in shampoo compositions such as an anionic, cationic, non 20 ionic, amphoteric or zwitteronic shampoo, 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 wave-setting lotion compositions, in restructuring compositions and in more specific cosmetic compositions such as 25 anti-dandruff, anti-seborrhoea and permanent waving compositions.

Certain cosmetic compositions for the hair, used in the process are novel and these form the subject of the present invention The compositions of the present invention comprise crosslinked polyamino-polyamide as used in the process claimed in Application No 8149/78, Serial No 1,604,473, and are in the form of an 30 aqueous, aqueous-alcoholic or alcoholic composition comprising at least one cosmetic adjuvant which is one or more electrolytes, foam stabilisers, hair strengthening agents, perfumes, colorants, preservatives, sequestering agents, thickeners, emulsifiers, anionic, cationic, amphoteric, zwitterionic or non-ionic surface active agents, synergistic agents, softening agents or cosmetic resins These 35 compositions are thus a modification of the compositions described and claimed in British Specification No 1,494,916 which are suitable for use as a shampoo and which comprise at least one anionic, cationic, non-ionic or amphoteric surfaceactive agent, an aqueous or aqueous alcoholic medium and at least one crosslinked polyamino-polyamide as used in the process of British Specification No 40

1,494,915.

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 according to the invention generally 45 have a p H of 2 to 11, and preferably 3 to 8.

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 so or alkaline earth metal salts of inorganic or organic acids, preferably the chlorides and acetates of sodium, potassium, ammonium and calcium, are used as electrolytes The amount of electrolyte is not critical It is preferably from O 01 to %, and advantageously from 0 4 to 3 %, of the total weight of the composition The ratio of electrolyte:polymer is suitably 0:1 to 15:1 55 The cosmetic compositions for the hair can be coloured and generally contain 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 polyamino 60 amides are usually present at the rate of 0 1 to 5 %, and preferably 0 1 to 3 %, by weight, relative to the total weight of the composition.

The compositions for the hair which form the subject of the present invention can be in the form of, for example, aqueous or aqueous-alcoholic solutions (the 1,604,474 alcohol being a lower alkanol such as ethanol or isopropanol), or in the form of creams, gels, dispersions or emulsions.

The cosmetic compositions for the hair, according to the invention, constitute, in particular, treatment creams to be applied before or after colouring or bleaching, before or after shampooing, or before or after permanent waving, 5 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 before or after permanent waving, the formulation of these carriers is based on soaps 10 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.

The soaps can be formed from natural or synthetic C,2-C,8 fatty acids (such as lauric acid, myristic acid, palmitic acid, oleic acid, ricinoleic acid, stearic acid 15 and isostearic acid), at concentrations of, say, 10 to 30 %O, and from alkalising agents (such as sodium hydroxide, potassium hydroxide, ammonia, monoethanolamine, diethanolamine and triethanolamine).

The fatty amides which can be used include the following compounds in particular: the mono or di-ethanolamines of acids derived from copra, of lauric 20 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 12-C,8 alcohols mixed with emulsifiers Amongst the fatty alcohols, there may be mentioned in 25 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:

Non-ionic surface-active agents such as oxyethyleneated or polyglycerolated 30 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, polyglycerolated oleyl alcohol containing 4 mols of glycerol, and 35 polyoxyethyleneated synthetic C 9-C 1, 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 oxyethyleneated, such as sodium lauryl sulphate, ammonium lauryl-sulphate, 40 sodium cetyl-/stearyl-sulphate, triethanolamine cetyl-/stearyl-sulphate, monoethanolamine 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 ethylene oxide) These constituents are generally present at concentrations of 3 to 45 % by weight.

Oleyl diethanolamide, copra mono or di-ethanolamide and stearyl monoethanolamide may be mentioned as examples of fatty amides These amides are used at concentrations of up to, say, 10 %. When the compositions of the invention constitute colouring creams, they

50 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 by adding a suitable alkalising agent to the dyeing carrier, for example by adding 55 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 leuco-derivatives of these compounds, can be added 60 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.

Amongst the anionic surface-active agents, the following compounds, as well as their mixtures, may be mentioned in particular: 65 1.604 474 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 18 chain, oxyethyleneated alkylamide-sulphates and ether-sulphates having linear C 12 to C 18 chains, alkylaryl-polyether-sulphates and monoglyceride-sulphates, 5 alkylsulphonates, of which the alkyl has a linear C 12 to C 18 chain, alkylamidesulphonates, alkylarylsulphonates, and alpha-olefin-sulphonates having linear C 12 to C 18 chains, alkylsulphosuccinates, alkyl-ether-sulphosuccinates, and alkylamidesulphosuccinates, of which the alkyl has a linear C 12-C 18 chain, 10 alkylsulphosuccinamates, of which the alkyl has a linear C 12 to C 18 chain, alkylsulphoacetates, of which the alkyl has a C 12 to C 18 chain, alkyl-phosphates, and alkyl-ether-phosphates, of which the alkyl has a C 12 to C 18, chain, alkylsarcosinates, alkylpolypeptidates, alkylamidopolypeptidates, 15 alkylisethionates, and alkyl-taurates, of which the alkyl has a C 12 to C, 8 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 polyglycol ethers of the formula Alk (OCH 2-CH 2) OCH 2-CO 2 H, in which Alk is a C 12 to C 18 linear chain and N is an integer from 5 to 15 20 Amongst the cationic surface-active agents which can be used by themselves or in mixtures, they may be mentioned in particular: fatty amine salts such as alkylamine acetates, quaternary ammonium salts such as the chlorides and bromides of alkyldimethylbenzylammonium, alkyltrimethylammonium, alkylmethylhydroxyethylammonium and dimethyldistearylammonium, and 25 alkylamidoethyltrimethylammonium methosulphates, alkylpyridinium salts and imidazoline derivatives.

Amine oxides having a cationic character, such as alkyldimethylamine oxide or alkylaminoethyldimethylamine oxide, may also be mentioned.

Amongst the non-ionic surface-active agents which can optionally be used in 30 mixtures with the abovementioned anionic surface-active agents, there may be mentioned: products resulting from the condensation of a monoalcohol, an a-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-) H, in which R denotes an aliphatic, cycloaliphatic or arylaliphatic radical having from 7 to 21 carbon atoms, 35 and their mixtures, it being possible for the aliphatic chains to contain ether, thioether and hydroxymethylene groups, and in which kn< 10, and 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, polyoxyethyleneated or polyglycerolated alcohols, alkylphenols 40 or fatty acids having a linear C 8 to C,8 fatty chain and most frequently containing from 2 to 15 mols of ethylene oxide, for example polyoxyethyleneated lauryl alcohol containing 12 mols of ethylene oxide, ethylene oxide/propylene oxide copolymers, condensates of ethylene oxide and of propylene oxide with fatty alcohols, polyoxyethyleneated fatty amides, polyoxyethylenated amines, 45 ethanolamides, glycol fatty acid esters, sorbitol fatty acid esters and sucrose fatty acid esters.

Amongst the amphoteric surface-active agents which can be used, there may be mentioned in particular: alkylamino-mono and -di-propionates, betains such as N-alkylbetaines, N-alkyl sulphobetaines and N-alkylamidobetains, and 50 cycloimidinium compounds (alkylimidazolines).

All these detergents, as well as numerous other detergents which are not mentioned here but can be used in 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 various adjuvants 55 such as, for example, perfumes, colorants, preservatives, thickeners, foam stabilisers, softening agents and cosmetic resins.

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 %, 60 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.

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 65 1,604,474 1,604,474 10 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 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 5 meaning a lotion which is applied after shampooing and before wavesetting; this lotion, which is not removed by rinsing, facilitates the subsequent wavesetting 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 10 contain: film-forming polymers such as polyvinylpyrrolidone, polyvinylpyrrolidone/vinyl acetate copolymers, and copolymers resulting from the 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, polyvinylpyrrolidone (PVP) /vinyl 15 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%)/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 20 molecular weight of the order of 1,000,000 and sold under the trademark "Gafquat 755 " by GAF Corporation, and the polymer having a 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-vinylpyrrolidone, 3 to 95 % by weight of dimethylaminoethyl 25 methacrylate and 2 to 50 %/ by weight of polyethylene glycol, such as those described in French Patent No 76/15,948 cationic polymers resulting from the condensation of piperazine or of its derivatives (I) with bifunctional compounds such as alkyl or alkylaryl dihalides, bis-epoxides, epihalogenohydrins or bisunsaturated derivatives, ( 2) with a primary amine, the two hydrogen atoms of which 30 can be substituted and which behaves as a bifunctional compound, or ( 3) both with an epihalogenohydrin and with a 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 35 preferably from 0 1 to 3 %, and the p H is generally from 3 to 9.

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 40 period of time.

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 45 cationic surface-active agents such as those described in the composition of the 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 (CH 2 CHOH-CH 2 (NH, in which R denotes an aliphatic, cycloaliphatic or arylaliphatic radical having 50 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 ln< 10, and 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 is between 1 and 10, and polyoxyethyleneated or polyglycerolated alcohols, 55 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.

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

Anionic or amphoteric surface-active agents can also be added 60 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 stearyl or ceyl/stearyl alcohols, for example, containing 10 mols of ethylene oxide.

Cationics such as those defined above can be added to these compositions 65 The anionic emulsions are formed from soaps Thus, there may be mentioned the emulsion comprising self-emulsifying glycerol stearate sold under the 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 lipopetides or with alkali metal stearates sold respectively under 5 the tradenames Lameform ZEM, PLM and NSM by Messrs Grunau.

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

The thickneners can be sodium alginate, gum arabic, cellulose derivatives such as methylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, 10 hydroxypropylcellulose and carboxymethylcellulose, or carboxylic polymers such as the "Carbopols" (Registered Trade Mark) It is also possible to obtain a thickener for 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 15 0.5 to 15 % by weight.

The p H of the rinsed lotions generally varies from 2 to 9 5.

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 20 1,527,085 and 1,519,979 below to this class of products.

The present invention is further illustrated by the following Examples.

Examples I and II illustrate the preparation of polymers used in the invention.

PREPARATION EXAMPLES EXAMPLE A 25

Polycondensation of adipic acid with diethylenetriamine in equimolar amounts.

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

-l-OC-(CH 2)4 CONH (CH 2-CH 2-NH)2-l 30 876 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 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 35 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 hard and brittle resin The resin is a transparent yellow-green colour and dissolves completely in water 40 EXAMPLE Ia

Preparation of the quaternised crosslinking agent of the formula:

CH 2 CH C N N CI 2 C C H 2 CE 3 CH CH 13 504 O 36.4 g ( 0 289 mol) of dimethyl sulphate are added, in the course of one hour, to 236 g of a chloroform solution containing 57 2 g ( 0 289 mol) of bis(epoxypropyl) 45 piperazine, whilst stirring the reaction medium at 30 C.

The quaternised derivative is then precipitated from its solution with a large excess of ether After drying, a very viscous oil is collected Its epoxide content is 5.19 milliequivalents/g EXAMPLE Ib 50

Crosslinking, using the crosslinking agent prepared in Example Ia, of the polyamino-amide polymer obtained by condensing adipic acid with diethylenetriamine 22 g ( 0 057 mol) of the quaternised crosslinking agent prepared in Example Ia are added, at ambient temperature, to 500 g of an aqueous solution containing 100 55 1,604,474 12 1,604,474 12 g ( 0 585 equivalent of amine) of the polyamino-amide prepared by condensing adipic acid with diethylenetriamine in equimolar amounts, according to Example A, and the temperature of the reaction medium is then brought to 90 C.

After 20 minutes, gelling of the solution is observed 698 g of water are then added rapidly A clear yellow-green coloured solution containing 10 % of active 5 material is obtained The viscosity, measured at 25 C and at a rate of shear of 87 93 seconds-', is 0 68 P.

EXAMPLE Ila

Preparation of the quaternised crosslinking agent of the formula: 10 CH 3 CH 3 I / CH 2 CH CH 2 N N CH 2 CH H 2 g ( 0 555 mol) of dimethyl sulphate are added, in the course of one hour, to 187 3 g of a chloroform solution containing 54 9 g ( 0 277 mol) of bis (epoxypropyl) piperazine, whilst stirring the reaction medium at 30 C.

The medium thickens during the addition and solidifies after several hours at 15 ambient temperature The paste is dissolved in hot dimethylformamide When cold, the solution yields white crystals having a melting point of 205 C and an epoxide number of 4 25 milliequivalentslg.

EXAMPLE I Ib

Crosslinking, using the crosslinking agent prepared in Example 20 I Ia, of the polyamino-amide polymer obtained by condensing adipic acid with diethylenetriamine g ( 0 0425 mol) of the crosslinking agent prepared above are added, at ambient temperature, to 476 g of an aqueous solution containing 95 2 g ( 0 557 equivalent of amine) of the polyamino-amide prepared according to Example A 25 The reaction mixture is stirred at 90 C for I hour and the concentration of active material in the solution is brought back to 10 % by adding 656 g of water.

The solution is a clear yellow-green colour The viscosity, measured at 25 C and at a rate of shear of 87 93 seconds-', is 0 27 P.

EXAMPLE Ia 30

The following wavesetting composition is prepared:

Compound of Example Ib 0 5 g of active material Quaternary polyvinylpyrrolidone copolymer having a 35 molecular weight of about 100,000 and marketed under the trade mark "Gafguat 734 " by Messrs.

General Aniline 0 4 g of active material 40 Perfume 0 1 g Colorants 0 01 g Water, q s p 100 cc The p H is 7 3.

When applied to hair which has been coloured, this wavesetting lotion makes 45 the wet hair easier to comb out When dry, the hair is soft and easy to style This softness effect remains after several shampoo treatments.

EXAMPLE lb

The following wavesetting lotion composition is prepared:

Compound of Example l Ib 0 6 g of 50 active material Quaternary polyvinylpyrrolidone copolymer having a molecular weight of about 100,000 and marketed under the trade mark "Gafquat 734 " by Messrs.

General Aniline 0 5 g Quaternised cellulose sold under the trade mark "JR 5 400 " by Messrs Union Carbide 0 3 g Ethyl alcohol, q s p 15 Perfume 0 1 g Water, q s p 100 cc The p H is adjusted to 8 10 When applied to hair which has been washed, this wavesetting lotion makes 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 2 a

The following brushing lotion is prepared: 15 Compound of Example Ib 0 5 g of active material Colorants 0 1 g Perfume 0 1 g Water, q s p 100 cc 20 The p H of the solution is adjusted to 5.

EXAMPLE 2 d

The following brushing lotion is prepared:

Compound of Example I Ib 0 8 g of active material 25 Ethanol, q s p 40 Colorants 0 05 g Perfume 0 1 g Water, q s p 100 cc The p H of the solution is adjusted to 7 30 EXAMPLE 3 a

A shampoo having the following composition is prepared:

Polyoxyethyleneated lauryl alcohol containing 12 mols of ethylene oxide 5 g Alkyl (C,2-C 18) dimethylcarboxymethylammonium 35 hydroxide, sold by Messrs Henkel under the trade mark "Dehyton AB 30 " 10 g Lauryl diethanolamide 3 g Compound of Example Ib 0 8 g of active 40 material Water, q s p 100 g The initial p H of 7 8 is brought back to a p H of 6 with lactic acid.

This shampoo is in a slightly opalescent clear form and is applied to dyed hair.

The wet hair is easy to comb out and softer The dried hair is full of life, bulky and 45 manageable.

EXAMPLE 3 b

A shampoo having the following composition is prepared:

Triethanolamine alkyl (C,2-C 14)-sulphate 12 5 g 50 Lauryl diethanolamide 2 g Compound of Example Ilb 0 7 g of active material Water, q s p 100 g 55 The spontaneous p H is 7 4.

1.604474 ll When applied to natural hair, this clear liquid shampoo ensures that the wet hair can be combed out easily It makes the wet hair slightly easier to comb out (sic) The dried hair is bulky, full of life and manageable.

EXAMPLE 3 c

S A shampoo having the following composition is prepared: 5 Alcohol (C 2-C 4) which is oxyethyleneated with 10 mols of ethylene oxide and is carboxymethylated, sold under the trade mark Akypo RLM 100 by Messrs Chem Y 3 5 g Polyoxyethyleneated lauryl alcohol containing 12 mols 10 of ethylene oxide 10 g Compound of Example I Ib 0 6 g of active material Dimethyldiallylammonium chloride homopolymer 15 having a molecular weight of about 100,000, sold under the trade mark "Merquat 100 " by Messrs.

Merck 0 4 g of active material 20 Water, q s p 100 g The spontaneous p H is 7 4.

When applied to dyed hair, this liquid shampoo makes the wet hair easier to comb out The dried hair is mangeable and glossy.

EXAMPLE 3 d 25 A shampoo having the following composition is prepared:

Alcohol (C 12-C 14) which is oxyethyleneated with 10 mols of ethylene oxide and is carboxymethylated, sold under the trade mark "Merquat 100 " by Messrs Chem Y 3 5 g 30 Polyoxyethyleneated lauryl alcohol containing 12 mols of ethylene oxide 10 g Compound of Example lb 0 6 g of active material 35 Dimethyldiallylammonium chloride homopolymer having a molecular weight of the order of 100,000, sold under the trade mark "Merquat 100 " by Messrs Merck 0 4 g of active 40 material Perfume 0 15 g Colorants 0 02 g Water, q s p 100 g The p H is adjusted to 7 45 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 3 e

A shampoo having the following composition is prepared:

R-CHOH-CH 2-O (CH 2 CHOH-CH 2 O-), H 10 g 50 R=C 9 to C,2 alkyl; n=mean statistical value of 3 5 Diethanolamide of copra fatty acids 3 g Diethanolamide of copra fatty acids 3 g Compound of Example I Ib 0 5 g of 55: active 55 ^- material 1.604474 1,604,474 15 OH CH 3 I 1 0 2 g of N ((CH 2) 2 N (OH 2)6 active I 2 material ca 53 CR 3 C 1 C 1Water, q s p 100 g The spontaneous p H of 8 6 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 The wet hair is easy to comb out When dry, the hair is well-cared for, manageable and 5 glossy.

EXAMPLE 3 f

A shampoo having the following composition is prepared:

R-CHOH-CH 2-O (CH 2-CHOH-CH 2 O-)n H 10 g R=C 9 to 12 alkyl; n=mean statistical value of 3 5 10 Triethanolamine alkyl (C 12-C,4)-sulphate 2 g Diethanolamide of copra fatty acids 3,g Compound of Example Ib 0 5 g of active material 15 CH 3 C 1 I I l N l@ (CH 2)3 N (CH 2)6 O 1 g of active I material CH 3 CH 3 ca C c 1:3 Water, q s p 100 g The initial p H of 7 9 is brought back to a p H of 6 with lactic acid.

This shampoo is in the form of a slightly opalescent liquid and is applied to dyed hair The wet hair is easy to comb out and soft The dried hair is full of life and 20 bulky.

EXAMPLE 3 g

A shampoo having the following composition is prepared:

R-CHOH-CH 2-O (CH 2-CHOH-CH 2-O-) -H 10 g R=C 9 to C 12 alkyl; n=mean statistical value of 3 5 25 Diethanolamide of copra fatty acids 2 g Compound of Example Ib 0 7 g of active material CH; CEI 3 + I l C 3 e 13 Br Br Water, q s p 100 g The spontaneous p H is 7.

1,604,474 I 5 This shampoo is in the form of a clear liquid and is applied to natural permed hair The wet hair is easy to comb out and soft When dry, the hair is full of life, bulky and easy to manage.

EXAMPLE 4 a

Structuring lotion applied without rinsing 5 The following composition is prepared:

Dimethylolethylenethiourea of the formula:

HCH 20 H s C=S 0 5 g CH 20 CH 2-N CH 2 OH Quaternary polyvinylpyrrolidone copolymers having a molecular weight of about 1,000,000, marketed 10 under the trade mark "Gafquat 755 " by Messrs.

General Aniline 0 5 g Compound of Example lb 0 4 g of active material 15 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 20 can be combed out easily and that it has a silky feel After wavesetting and drying, the hair is glossy and full of life.

In our Application No 8148/78, Serial No 1,604,472, we describe and claim a composition suitable for application to the hair which comprises at least one watersoluble polyaminoamide derivative which is a condensation product of a 25 polyalkylene-polyamine with a polycarboxylic acid, said product having been reacted with a bifunctional alkylating agent of the formula:

R 1 R 2 R 1 R 2 -x/ 2 H N + +qO -2 _ Q:, in which x is 0 or an integer from I to 7, A denotes a -CH-CH or -CH-CH 2 30\/ 2 H-11 30 O OH R 3 group in which R 3 denotes halogen, R, and R 2 denote, independently of one another, an alkyl or hydroxyalkyl group containing I to 4 carbon atoms, and B represents an alkylene group containing 2 to 6 carbon atoms, a -CH 2-CH-CH 2I OH group, or a group of formula: 35 g 3 (CH 2), NH O NH (CH 2)v?mm < r 1,604,474 in which y is an integer from 1 to 4 and Q denotes halogen, sulphate or methosulphate, and at least one water soluble high molecular weight (as hereinbefore defined) quaternary ammonium homopolymer or copolymer containing chain recurring units of the formula:

C% 2 C H 2-ROC /CR c 21 I (I) H 2 C CH 2 R R in which R denotes a hydrogen atom or a methyl group, and R and R' denote, independently of one another, an alkyl group having from I to 22 carbon atoms, a hydroxyalkyl group, or a lower amidoalkyl group, or R and R' together with the nitrogen atom to which they are bonded, denote a heterocyclic group, said units being associated with a cosmetically acceptable anion No claim is made herein to 10 these compositions.

In our Application No 80 24085, Serial No 1,604,475, we describe and claim a polyamino-polyamide polymer containing one or more piperazino units 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 15 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 bissecondary diamine with (i), (ii), (iii) or (iv), with one or more polyamines selected from a bis-primary, mono or di-secondary polyalkylene-polyamine, up to 50 mol % 20 of this polyamine optionally being replaced by a bis-primary amine or bissecondary 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 being:

(I) a simple bifunctional compound which is either ( 1 I) a bishalogenohydrin 25 resulting from the reaction of an epihalogenohydrin with piperazine, ( 2) a bis-azetidinium 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 30 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 bisunsaturated 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), which is a compound as 35 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 1):(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 40 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, 45 with a compound (b 3) which is a primary amine, a bis-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 so piperazine bis-epoxide, the molar ratio of compound (b 4); 50 1,604,474 x u 7 X-,epihalogenohydrin being from 0 1:1 to 0 9:1, and ( 10) an oligomer obtained by reacting a compound (as), which is either (I') a bishalogenohydrin resulting from the reaction of an epihalogenohydrin with a piperazine, ( 2) a bis-halogenoacyldiamine containing a piperazino radical, or ( 4) a bis-epoxide containing a piperazino radical, with a bis 5 tertiary diamine (b 5) the molar ratio (b 5):(a J) 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 polyamino-polyamide 10 possessing the following characteristics: ( 1) 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 15 ( 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 as well as compositions containing them No claim is made herein to these compositions.

Further in our Application No 8147/78, Serial No 1,604,471, we describe and 20 claim a composition suitable for the hair which comprises at least one crosslinked polyamino-amide and at least one cationic polymer having a molecular weight of at least 1500 comprising repeat units of the formula:

e R 1 R 2 xe NANI I I Xe N-A-N-BR 3 R 4 in which each of R 3 and R 4, which are identical or different, represents an alkyl 25 radical having I to 3 carbon atoms, each of R, and R 2, which are identical or different, represents an alkyl radical having I to 3 carbon atoms, or a hydroxyalkyl radical having 1 to 3 carbon atoms, and, if R 2 =R 4 =CH 3 and R,=R 3, R, and R 3 can also represent an alkyl group having 4 to 8 carbon atoms, and, if R 2 =R 4 =R,=CH 3, R 3 can also represent a benzyl group, a cyclohexyl group, or an alkyl group having 30 4 to 12 carbon atoms, and each of A and B, which are identical or different, represents a linear or branched alkylene radical having 2 to 20 carbon atoms in the chain, or a -(CH 2)-Z(-C H,)n CH-CAH CH, or -CH,-CH(OH)CH 2 radical, N being 2 or 3, and Z representing either the -0 O-group or the -NH-CO-NH group, and X represents an anion 35 No claim is made herein to these compositions Subject to these disclaimers.

Claims (1)

1. WHAT WE CLAIM IS:-

   I An aqueous, alcoholic or aqueous alcoholic composition suitable for application to the hair which comprises a polyamino-polyamide polymer prepared by crosslinking a polyamino-polyamide obtained by the polycondensation of one or 40 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 bissecondary diamine with (i), (ii), (iii) or (iv), with one or more polyamines selected 45 from a bis-primary, mono or di-secondary polyalkylene-polyamine, up to 50 mol o O of this polyamine optionally being replaced by a bis-primary amine or bissecondary diamine with the proviso that the maximum percentage is 20 mol % O when the amine is hexamethylene diamine, the crosslinking agent being:

   (I) a simple bifunctional compound which is either (I) a bishalogenohydrin 50 resulting from the reaction of an epihalogenohydrin with a primary amine, a bis-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:

   1.604474 1 R 9 1 T O4 1 X CH 3 I CH 3 X r CH 3 X (CH 2)X (Z)m _ Nm CH 3 Xi -(CH 2)x X (F 1) n in which X denotes Cl or Br, Z denotes C CH-C -CR C,Y -CH CH / x is 1 to 3, m is 0 or 1, and N is 0 or 1, 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 6 hydrocarbon radical or a 2hydroxypropylene radical; (II) an oligomer obtained by reacting a compound (a), which is a compound as defined under ( 2), ( 3) or ( 4) above, or ( 5) an epihalogenohydrin, ( 6) a bisepoxide or ( 7) a bis-unsaturated compound, with a compound (b) which is a primary amine, a bis-secondary diamine, a bis-mercaptan or a bisphenol, the molar ratio of (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 compound as defined under ( 1), ( 3), ( 4) or ( 6) above, with a bis-tertiary diarnine (b,), the I 55 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 ( 1 ') a bis-halogenohydrin resulting from the reaction of an epihalogenohydrin with piperazine, a bis-phenol or a bis-mercaptan, ( 2) a bis-azetidinium compound, ( 3) a bis-halogenoacyldiamine, ( 4) a bis(alkyl halide) of formula (F 1), ( 6) a bis-epoxide, ( 7) a bis-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-secondary diamine, a bismercaptan 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 epihalogenohydrin (compound a 4) with a bifunctional compound (b 4) which is piperazine, a bismercaptan, a bisphenol 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 reacting a compound (a 5), which is either ( 1 ') a bishalogenohydrin resulting from the reaction of an epihalogenohydrin with piperazine, a bis-phenol or a bis-mercaptan, ( 2) a bishalogenoacyldiamine, ( 3) a bis-(alkyl halide) of formula (F,), or ( 4) a bisepoxide, with a bis-tertiary diamine (b 5), 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, the molar ratio (b 5):(a 5) being from 0 1:1 to 0 9:1, said crosslinking agent being used in an amount of 0 025 to 0 35 mol per amine group of the polyamino-polyamide, said polyamino-polyamide possessing the following characteristics:

   ( 1) 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 ( 3) it does not possess any reacting group and, in particular, it does not have any alkylating groups and is chemically stable said composition comprising at least cosmetic adjuvant which is one or more electrolytes, foam stabilisers, hair strengthening agents, perfumes, colorants, preservatives, sequesterintg agents, thickeners, emulsifiers, anionic, cationic, amphoteric, zwitterionic or non-ionic so 50 surface-active agents, synergistic agents, softening agents or cosmetic resins.

   2 A composition according to claim I 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.

   3 A composition according to claim 1 or 2 in which the polyalkyleneIs 1.604 474 polyamine is diethylenetriamine, dipropylenetriamine or triethylenetetramine, or a mixture thereof with ethylenediamine, hexamethylenediamine or piperazine.

   4 A composition according to any one of claims I to 3 in which the polyaminopolyamide is obtained by condensing adipic acid with diethylenetriamine.

   5 A composition according to any one of claims 1 to 4 in which the polyamino 5 polyamide 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 composition according to claim 5 in which the polymer has been crosslinked to the extent of 0 025 to 0 2 mol of crosslinking agent per amine group of the polyamino-polyamide 10 7 A composition according to claim 5 in which the polymer has been crosslinked to the extent of 0 025 to 0 1 mol of crosslinking agent per amine group of the polyamino-polyamide.

   8 A polymer according to any one of claims I to 7 in which the crosslinking agent is: 15 a bis-halogenohydrin of the formulae:

   ( 1) X-CH 2 "-c H-CH 2LN 21 "N 2-CI-CH 2 X (i) x 2 ca 2 O N 3 OH I in which n' is I to 4, ( 2) X-CH 2 CHOCH 2-KN-2 N-CH 2-CHOH-CH 2-N N CH 2-CHOH-CH 2 X, ( 3) X-CH 2-CHOH-CH 2 N (CH 2),N CH 2 CHOH-CH 2 X 20 I I CH 3 CH 3 in which n" is 2 to 6, ( 4) X-CH 2-CHOH-CH 2-N-CH 2-CHOH-CH 2 X R in which R=C H 2 + 1 and n=l to 18, or R= (CH 2 CH 2-O)H and m=l or 2, ( 5) X-CH 2-CHOH-CH 2-O-lCH 2-CH 2 Olp CH 2 CHOH-CH 2 X in which p is O to 25, 25 CH ( 6) x CH 2-O-C Ec H2 _ O Y\ 3 CH 2 CHOHCH 2 x ( 7) X-CH 2-CHOHCH 2-S (CH 2) S CH 2-CHOH-CH 2 X in which q is 2 to 6, and X denotes Cl or Br; a bis-azetidinium compound of formula:

   ( 8) 11, CH 2 -CHO -CH 2 N N -OH 30 ,+ Cl C 1 bis-chloroacetylethylenediamine; bis-chloroacetylpiperazine; bis-bromoundecanoylethylenediamine; bis-bromoundecanoylpiperazine; a bis-halogenoacyldiamine of the formula: 35 ( 9) X (CH 2)n,,,-CON-A NCO (CH 2)n,,X 1 R R, R, 1.604474 2 n 21 1,604,474 hi in which X=Cl or Br, A=-CH 2-CH 2-, -CH 2-CH 2-CH 2 or -C-, n"'=l to 10, and R,=R 2 =H, or R, and R 2 together denote the ethylene radical; with the proviso that when A denotes -CH 2-CH 2-CH 2 or -C 5 It R, anfid R 2 must denote hydrogen or a bis-(alkyl halide) of the formula (F,).

   9 A composition 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.

   A composition according to any one of claims I to 8 in which compound o 10 (b) is piperazine or ethane-l,2-dithiol 10 11 A composition according to any one of claims I to 8 in which compound (a) is a compound ( 1), ( 2) bis-azetidinium, ( 3), ( 4), ( 5), or ( 6) and compound (b) is a bisphenol.

   12 A composition according to claim 11 in which compound (b) is bisphenol A or 2,2 ( 4,4 'dihydroxydiphenyl) propane 15 13 A composition according to any one of claims I to 7 in which compound (b,) is a bis-tertiary diamine.

   14 A composition according to claim 13 in which the compound (b,) is' NN,N,N',N' tetramethyl ethylene -, -propylene, -butylene or hexamethylenediamine 20 A composition according to any one of claims I to 14 in which the alkylating agent (c) is dimethyl sulphate.

   16 A composition according to any one of claims 1 to 11 in which the modified bis-azetidinium compound is derived from a bis-halogenohydrin in which the Z 5 halogenohydrin units are bonded to the remainder of the molecule by tertiary 25 nitrogen groups, and contains either two azetidinium groups or one azetidinium group and one halogenohydrin group 17 A composition according to any one of claims I to 7 in which the crosslinking agent is a compound of the formula:

   O/ \ ( 1) CE-,C -E 30 I\/ ( 1) CH -0 CH CH 2 X CH 2 CH CH 2 \ CH 3 CH Soe \ 0/ CH CH l/,i 3 ( 2) CH CH CH 2 -N N CH 2 C CH -H 2 ( /NO_ 2 _C 2 _N//N CH CH/ / CH 34 CH 3 SO 4 o ( 3) O N Cj H 2 C 2 N NC -C CN N-CO-C-H= 2-NNC Hi CH 2 CO N\ CO-CH=CH 2 ( 4) C 1 CH 2 CH OH CH 2 N N CH 2 CH OH CH 2 Ci CCH 3 \ C N, ( 5) Cl CH-,-CHOH-CH, N/ XN-CH 9 -CHOH-CHI 9 'Cl"CH 35 O 4 e ( 6) O m C 2 -C Ho" C 2 > O + + Cl Cl( 7) Cl C 2 COM N-CO CH 2 Cl ( 8) Cl CH 2 CH CH 2 L Nm CH 2 CH OH -CH 2 j Cl r/\ 1 ( 9) Cl Cia 2 OCc CE 2 o NC 2-CH C CE 2 Cl or ( 10) Br (C% 2)10-CO N N CO -(CE 2)10 Br.

   18 A composition according to any one of claims I to 17 which is in the form of a shampoo and contains a non-ionic, anionic, cationic, amphoteric or Zwitterionic surface-active agent.

   19 A composition according to any one of claims I to 17 which contains a hair 10 restructuring agent.

   A composition according to any one of claims I to 17 which is in the form of a treatment cream and contains a soap or fatty alcohol and an emulsifier.

   21 A composition according to any one of claims I to 17 which is in the form of a colouring cream and contains an alkalising agent and a colorant 15 22 A composition according to any one of claims 1 to 17 which is in the form of a brushing lotion or non-rinsed reinforcing wave setting lotion.

   23 A composition according to any one of claims 1 to 17 which is in the form of an emulsion.

   24 A composition according to any one of claims 1 to 17 which is in the form 20 of a reducing composition for permanent waving.

   A composition according to any one of claims I to 24 which has a p H of 2 to 11.

   26 A composition according to claim 25 which has a p H of 3 to 8.

   27 A composition according to any one of claims I to 26 which contains the 25 crosslinked polymer in an amount from 0 1 to 5 % by weight based on the total weight of the composition.

   28 A composition according to any one of claims I to 27 which contains a water-soluble electrolyte.

   29 A c 6 mposition according to claim 28 in which the electrolyte is a sodium, 30 potassium, ammonium or calcium chloride or acetate.

   A composition according to claim 28 or 29 in which the electrolyte is present in an amount from 0 01 to 5 % by weight based on the total weight of the composition.

   1,604,474 23 1,604,474 23 31 A composition according to any one of claims I to 30 which contains a cosmetic polymer.

   32 A composition according to claim I substantially as described in any one of Examples Ia to 8 b.

   J A KEMP & CO, Chartered Patent Agents, 14, South Square, Gray's Inn, London WC 1 R 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.