CH632409A5 - Process for preparing a cosmetic composition for hair - Google Patents

Description

The subject of the present invention is the process for preparing a cosmetic composition defined in claim 1. In this crosslinked polyamide is prepared by the crosslinking of a polyaminopolyamide obtained by polycondensation of an acid compound chosen from: i) organic acids dicarboxylics, ii) mono- and dicarboxylic acids with ethylenic double bond, iii) esters of the abovementioned acids, iv) mixtures of these compounds, on a polyamine chosen from polyalkylene / bisprimary and mono- or dis-secondary polyamines, 0 to 20 mol% of this polyamine which can be replaced by hexamethylenediamine or 0 to 40% of this polyamine which can be replaced by a bisprimary amine, preferably ethylenediamine, or by a bissecondary diamine, preferably piperazine; crosslinking is carried out using a crosslinking agent chosen from the group formed by:

I) the simple bifunctional compounds chosen from the group formed by: 1) bishalohydrins resulting from the reaction of an epihalohydrin with a primary amine, a bissecondary diamine, a bisphenol and / or a bismercaptan, 2) bisazetidiniums, 3) bishaloacyldiamines, 4) alkyl bishalides represented by the general formula:

X - (CH „) (Z) -2 x m ch

3 ©

not

I

ch3

xö

ch

- Ai - H

3 ©

ch,

x

.0

(ch2) x - X

(F1}

where X - Cl or Br, Z denotes C

ch - ch

%

=

x = 1 to 3

ch '

m = 0or 1, n = 0 or 1,

m and n cannot at the same time denote 1; moreover, when m = 1, x = 1; Ai denotes a divalent saturated hydrocarbon radical in C2, C3, C4 or C6 or alternatively the 2-hydroxypropylene radical;

II) the oligomers obtained by reaction of a compound chosen from the group formed by compounds 1), 2), 3), 4) above, 5) epihalohydrins, 6) bisepoxides, 7) bisinsaturated derivatives , with a compound b which is a bifunctional compound reactive with respect to the compound a and chosen from the group formed by primary amines, bissecondary diamines, bismercaptans and bisphenols, the molar ratio b: a being between 0 , 1 and 0.9,

Ilbis) the oligomers obtained by reaction of a compound at selected from the group formed by compounds 1), 3), 4), 6) above with a bistertiary diamine bi which is a reactive bifunctional compound

screw of the compound a t, the molar ratio b i: a t being between 0.1 ■ and 0.9;

III) the quaternization product of a compound a2 chosen from the group formed by: 1) bishalohydrins resulting from reaction 65 of an epihalohydrin with piperazine, a bisphenol and / or a bismercaptan, 2) bisazetidiniums, 3) bishaloacyldiamines, 4) alkyl bishalides of formula Fj, 6) bisepoxides, 7) bisinsaturated derivatives, 8) oligomers II obtained by reaction of a

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compound a3 chosen from the group formed by compounds 1), 2), 3), 4), 6), 7) above, with a compound b3 which is a bifunctional compound reactive with respect to compound a3 and chosen from the group formed by primary amines, bissecondary diamines, bismercaptans and bisphenols, the molar ratio b3: a3 being between 0.1 and 0.9.9) the oligomers obtained by reaction of an epihalohydrin (compound a4) with a bifunctional compound b4 chosen from piperazine, bismercaptans, bisphenols, piperazine bisepoxides, the molar ratio of compound b4: epihalohydrin being between 0.1 and 0.9.10) the oligomers obtained by reaction of a compound a5 chosen from the group formed by: 1) bishalohydrins resulting from the reaction of an epihalohydrin with piperazine, a bisphenol and / or a bismercaptan, 2) bishaloacyldiamines, 3) alkyl bishalides of formula Fi, 4) bisepoxides, with a compound bs chosen from the group of bist diamines ertiaries, the molar ratio b5: a5 being between 0.1 and 0.9, comprising tertiary amine groups which can be alkylated, with an alkylating agent c chosen from the group formed by chlorides, bromides, iodides, sulfates, mesylates and tosylates of methyl or ethyl, benzyl chloride or bromide, ethylene oxide, propylene oxide and glycidol.

The acids which can be used for the preparation of the polyaminopoly-amides A are chosen from saturated organic dicarboxylic acids having from 6 to 10 carbon atoms, for example adipic acids, 2,2,4-trimethyl and -2,4,4 adipic, terephthalic, aliphatic mono- and dicarboxylic acids with ethylenic double bonds, for example acrylic, methacrylic, itaconic acids.

Among the preferred acids are adipic acid and the compounds for adding an alkylenediamine with unsaturated acids such as acrylic, methacrylic and itaconic acids.

Adipic acid is particularly preferred.

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

The polyamines which can be used for the preparation of polyamino-polyamides A are chosen from polyalkylene / bisprimary, mono- or disecondary polyamines, for example diethylenetriamine, dipropylenetriamine, triethylenetetramine and their mixtures.

The polycondensation is carried out by known methods, by mixing the reagents, then heating between 80 and 250 ° C, and preferably between 100 and 180 ° C for 1 to 8 h depending on the reagents used. After heating at total reflux for 1 to 1 hour, the water or alcohol formed during the polycondensation is removed, first at ordinary pressure, then under reduced pressure.

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

In carrying out the reaction, an amount of dicarboxylic acid and amines is preferably used in equimolar proportions.

According to a preferred method of preparation, the polyalkylene / polyamine is preferably polycondensed preferably chosen from diethylenetriamine, triethylenetetramine, dipropylenetriamine and their mixtures, either i) on a dicarboxylic acid, preferably adipic acid or its ester dimethyl, or ii) on the intermediate product of one molecule of ethylenediamine and two molecules of methyl ester of an ethylenically unsaturated acid such as methyl acrylate, methacrylate or itaconate.

The reactions for adding ethylenediamine to the unsaturated esters are carried out by mixing the reactants between 5 and 80 ° C., and the polycondensation reactions by heating for 30 to 60 min at reflux, then with elimination of the methyl alcohol at 120-150 ° C, or water at 140-175 ° C, first at ordinary pressure, then under a partial vacuum of 15 mm of mercury.

The polyaminopolyamides A thus obtained have a viscosity in water at 10% and at 25 ° C of less than 3 cPo.

The constitution of the preferred polyaminopolyamides A can be represented by the general formula (I)

-t-OC-R-CO-ZH- (I)

where R represents a bivalent radical which derives from the acid used or from the adduct of the acid with the bisprimary or bissecondary amine.

Among the preferred meanings of R, the following can be cited:

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. - (ch2) 4-,

-ch2-ch2-nh-ch2-ch2-nh-ch2-ch2-,

-ch-ch2-nh-ch2-ch2-nh-ch2-ch-, I I

ch3 ch3

- CH - CH2

\

/ CH2

CH -

N - CH ~ - CH,

NOT

CE0 - G

2 II

These radicals are derived respectively from terephthalic acid, adipic acid, from the addition product of ethylenediamine on acrylic, methacrylic and itaconic acids or their esters. Z represents:

1) in the proportions of 60 to 100 mol%, the radical 55

—NH - [(CH2) X — NH -4H (I)

where x = 2 and n = 2 or 3 or else x = 3 and n = 2,

this radical deriving from diethylenetriamine, triethylene- 60

tetramine or dipropylenetriamine;

2) in the proportions of 0 to 40 mol%, the radical (II) above, in which x = 2 and n = 1 and which is derived from ethylenediamine, or the radical

X

it

0

- CH.

O

derived from piperazine;

3) in the proportions of 0 to 20 mol%, the radical - NH— (CH2) 6 — NH - deriving from hexamethylenediamine.

The polyaminopolyamides thus obtained are then crosslinked by adding a crosslinking agent chosen from those described above.

The crosslinking reactions are carried out between 20 and 90 ° C, starting from aqueous solutions of 20 to 30% of polyaminopolyamide to which the crosslinking agent is added in very small fractions, until a significant increase in viscosity is obtained, but without however reaching the gel which would no longer dissolve in water. The concentration is then quickly adjusted to 10% by adding water and the reaction medium possibly cooled.

According to a preferred characteristic of the invention, polyaminopolyamide polymers of 0.025 to 0.35 mol of crosslinking agent are used for the crosslinking by amine group of the polyaminopolyamide. An interesting 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 polyaminopolyamide. Another 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.

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The proportions of crosslinker to be used, which vary according to the nature of the polyaminopolyamide and of the crosslinker, can be easily determined by adding the desired crosslinking agent to an aqueous solution of the polyaminopolyamide until the viscosity of a 10% solution is , at 25 ° C, between 3 cPo and the gel state, while retaining perfect solubility in water.

The crosslinked polymers according to the present invention keep well and are compatible with anionic surfactants while ensuring good disentangling of wet hair. This compatibility with anionic surfactants can be further improved by alkylation of the secondary amino groups of the crosslinked polyaminoamides. The alkylation increases the water solubility of the crosslinked polyaminoamides in the presence of anionic surfactants.

As an alkylating agent, it is possible to use:

1) an epoxide, for example glycidol, ethylene oxide, propylene oxide;

2) a compound with an ethylenic double bond, for example acrylamide, acrylic acid;

3) chloracetic acid;

4) an alkanesulfone, for example propanesulfone or butanesulfone.

The alkylation of the crosslinked polyaminoamides is carried out in aqueous solution, at a concentration of 10 to 30%, at a temperature between 10 and 95 ° C.

The crosslinked polymers according to the invention can be used in different cosmetic compositions for hair, for the treatment of normal hair, and more particularly of sensitized hair. They can also be used at concentrations of 0.1 to 5%, preferably 0.2 to 2.5% and advantageously 0.3 to 1.3% in cosmetic compositions for hair, and more particularly in compositions shampoos, such as anionic, cationic, nonionic, amphoteric or zwitterionic shampoo, coloring shampoo, dye, styling gel, styling lotion, brushing lotion, styling lotions, rinsed lotion , non-rinsing strengthening styling lotion, in restructuring compositions, in more specific cosmetic compositions such as dandruff, antiseborrhoeic, permanent compositions.

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The subject of the invention is therefore also a cosmetic composition for hair containing at least one crosslinked polymer soluble in water, chosen from crosslinked polymers obtained by the crosslinking of a polyaminopolyamide prepared by polycondensation of an acidic compound chosen from: i ) organic dicarboxylic acids, ii) mono- and dicarboxylic aliphatic acids with ethylenic double bond, iii) esters of the abovementioned acids, iv) mixtures of these compounds, on a polyamine chosen from polyalkylene / bisprimary and mono polyamines - or secondary, 0 to 20 mol% of this polyamine which can be replaced by hexa-methylenediamine or 0 to 40% of this polyamine which can be replaced by a bisprimary amine, preferably ethylenediamine or by a bissecondary amine, preferably piperazine, the crosslinking being carried out by means of a crosslinking agent chosen from the group formed by:

I) the compounds chosen from the group formed by: 1) bishalohydrins, 2) bisazetidiniums, 3) bishaloacyls of diamines, 4) alkyl bishalides;

II) the oligomers obtained by reaction of a compound chosen from the group formed by: 1) bishalohydrins, 2) bisazetidiniums, 3) bishaloacyls of diamines, 4) alkyl bishalides, 5) epihalohydrins, 6 ) diepoxides, 7) bisunsaturated derivatives, with a compound b which is a bifunctional compound reactive with respect to compound a;

III) the quaternization product of a compound chosen from the group formed by compounds a and oligomers II and comprising tertiary amine groups which can be alkylated with an alkylating agent c chosen from the group formed by chlorides, bromides, iodides, sulfates, methyl or ethyl mesylates and tosylates, benzyl chloride or bromide, ethylene oxide, propylene oxide and glycidol.

The crosslinking is advantageously carried out by means of a crosslinking agent chosen from the following subgroups:

I) the simple bifunctional compounds chosen from the group formed by: 1) bishalohydrins resulting from the reaction of an epihalohydrin with a primary amine, a bissecondary diamine, a bisphenol and / or a bismercaptan, 2) bisazetidiniums, 3) bishaloacyldiamines, 4) alkyl bishalides represented by the general formula:

"V * <Z) m

CH

L

3

©.

CH „

X

.0

CH

al - N

3

e

CH „

X

.0

(CVx * X

(V

where X = Cl or Br, Z denotes

Z® "CH \

: /vs

CH = CH

x = 1 to 3

m = 0or l, n = 0or 1,

m and n cannot at the same time denote 1; moreover, when m = 1, x = 1;

Ai denotes a divalent saturated hydrocarbon radical in C2, C3, C4 or C6 or alternatively the 2-hydroxypropylene radical;

II) the oligomers obtained by reaction of a compound chosen from the group formed by compounds 1), 2), 3), 4) above, 5) epihalohydrins, 6) bisepoxides, 7) bisinsaturated derivatives , with a compound b which is a bifunctional compound reactive with respect to the compound a and chosen from the group formed by primary amines, bissecondary diamines, bismercaptans and bisphenols, the molar ratio b: a being between 0 , 1 and 0.9;

Ilbis) the oligomers obtained by reaction of a compound a! chosen from the group formed by compounds 1), 3), 4), 6) above with a bistertiary diamine bx which is a reactive bifunctional compound vis-à-vis compound a ,, the molar ratio bx: aj being understood between 0.1 and 0.9;

III) the quaternization product of a compound a2 chosen from the group formed by: 1) bishalohydrins resulting from the reaction of an epihalohydrin with piperazine, a bisphenol and / or a bis-65 mercaptan, 2) bisazetidiniums, 3) bishaloacyldiamines, 4) alkyl bishalides of formula F1; 6) bisepoxides, 7) bisunsaturated derivatives, 8) oligomers II obtained by reaction of a compound a3 chosen from the group formed by compounds 1), 2), 3),

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632409

4), 6), 7) above with a compound b3 which is a bifunctional compound reactive with respect to the compound a3 and chosen from the group formed by primary amines, bissecondary diamines, bismercaptans and bisphenols, the molar ratio b3: a3 being between 0.1 and 0.9.9) the oligomers obtained by reaction of an epihalohydrin (compound a4) with a bifunctional compound b4 chosen from piperazine, bismercaptans, bisphenols, bisepoxides of piperazine, the molar ratio of compound b4: epihalohydrin being between 0.1 and 0.9.10) the oligomers obtained by reaction of a compound as chosen from the group formed by: 1) the bishalohydrins resulting from the reaction of an epihalohydrin with piperazine, a bisphenol and / or a bismercaptan, 2) bishaloacyldiamines, 3) alkyl bishalides of formula 4) bisepoxides, with a compound b5 chosen from the group of bistertiary diamines, the molar ratio b5: a5 being between 0.1 and 0.9, com carrying tertiary amine groups which can be alkylated, with an alkylating agent c chosen from the group formed by methyl or ethyl chlorides, bromides, iodides, sulfates, mesylates and tosylates, benzyl chloride or bromide, ethylene oxide , propylene oxide and glycidol.

The cosmetic composition is characterized in that the crosslinking is carried out by means of 0.025 to 0.35 or else from 0.025 to approximately 0.2 or else from 0.025 to approximately 0.1 mol of crosslinking agent per amine group of the polyaminoamide; in the composition obtained, the crosslinked polymer having all of the following characteristics:

1) it is perfectly soluble in water at 10% without gel formation;

2) the viscosity of a 10% polymer solution in water at 25 ° C is greater than 3 cPo;

3) it does not contain a reactive group and, in particular, it does not have an alkylating property and it is chemically stable.

The cosmetic compositions for hair containing a crosslinked polymer according to the invention can have a pH of between 2 and 11 and preferably between 3 and 8.

The cosmetic compositions for hair according to the invention to be applied to sensitized hair advantageously contain an electrolyte. The presence of the electrolyte in the composition reduces or eliminates the tendency of sensitized hair to permanently fix the polymers. The electrolytes used are alkaline or alkaline earth salts of mineral or organic acids, soluble in water and, preferably, the chlorides and acetates of sodium, potassium, ammonium and calcium. The amount of electrolyte is not critical. It is preferably between 0.01 and 5% and advantageously from 0.4 to 3% of the total weight of the composition. The electrolyte: polymer ratio is between 0: 1 and 1.5: 1.

The cosmetic compositions for hair can be colored and contain from 0.01 to 0.5% of dyes of the total weight of the composition. They also 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 present in an amount of 0.1 to 5% and preferably from 0.1 to 3% by weight of the total weight of the composition.

The hair compositions which are the subject of the present application can be presented in the form of aqueous or hydroalcoholic solutions (the alcohol being a lower alkanol such as ethanol or isopropanol), or in the form of creams, gels , dispersions or emulsions.

In addition to crosslinked polyaminopolyamides, the cosmetic compositions generally comprise various adjuvants usually used in cosmetic compositions for hair. The adjuvants generally present in these cosmetic compositions are, for example, perfumes, dyes, preserving agents, sequestering agents, thickening agents, emulsifying agents, anionic, cationic, amphoteric, zwitterionic or nonionic surfactants, synergists, softeners, polymers or cosmetic resins, in particular nonionic or cationic.

The cosmetic compositions for hair according to the invention constitute in particular treatment creams to be applied before or after coloring or bleaching, before or after shampooing, before or after a perm, coloring products, shampoos, rinsed lotions to be applied before or after shampooing, styling lotions, brushing lotions, structuring lotions.

When the compositions of the invention constitute treatment creams to be applied before or after coloring or bleaching, before or after shampooing, before or after a perm, these supports are formulated based on soaps or fatty alcohols in the presence of emulsifiers. They can also contain fatty amides, glycerin, polymers, perfumes, dyes.

The pH of these creams is between 3 and 9 and preferably between 5 and 9.

Soaps can be made from natural or synthetic C, 2-C18 fatty acids (such as lauric acid, myristic acid, palmitic acid, oleic acid, ricinoleic acid, l stearic acid and isostearic acid) at concentrations between

10 and 30% and basifying agents (such as soda, potash, ammonia, monoethanolamine, diethanolamine, tri-ethanolamine).

Among the fatty amides, use may in particular be made of the following compounds: the mono- or diethanolamides of the acids derived from coconut, lauric acid or oleic acid at concentrations of between 0 and 10%.

Among the fatty alcohols, it is possible to use in particular the oleic, tetradecyl, cetyl, stearyl and isostearyl alcohols at concentrations of between 0 and 10%.

Creams can also be formulated from natural or synthetic Ci2-Cla alcohols in mixture with emulsifiers. Among the fatty alcohols, mention may in particular be made of: alcohol derived from coconut fatty acids, tetradecyl alcohol, cetyl alcohol, stearyl alcohol, hydroxystearyl alcohol at concentrations of between 5 and 25%.

Emulsifiers can belong to the following classes:

- Non-ionic surfactants, such as oxy-ethylenated or polyglycerolated fatty alcohols, such as, for example, polyoxyethylenated oleic alcohol with 10 mol of ethylene oxide, oxy-ethylenated cetyl alcohol with 6 to 10 mol of ethylene oxide, oxyethylenated cetylstearyl alcohol with 10 mol of ethylene oxide, stearyl alcohol with 10.15 or 20 mol of ethylene oxide, polyglycerolated oleic alcohol with 4 mol of glycerol and synthetic fatty alcohols in Cg-C15 polyoxyethylenated with 5 or 10 mol of ethylene oxide. These nonionic agents are present in an amount of 5 to 25% by weight.

- Anionic surfactants, such as alkyloxyethylenated sulfates or not, such as sodium lauryl sulfate, ammonium lauryl sulfate, sodium cetyl stearyl sulfate, triethanolamine cetyl stearyl sulfate, monoethanolamine lauryl sulfate, lauryl ether sulfate oxyethylenated sodium (with 2.2 mol of ethylene oxide for example) and oxyethylenated monoethanolamine laurylethersulfate (with 2.2 mol of ethylene oxide for example). These constituents are present at concentrations of between 3 and 15% by weight.

As examples of fatty amides, mention may be made of oleic diethanolamide, coconut mono- or diethanolamide, monoethanol-stearic amide. These amides are used at concentrations between 0 and 10%.

- When the compositions of the invention constitute coloring creams, they comprise, in addition to the crosslinked polyaminoamide, various ingredients allowing presentation in the form of the creams defined above, to which an alkalizing agent and dyes are added.

The pH of these compositions is generally between 9 and 11, and

It can be adjusted by adding a suitable basifying agent to the dye support, for example by adding ammonia, monoethanolamine, diethanolamine or triethanolamine.

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The dyes belong to the class of oxidation dyes to which direct dyes such as azo, anthraquinone, nitro derivatives of the benzene series, indamines, indoanilines, indophenols or other oxidation dyes can be added. such as the leuco derivatives of these compounds.

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

Among the anionic surfactants, mention may be made in particular of the following compounds, as well as their mixtures: alkali salts, magnesium salts, ammonium salts, amine salts or amino alcohol salts of the following compounds:

- alkylsulphates, alkylethersulphates in which the alkyls has a linear chain from Q 2 to C, 8, alkylamidesulphates and ethoxylated ethersulphates with linear chains from C12 to Ci8, alkylarylpolyethersulphates, monoglyceride sulphates.

- alkylsulfonates in which the alkyl has a straight chain from C12 to Cj 8, alkyllamidesulfonates, alkylarylsulfonates, <x-olefinesulfonates with straight chains from Ct 2 to Q 8;

- alkylsulfosuccinates, alkylethersulfosuccinates, alkylamidesulfosuccinates in which the alkyl has a linear chain of C12-C18;

- alkyl sulfosuccinamates whose alkyl has a linear chain from C12 to C18;

- alkyl sulfoacetates in which the alkyl has a chain from C12 to C18;

- alkylphosphates, alkyl etherphosphates whose alkyl has a chain of Ci2 to C18;

- alkylsarcosinates, alkylpolypeptidates, alkyllamidopoly-peptidates, alkylisethionates, alkylauraurates in which the alkyl has a chain of C12 to Ci8;

- fatty acids such as oleic, ricinoleic, palmitic, stearic acid, coconut oil acids, or hydrogenated coconut oil, carboxylic acids, carboxylic acids of polyglycolic ethers of formula Alk - (OCH2 - CH2) n - OCH2 - C02H, with Alk having a linear chain from C12 to C18 and n being an integer from 5 to 15.

Among the cationic surfactants which can be used alone or as a mixture, there may be mentioned in particular:

- salts of fatty amines, such as alkylamine acetates,

- quaternary ammonium salts such as chlorides, alkylmethylbenzylammonium bromides, alkyltrimethylammonium, alkylmethylhydroxyethylammonium, dimethyl-distearylammonium, alkyl metamidoethyltrimethylammonium methosulphates,

- alkylpyridinium salts,

- imidazoline derivatives.

Mention may also be made of amine oxides of a cationic nature, such as alkyl dimethylamine oxide or alkylaminoethyl dimethylamine oxide.

Among the nonionic surfactants, which can optionally be used in admixture with the anionics mentioned above, there may be mentioned:

- condensation products of a monoalcohol, an α-diol, an alkylphenol or an amide with glycidol, for example the compounds of formula

R - CHOH - CH2 - O - (CH2 - CHOH - CH2 - O ^ H

in which R denotes an aliphatic, cycloaliphatic or arylaliphatic radical having from 7 to 21 carbon atoms and their mixtures, the aliphatic chains possibly comprising ether, thioether and hydroxymethylene groups and 1 ^ n ^ 10; compounds of formula RO [C2H30 (CH20H)] n H in which R denotes an alkyl, alkenyl or alkylaryl radical having from 8 to 22 carbon atoms and n denotes a number between 1 and 10,

- alcohols, alkylphenols or polyethoxylated or polyglycerolated fatty acids with a linear fatty chain, Cs to C18, most often comprising from 2 to 15 mol of ethylene oxide, for example polyoxyethylene lauric alcohol with 12 mol of oxide of ethylene,

- copolymers of ethylene and propylene oxides,

- condensates of ethylene and propylene oxides on fatty alcohols,

- polyethoxylated fatty amides,

- polyethoxylated fatty amines,

- ethanolamides,

- fatty acid esters of glycol,

- fatty acid esters of sorbitol,

- fatty acid esters of sucrose.

Among the amphoteric surfactants which can be used, there may be mentioned in particular:

- mono- and dipropionate alkylamino,

- betaines, such as N-alkylbetaines, N-alkylsulfobetaines, N-alkylamidobetaines,

- cycloimidiniums (alkylimidazolines).

All these detergents, as well as many others not mentioned here but usable 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 various adjuvants such as, for example, perfumes, dyes, preservatives, thickeners, foam stabilizers, softening agents, cosmetic resins.

Among the foam stabilizers, mention may be made of fatty amides and in particular coconut mono- or diethanolamides, lauric mono- or diethanolamide.

In these shampoos, the detergent concentration is generally between 3 and 50% by weight, relative to the total weight of the composition, preferably from 3 to 20%, and the pH is generally between 3 and 9.

- • When the compositions of the invention constitute lotions, they can be styling lotions, shaping lotions (called brushing lotions), non-rinsed lotions for strengthening styling, rinsed lotions (called rinses ), etc.

By shaping lotion or brushing lotion is meant a lotion applied after shampooing and which promotes shaping of the hair, this shaping being carried out, on wet hair, using a brush, at the same time as drying the hair using a hand dryer.

The term “non-rinsed lotions for strengthening styling” means a lotion applied after shampooing and before styling; this lotion, which is not removed by rinsing, facilitates subsequent styling and lengthens its duration.

These lotions comprise, in aqueous, alcoholic or hydroalcoholic solution, at least one crosslinked polyaminoamide as defined above. They can also contain film-forming polymers such as polyvinylpyrrolidone, polyvinyl-pyrrolidone / vinyl acetate copolymers, copolymers resulting from the copolymerization of vinyl acetate and an alkyl vinyl ether.

Among the preferred resins, mention may be made of polyvinylpyrrolidone having a molecular weight of 10,000 to 70,000, polyvinylpyrrolidone (PVP) / vinyl acetate (AV) copolymers having a molecular weight of 30,000 to 200,000, the PVP: AV ratio being between 30:70 and 70:30, the terpolymers methyl methacrylate (15-25%) / stearyl methacrylate (18-28%) / dimethyl-aminoethyl methacrylate (52-62%) quaternized or not by sulfate methyl.

- Quaternary polyvinylpyrrolidone copolymers, such as for example the polymer having a molecular weight of the order of

1,000,000 sold under the brand name Gafquat 755 by the GAF Corporation, and the polymer having a molecular weight of the order of 100,000 sold under the brand name Gafquat 734 by the GAF Corporation, cationic graft copolymers resulting from the copolymerization from 3 to 95 % by weight of N-vinylpyrrolidone, from 3 to 95% by weight of dimethylaminoethyl methacrylate and from 2 to 50% by weight of polyethylene glycol such as those described in French patent number 76.15948 of the holder, of the resulting cationic polymers condensation of piperazine or its derivatives: 1) on compounds

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bifunctionals such as alkyl or alkyl aryl dihalides, bisepoxides, epihalohydrins, bisunsaturated derivatives,

2) on a primary amine in which the two hydrogen atoms can be substituted and which behaves like a bifunctional compound;

3) both on an epihalohydrin and on a hydroxylated amine such as diglycolamine, 2-amino 2-methyl 1,3-propanediol or on an amino acid such as glycine, quaternized celluloses such as JR 400 sold by the Union Carbide company.

In these lotions, the polymer concentration is generally between 0.1 and 5% and preferably between 0.1 and 3%, and the pH is generally between 3 and 9.

By rinsed lotions is meant a lotion which is applied before or after coloring or bleaching, before or after shampooing, or between the two stages of a shampoo, before or after permanent, to obtain a conditioning effect of the hair and that the we rinse after a pause.

These compositions can be:

- aqueous or hydroalcoholic solutions with or without surfactants,

- emulsions, or

- gels.

These compositions can be pressurized as an aerosol. The surfactants which can be used in the rinsed lotions are mainly nonionic or cationic surfactants such as those described in the composition of the shampoos and more particularly:

- condensation products of a monoalcohol, an o-diol, an alkylphenol or an amide with glycidol, for example, the compounds of formula r - choh — chj — o— (ch2 — choh— ch2 — h in which R denotes an aliphatic, cycloaliphatic or arylaliphatic radical having from 7 to 21 carbon atoms and their mixtures, the aliphatic chains possibly comprising ether, thioether and hydroxymethylene groups and 1 10; compounds of formula ro [c2:30 ( ch20h)} hh in which R denotes an alkyl, alkenyl or alkylaryl radical having from 8 to 22 carbon atoms and n is between 1 and 10;

- alcohols, alkylphenols or polyethoxylated or polyglycerolated fatty acids with a linear fatty chain C8 to C! 8 most often comprising from 2 to 15 mol of ethylene oxide.

The concentration of surfactants in rinsed lotions can vary from 0 to 7%.

Anionic or amphoteric surfactants can also be added.

- When the compositions are in the form of emulsions, they can be nonionic or anionic. The nonionic emulsions consist of a mixture of oils, and / or waxes, fatty alcohols and polyethoxylated fatty alcohols such as stearyl or ketylstearyl polyethoxylated alcohols, for example with 10 mol of ethylene oxide. Cationic agents, such as, for example, those defined above, can be added to these compositions.

Anionic emulsions are made from soaps. Mention may thus be made of the emulsion constituted by self-emulsifiable glycerin stearate sold under the name Imwitor 960 K by the company Dynamit Nobel and the emulsions consisting of a combination of glycerin monostearate with esters of citric acid or else with fatty alcohols and lipopeptides or with alkaline stearates, sold respectively under the names Lameform ZEM, PLM and NSM by the company Grunau.

- When the compositions are in the form of gels, they contain thickeners in the presence or absence of solvents.

The thickeners can be sodium alginate or gum arabic or cellulose derivatives such as methylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropyl-cellulose, carboxymethylcellulose or carboxylic polymers such as Carbopols. A thickener for lotions can also be obtained by mixing polyethylene glycols and polyethylene glycol stearates or distearates, or by mixing phosphoric esters and amines.

The thickener concentration can vary from 0.5 to 30% and preferably from 0.5 to 15% by weight.

The pH of rinsed lotions generally ranges from 2 to 9.5.

When the compositions of the invention constitute restructuring lotions, they contain products which strengthen the keratin chain of the hair.

To this class of products belong the methylol derivatives such as those described in French patents Nos 1527085 and 1519979 of the holder.

The invention will be better understood using the following non-limiting examples.

Examples of preparation

Example A

Polycondensation of adipic acid and diethylenetriamine in equimolar amounts. The constitution of the polymer obtained can be characterized by the following motif:

-f - OC - (CH2) 4 - CONH - (CH2 - CH2 - NH) 2 - | -

To 619 g (6 mol) of diethylenetriamine is added, with stirring and under a nitrogen atmosphere, in 15 min, 876 g (6 mol) of adipic acid. The reaction mixture is then heated to 145-150 ° C, the temperature at which water condensation is noted. It is maintained at reflux for 45 min, then the water is removed by distillation at ordinary pressure for 2 h, then under reduced pressure (15 mm Hg) for 1 h. The heating temperature gradually increases to 170 ° C.

The product thus obtained is poured hot. After cooling, it takes the form of a hard and brittle resin. It is transparent yellow-green in color and completely dissolves in water.

Example the

Preparation of the quaternized crosslinker of formula:

V "\

çh_ ch - ch - n n - ch - ch ch,

H0 / P— '2_ \ 0 /

ch3 ch_so.

3 4

To 236 g of chloroform solution containing 57.2 g (0.289 mol) of bis (epoxypropyl) piperazine, 36.4 g (0.289 mol) of dimethyl sulphate are added over 1 hour while maintaining the reaction medium with stirring at 30 ° C.

The quaternized derivative is then precipitated from its solution in a large excess of ether. After drying, a very viscous oil is collected. Its epoxy titer is 5.19 mEq / g.

Example Ib

Crosslinking, with the crosslinking agent prepared in example la, of the polyaminoamide polymer obtained by condensation of adipic acid on diethylenetriamine.

To 500 g of aqueous solution containing 100 g (0.585 Eq of amine) of polyaminoamide prepared by condensation of equimolar amounts of adipic acid and of diethylenetriamine, according to Example A, 22 g (0.057 mol) are added at room temperature. ) of the quaternized crosslinker prepared in example la, then the temperature of the reaction medium is brought to 90 ° C.

After 20 min, a gelation of the solution is observed. 698 g of water are then quickly added. A clear yellow-green solution containing 10% active material is obtained. The viscosity measured at 25 ° C is 0.68 Po at 87.93 s "1.

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Example IIa

Preparation of the quaternized crosslinker of formula:

CH-

CH,

CÏÏ2 - CH ~ CH2 ~ CHp- C \ -

+ + O

CH-.SO, "7 * +

ch3so4 "

A 187.3 g of chloroform solution containing 54.9 g 15

(0.277 mol) of bis (epoxypropyl) piperazine, 70 g (0.555 mol) of dimethyl sulphate are added over 1 hour while maintaining the reaction medium with stirring at 30 ° C.

The medium thickens during the addition and solidifies after several hours at room temperature. The dough is dissolved at 20

hot in dimethylformamide. When cold, the solution leaves white crystals with a melting point = 205 ° C and an epoxy index of 4.25 mEq / g.

Example IIb

Crosslinking, with the crosslinking agent prepared in Example Ha, of the polyaminoamide polymer obtained by condensation of adipic acid on diethylenetriamine.

To 476 g of aqueous solution containing 95.2 g (0.557 Eq of amine) of polyaminoamide prepared according to example A, 20 g (0.0425 mol) of the crosslinking agent prepared above are added at room temperature. The reaction mixture is kept stirring at 90 ° C for 1 h, then the solution is brought to 10% of active material by the addition of 656 g of water.

The solution is clear, yellow-green in color. The viscosity measured at 25 ° C is 0.27 Po at 87.93 s-1.

Illa example

Preparation of a bisunsaturated oligomer crosslinker obtained from piperazine bisacrylamide and piperazine in the molar proportions of 3/2 and having the formula:

ch2 = ch-

n -co-ch „-ch„

-n ^ ^ ji-ch2-ch2-

's /

-co-ch = ch „

To 380 g of aqueous solution containing 194 g of bisacrylamide (1 mol) is added, within 1 h, between 10 and 15 ° C, 223 g of aqueous solution containing 56.8 g (0.66 mol) of piperazine. The reaction medium is then left for 24 h at room temperature. The solution becomes cloudy and thickens. It is clarified by heating, then poured dropwise into 51 of acetone. The crosslinker precipitates. After filtration and drying, a white solid is collected, the dry extract of which is 80%.

Example Illb

Crosslinking, with the crosslinking agent prepared in example lila, of the polyaminoamide polymer obtained by condensation of adipic acid on diethylenetriamine.

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To 370 g of aqueous solution containing 111 g (0.649 Eq of amine) of polyaminoamide prepared according to Example A, 50 g of the crosslinker prepared above is added at room temperature, then the temperature of the reaction medium is brought to 90 ° C. After 30 min, the medium gels. The solution is quickly brought back to 10% of dry extract by adding 1050 g of water.

A clear yellow-green solution is obtained, the viscosity of which, measured at 25 ° C., is equal to 58 cPo.

35 Example IVa

Crosslinker bishalohydrin oligomer prepared from epichlorohydrin and piperazine in molar proportions of 5/4 and having the formula:

Cl CH2 CH OH - CH2 — f— ^ - CH2 - CH OH - OHg- ^ Cl n = 4

To 541 g of aqueous solution containing 69.4 g (0.806 mol) of piperazine, 92.5 g (1 mol) of epichlorohydrin are added for 1 h, without exceeding 20 ° C. The reaction medium is still kept stirring for 1 hour at 20 ° C. and then, at the same temperature, 60 g (0.6 mol) of 40% sodium hydroxide are added over 1 hour.

Example IVb

Crosslinking, with the crosslinking agent prepared in Example IVa, of the polyaminoamide polymer obtained by condensation of adipic acid on diethylenetriamine.

To 787.5 g of aqueous solution containing 157.5 g (0.92 mEq in amine) of polyaminoamide prepared according to Example A, 268 g of aqueous solution containing 54.9 g of crosslinker prepared is added at room temperature above. The temperature of the reaction medium is maintained for 4 h 50 min at 90 ° C. A gelling is then observed. By rapid addition of 1100 cm 3 of water, a clear solution with 9.85% of active material is obtained, the viscosity of which, measured at 25 ° C., is equal to 73 cPo.

Example Va

55 Preparation of the quaternized crosslinker of formula:

Cl CH2-CH0H-CH2-

CH-

/ N - CIÎ2 - CHOH - CH2

CH2S0 "? 4

not

-J n

Cl n = 4

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To 330 g of aqueous solution containing 67.7 g (0.752 Eq of amine) of the crosslinking agent prepared in Example IVa, 47.4 g (0.376 mol) of sulfate are added over 1 hour and without exceeding 30 ° C. dimethyl. The reaction medium is kept stirring for a further 2 hours at this temperature.

Example Vb

Crosslinking, with a crosslinker prepared in Example Va, of the polyaminoamide polymer obtained by condensation of adipic acid on diethylenetriamine.

To 327.7 g of aqueous solution containing 65.5 g (0.383 Eq of amine) of polyaminoamide prepared according to Example A, 155 g of aqueous solution containing 47.25 g of crosslinker prepared above is added at room temperature -above. After 4 h of heating at 85 ° C., the reaction medium gels.

By rapid addition of 645 g of water, a clear solution containing 10% of active material is obtained. The viscosity measured at 25 ° C is 0.47 Po at 67.18 s-1.

j q Example Via

Preparation of the bisazetidinium crosslinker of formula:

- CH2 - CHOH - CH2 -

Oh

50 g (0.212 mol) of 1,3-propanol-2 bispiperazine, prepared by adding epichlorohydrin to the piperazine, according to example 15 of French application N ° 74.42279 of November 29, 1971, dissolved in 100 g absolute alcohol, 43.5 g (0.47 mol) of epichlorohydrin is added between 0 and 5 ° C. The reaction medium is left for 24 h at 0 ° C,

then the crosslinker is precipitated from its solution in a large excess of ether. A white solid is isolated having a softening point around 120 ° C.

Example VIb

Crosslinking, with a crosslinker prepared in Example Via, of the polyaminoamide polymer obtained by condensation of adipic acid on diethylenetriamine.

To 386 g of aqueous solution containing 77.2 g (0.452 Eq of amine) of polyaminoamide of Example A, 15.4 g (0.036 mol) of crosslinker prepared above is added at room temperature. After 3s 2 Zi h of heating at 90 ° C, the medium gels. By rapid addition of 525 g of water, a clear solution containing 10% of active material is obtained. The viscosity measured at 25 ° C is 0.7 Po at 67.18 s ~~ 1.

Example Vlla 40

Preparation of bis (chloroacetyl) piperazine crosslinker of formula:

cl ch2 - co y it co ch2 cl

45

This crosslinker is prepared by condensation of two molecules of chloroacetyl chloride on a molecule of piperazine in the presence of sodium hydroxide.

Example Vllb 50

Crosslinking, with the crosslinking agent prepared in Example VIIa, of the polyaminoamide polymer obtained by condensation of adipic acid on diethylenetriamine.

To 1000 g of aqueous solution containing 200 g (1.170 Eq of amine) of the polyaminoamide of Example A, the following is added, at temperature 55

ambient, 24 g (0.1 mol) of bis (chloroacetyl) piperazine, then the temperature of the reaction medium is brought to 90 ° C. After 30 min of heating, a gelling of the medium is observed.

1216 g of water are quickly added and heating is continued at 80 ° C for 1 h. A clear solution containing 10% of active material is obtained, the viscosity of which, measured at 25 ° C., is 0.29 Po at 88.41 s "1.

Example Villa

Preparation of the bis- (1,1-bromo-undecanoyl) piperazine crosslinker of formula:

Br (CH2) 10 CO \ CO (CH2) 1QBr

This crosslinker is prepared by condensation of a molecule of piperazine with two molecules of bromo-undecanoyl bromide in the presence of sodium hydroxide.

Example VlIIb

Crosslinking, with the crosslinker prepared in Example Villa, of the polyaminoamide polymer obtained by condensation of adipic acid on diethylenetriamine.

To 113.3 g of aqueous solution containing 56.7 g (0.33 Eq of amine) of polyaminoamide of Example A, 60 g of an isopropanolic solution containing 10 g (0.017 mol) are added at room temperature ) of bis- (1,1-bromo-undecanoyl) piperazine. The reaction medium is heated for 2 hours at reflux of solvent. Isopropanol is then distilled, while adding water until an aqueous solution of resin containing 10% of active material is obtained. The solution is slightly opalescent, its viscosity measured at 25 ° C is 0.052 Po at 87.93 s "1.

Example IXa

Preparation of an oligomer crosslinking agent of formula:

Cl CH2-CH 0H-CH2 -

/ ^ -N /

CH2-CH0H-CH,

Cl

from epichlorohydrin and piperazine in polar proportions 4/3.

To 1149 g of aqueous solution containing 172 g (2 mol) of piperazine, 246.7 g (2.66 mol) of epichlorohydrin are added over 1 hour, while maintaining the reaction medium with stirring at 20 ° C.

After another hour of stirring at 20 ° C., 133 g (1.33 mol) of 40% sodium hydroxide are added at the same temperature and within 1 hour. A precipitation is observed during neutralization. 638 g of water are added and the mixture is heated for a few minutes at 50 ° C. to obtain a clear solution.

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Example IXb

Crosslinking, with the crosslinking agent prepared in Example IXa, of the polyaminoamide polymer obtained by condensation of adipic acid on diethylenetriamine.

To 2000 g of aqueous solution containing 400 g (2.34 Eq of amines) of polyaminoamide prepared according to example A, 584 g of aqueous solution containing 99.8 g of crosslinker prepared in example IXa is added, then the reaction medium is kept stirring at 90 ° C for 5 h. 2414 g of water are then added to obtain a clear solution containing 10% of active material and whose viscosity measured at 25 ° C. is 0.22 Po.

Example Xa

Preparation of an oligomer crosslinking agent of formula:

Cl CH2-CH oh-ch2

"N - ch2-ch 0h-ch2-

Cl

from epichlorohydrin and piperazine in molar proportions 3/2.

To 1221 g of aqueous solution containing 172 g (2 mol) of piperazine, 277.5 g (3 mol) of epichlorohydrin are added over 1 hour and at 20 ° C., keeping the reaction medium under stirring and at 20 ° C. After another hour of stirring, 100 g (l mol) of sodium hydroxide in 40% solution in water are added at a temperature of 20 ° C.

By adding 727.5 g of water and after a few minutes of heating, a clear solution is obtained.

Example Xb

Crosslinking, with the crosslinker prepared in Example Xa, of the polyaminoamide polymer obtained by condensation of adipic acid on diethylenetriamine.

To 2000 g of aqueous solution containing 400 g (2.34 Eq of amines) of polyaminoamide prepared according to example A, 472 g of aqueous solution containing 83.8 g of crosslinker prepared in example Xa are added.

The reaction medium is kept stirring at 90 ° C and, after 4 h of heating, a gelling of the solution is observed.

The solution is quickly brought to 10% of active material by the addition of 2326 g of water.

A clear solution is obtained, the viscosity of which is 0.64 Po at 88.4 s-1.

Example the

The following rinse composition is prepared:

- Compound of example VIb 0.5 g active ingredient

CH,

I

n i

ch-

©

(ch2) 6 -

br

, ©

CH-,

»5

N © i

CH,

CH0 - CHOH - CH.

Br ©

0.5 g active ingredient

- R - CHOH - CH2 - O - (CH2 - CHOH - CH2 -O ^ H 0.7 g R = alkyl Cg to C10; n = mean statistical value of 3.5

- Acid phosphoric ester of oleic alcohol

ethoxylated sold under the name Diva- 5 "

SO linen by Zschimmer and Schwarz 0.4 g

- Eauq.s.p 100 g

The pH of this solution is 7-8.

This rinse composition is applied to previously washed hair. The detangling of the hair thus treated is excellent. Dry hair is particularly plump, shiny and easy to comb.

Example Ib

The following rinse composition is prepared:

- Polymer obtained by condensation of equimolar amounts of adipic acid and diethylenetriamine and crosslinking with 0.11 mol of epichlorohydrin per amine group (according to example 1 of the main patent) 0.5 g active material

- Compound of example VHIb 0.5 g active ingredient

- R-CH0H-CH2-0- (CH2-CH0H-CH2-C% H 0.7g R = C9 to C10 alkyl; n = mean statistical value of 3.5

- Acid phosphoric ester of ethoxylated oleic alcohol sold under the name Diva-

SO linen by Zschimmer and Schwarz 0.4 g

- Eauq.s.p 100 g

The pH of this solution is 7-8.

This rinse composition is applied to previously washed hair. The detangling of the hair thus treated is excellent. Dry hair is particularly plump, shiny and easy to comb.

Example the

An emulsion having the following composition is prepared:

- Vaseline oil 15 g

- Partially sulfated cetylstearyl alcohol sold under the name lanette wax 2.5 g

- Polyethoxylated cetylstearyl alcohol with 10 mol of ethylene oxide sold under the trade name of Simulsol 1951 RD. . 2.5g

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632409

- Compound of example Vllb 0.7 g

- Eauq.s.p 100 g

The pH of this solution is 9.5.

The application, followed by rinsing this rinse in the form of an emulsion on the hair, makes it easier to disentangle it, brings it softness and gives a good nervousness to the hairstyle.

Example ld

An emulsion having the following composition is prepared:

- Vaseline oil 15 g

- Lanette wax (partially sulfated cetylstearyl alcohol) 2.5 g

- Polyethoxylated cetylstearyl alcohol with 10 mol of ethylene oxide, sold under the trade name of Simulsol 1951 RD. . 2.5g

- Compound of example Illb 0.5 g

- Eauq.s.p 100 g

The pH of this solution is 9.

10 This rinse is applied to the hair, left on for a few minutes, then rinsed. Detangling is facilitated, the hair has a harder feel, the nervousness of the hairstyle is improved.

Example 2a ch5 ch3

t I

N © (Gh2) 6 - n ® ch2-ch0h-ch2-

cïï5 ch5

Br "Br"

0.5 g active ingredient

- Compound of example VIb 0.5 g active material 30

- Quaternary polyvinylpyrrolidone copolymer having a molecular weight of approximately 100,000 sold under the name of

Gafquat 734 by General Aniline 0.4 g active ingredient

- Perfume 0.2 g 35

- Dyes 0.05 g

- Eauq.s.p 100 g

The pH is 7.3.

Applied to colored hair, this styling lotion facilitates detangling wet hair.

Dry hair is soft and easy to style. This soft effect persists after several shampoos.

Example 2b

The following styling composition is prepared:

- Compound of example Ib 0.5 g active ingredient

- Quaternary polyvinylpyrrolidone copolymer having a molecular weight of approximately

100,000 sold under the name Gaf- 50

quat 734 by the company General Aniline. . 0.4 g active ingredient

- Perfume 0.1 g

- Dyes 0.01 g

- Eauq.s.p 100 g

The pH is 7.3. 55

Applied to colored hair, this styling lotion facilitates detangling wet hair.

Dry hair is soft and easy to style. This soft effect persists after several shampoos.

Example 2c

The following setting lotion composition is prepared:

- Compound of Example IIb 0.6 g active ingredient

- Quater- 65 polyvinylpyrrolidone copolymer having a molecular weight of approximately

100,000 sold under the name Gafquat 734 by the company General Aniline 0.5 g

- Quaternized cellulose sold under the name of JR 400 by the company Union Carbide 0.3 g

- Ethyl alcohol q.s.p 15 °

- Perfume 0.1 g

- Eauq.s.p 100g

The pH is adjusted to 8.

Applied to washed hair, this styling lotion facilitates detangling. After drying and styling, the hair is soft, shiny and easy to comb. This effect persists after several shampoos.

Example 2d

The following setting lotion composition is prepared:

- Compound of Example IVb 0.3 g active ingredient

- Quaternary polyvinylpyrrolidone copolymer having a molecular weight of approximately 100,000 sold under the name of

Gafquat 734 by General Aniline 0.5 g

- Quaternized cellulose sold under the name JR 400 by the company Union

Carbide 0.3 g

- Ethyl alcohol q.s.p 15 °

- Perfume 0.1 g

- Eauq.s.p 100 g

The pH is adjusted to 8.

Applied to washed hair, this styling lotion facilitates detangling. After drying and styling, the hair is soft, shiny and easy to comb. This effect persists after several shampoos.

Example 3a

The following lotion is prepared for brushing:

- Compound of example Vb 0.6 g active ingredient

- Ethanol q.s.p 10 °

- Dyes 0.1 g

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- Perfume 0.1 g

- Eauq.s.p 100 g

The pH of the solution is adjusted to 7.

Example 3b

The following lotion is prepared for brushing:

- Compound of example Illb 0.4 g active ingredient

- Ethanol q.s.p 10 °

- Dyes 0.1 g

- Perfume 0.1 g

- Eauq.s.p 100 g

The pH of the solution is adjusted to 8.

Example 3c

The following lotion is prepared for brushing:

- Compound of example VlIIb 0.5 g active ingredient

- Ethanol q.s.p 20 °

- Dyes 0.2 g

- Perfume 0.1 g

- Eauq.s.p 100 g

The pH of the solution is adjusted to 6.

Example 3d

The following lotion is prepared for brushing:

- Compound of example Ib 0.5 g active ingredient

- Dyes 0.1 g

- Perfume 0.1 g

- Eauq.s.p 100 g

The pH of the solution is adjusted to 5.

Example 3rd

The following lotion is prepared for brushing:

- Compound of Example IIb 0.8 g active ingredient

- Ethanol q.s.p 40 °

- Dyes 0.05 g

- Perfume 0.1 g

- Eauq.s.p 100 g

The pH of the solution is adjusted to 7.

Example 3f

The following lotion is prepared for brushing:

- Compound of example Vllb 0.6 g active ingredient

- Dyes 0.05 g

- Perfume 0.15 g

- Eauq.s.p 100 g

The pH of the solution is adjusted to 6.

The brushing lotions which are the subject of Examples 3a-3f are applied to wet hair and towel-dried after shampooing. The hair is shaped using a brush, while drying the hair using a hand dryer.

There is a very good passage of the brush and prolonged holding of the hairstyle. We also find that the hair is shiny and soft.

Example 4a

A shampoo of the following composition is prepared:

- Alcoyl C12-C14 triethanolamine sulfate 5 g

- R-CH0H-CH2-0- (CH2-CH0H-CH2-C% H 5g R = alkyl CQ to C10; n = mean statistical value of 3.5

- Lauric diethanolamide 3 g

- Compound of example VIb 1 g

- Perfume 0.1 g

- Dyes 0.01 g

- Eauq.s.p 100 g

The pH is adjusted with triethanolamine to 8.

This shampoo comes in the form of a clear liquid. It facilitates the detangling of wet hair and brings discipline and body to the hair.

Example 4b

A shampoo of the following composition is prepared:

- R-CH0H-CH2-0- (CH2-CH0H-CH2-0 ^ H 10g R = C9 to C12 alkyl; n = mean statistical value of 3.5

- Coconut diethanolamide 3 g

- Dye from Example Illb 1 g active ingredient

- Eauq.s.p 100 g

The initial pH is 8.7, then it is reduced to 6 with lactic acid. Applied on natural hair, this shampoo comes in a clear liquid form. It facilitates the detangling of wet hair. Dried hair is swelling and nervous.

Example 4c

A shampoo of the following composition is prepared:

- Ammonium lauryl sulfate 25 g

- Diethanolamide of coconut fatty acids. . 2 g

- Compound of example VlIIb 1 g active ingredient

- Eauq.s.p 100 g

The initial pH is 8.1, then it is reduced to 7.7 with lactic acid.

Applied to permed dyed hair, this limpid, slightly opalescent shampoo ensures proper disentangling of wet hair. After drying, the hair is swelling and nervous.

Example 4d

A shampoo of the following composition is prepared:

- Polyoxyethylenated lauryl alcohol with

12 mol of ethylene oxide 5 g

- Alkyl hydroxide (C12-Ci8) dimethylcarboxymethylammonium sold by the company Henkel under the trade name Dehyton AB 30 10g

- Lauric diethanolamide 3 g

- Compound of example Ib 0.8 g active ingredient

- Eauq.s.p 100 g

The initial pH is 7.8, then it is reduced to 6 with lactic acid. Applied to dyed hair, this shampoo comes in a clear, slightly opalescent form. Wet hair is easy to untangle and is softer. Dried hair is nervous, swelling and disciplined.

Example 4e

A shampoo of the following composition is prepared:

- Alcohol (C12-C14) triethanolamine sulfate 12.5 g

• - Lauric diethanolamide 2 g

- Compound of Example IIb 0.7 g active ingredient

- Eauq.s.p 100 g

The pH is 7.4, spontaneous.

Applied to natural hair, this limpid liquid shampoo ensures good detangling of wet hair. It slightly facilitates the disentangling of wet hair. Dry hair is plump, nervous and disciplined.

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Example 4f

A shampoo of the following composition is prepared:

- Alcohol (CI2-CÏ4) ethoxylated with 10 mol of ethylene oxide and carboxymethylated, 5

sold under the name Akypo

RLM 100 by Chem Y 3.5 g

- Polyethoxylated lauryl alcohol with 12 mol of ethylene oxide 10 g

- Compound of Example IIb 0.6 g active ingredient m

- Homopolymer of dimethyldi-allylammonium chloride with a molecular weight of approximately 100,000, sold under the name of

Merquat 100 by Merck .... 0.4 g active ingredient

- Eauq.s.p 100 g 15

The pH is 7.4, spontaneous.

Applied to dyed hair, this liquid shampoo improves the detangling of wet hair. Dried hair is disciplined and shiny.

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Example 4g

A shampoo is prepared having the same composition as in Example 4f, except that 0.6 g of compound of Example IIb is replaced by 0.5 g of compound of Example VlIIb.

The properties of this shampoo are similar to those of 25

shampoo from Example 4f.

Example 4h

A shampoo of the following composition is prepared:

- Alcohol (Ci 2-C14) ethoxylated with 10 mol 30 of ethylene oxide and carboxymethylated,

sold under the name Akypo

RLM 100 by Chem Y 3.5 g

- Polyethoxylated lauryl alcohol with 12 mol of ethylene oxide 10 g 35

- Compound of example Ib 0.6 g active ingredient

- Homopolymer of dimethyldi-allylammonium chloride with a molecular weight of approximately 100,000, sold under the name of

Merquat 100 by Merck .... 0.4 g active ingredient 40

- Perfume 0.15 g

- Dyes 0.02 g

- Eauq.s.p 100 g

The pH is adjusted to 7.

Applied to dyed hair, this shampoo ensures good detangling of wet hair and gives dry hair nervousness and bulk.

Example 4i

A shampoo of the following composition is prepared:

- Hydroxypropylmethylcellulose 0.2 g

- Diethanolamide of coconut fatty acids. . 3 g

- Alkoyl (C12-C14) triethanolamine sulfate 10 g

- Compound of example Vllb 0.8 g active ingredient

- Perfume 0.15 g

- Dyes 0.01 g

- Eauq.s.p 100 g

The pH is adjusted to 7.8.

Applied to natural permed hair, this shampoo ensures good disentangling of wet hair and gives dry hair nervousness and bulk.

Example 4d

A shampoo of the following composition is prepared:

- Polyethoxylated lauryl alcohol with 12 mol of ethylene oxide 7 g

- r-choh-ch2-o- (ch2-choh-ch2-o ^ h 7g

R = C9 to C10 alkyl; n = mean statistical value of 3.5

- Diethanolamide of coconut fatty acids. . 2 g

- Compound of Example IVb 0.8 g active ingredient

- Perfume 0.1 g

- Dyes 0.01 g

- Eauq.s.p 100 g

The pH is adjusted to 7.2.

Applied to dyed hair, this shampoo ensures good detangling of wet hair and gives dry hair nervousness and bulk.

Example 4k

A shampoo of the following composition is prepared:

- R-CH0H-CH2-0- (CH2-CH0H-CH2-0 ^ H 10 g R = C9 to C12 alkyl; n = mean statistical value of 3.5

- Diethanolamide of coconut fatty acids. . 3 g

- Compound of Example IIb 0.5 g active material f3

N © I

CH,

CH-

- (CH2) 2 - N © (CH2) g

Cl '

CUCI "

0.2 g active ingredient

Water q.s.p 100 g

The pH, spontaneous at 8.6, is reduced to 6 with lactic acid. Applied on natural hair, this shampoo comes in the form of a clear liquid. Wet hair is easy to untangle. Dry hair is treated, disciplined and shiny.

Example 41

A shampoo of the following composition is prepared:

- R-CH0H-CH2-0- (CH2-CH0H-CH2-0 ^ H 10 g R = alkyl C9 à.Ci2; n = mean statistical value of 3.5

- Alcoyl (C12-C14) triethanolamine sulfate 2 g

- Diethanolamide of coconut fatty acids. . 3 g

- Compound of example Ib 0.5 g active ingredient

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ch-

ch,

I 'I

N0 (CH2) 5 ^ sN © S> (CH2) 6-

i i

CH-

c1 o

Water q.s.p 100 g ch;

cl ©

0.1 g active ingredient

The initial pH is 7.9, then it is reduced to 6 with lactic acid. Applied to dyed hair, this shampoo comes in a slightly opalescent liquid form. Wet hair is easy to untangle and soft. Dry hair is nervous and swelling. 20

Example 4m

A shampoo of the following composition is prepared:

Alcohol (Ci2-C14) ethoxylated with 10 mol of ethylene oxide and carbomethylated, sold under the name Akypo RLM 100 by the company Chem Y 3g

Polyethoxylated lauryl alcohol with 12 mol of ethylene oxide 7 g

Diethanolamide lauric 3 g

Compound of example Illb 0.6 g active ingredient ch-

I

N0

ch3

- -f- NÖ * (CH2) 4 -

Cl

CII-

IT @ -1

CH,

?

(ch2) 6

0.3 g active ingredient

- Eauq.s.p 100 g

The initial pH is 4.5, then it is brought to 7.2 with triethanolamine.

Applied to dyed hair, this shampoo comes in a clear liquid form. Wet hair is easy to untangle. Dry hair is treated, shiny.

Cl

Example 4n

. A shampoo of the following composition is prepared:

- R - CHOH - CH2 - O - (CH2 - CHOH - CH2 - C% H 10 g R = alkyl C9 to C10; n = mean statistical value of 3.5

- Diethanolamides of coconut fatty acids. 2 g

- Compound of example Ib 0.7 g active material

CH-

N + l

CH,

• (CHp)

■ 2J6

Br

CH,

1 3

- + N - (CH2) 4-I

ch3

Br ~

0.3 g

Water q.s.p 100 g

The pH is 7, spontaneous.

Applied to natural permed hair, this shampoo comes in a clear liquid form. Wet hair is easy to untangle and soft. Dry hair is nervous, plump and easy to discipline.

Example 4o

A shampoo of the following composition is prepared:

- Alcoyl Q2-Q 4 triethanolamine sulfate 10 g

60 - Lauric diethanolamide 2 g

- Hydroxypropylmethylcellulose 0.2 g

- Compound of example Vb 0.8 g

- • Perfume 0.1 g

- Dyes 0.01 g

65 - Eauq.s.p 100 g

The pH is adjusted to 8 with triethanolamine.

This clear liquid shampoo improves the detangling of wet hair; it ensures good discipline and treated dry hair.

21

632409

Example 4p

A shampoo of the following composition is prepared:

- Alcoyl C12-C14 triethanolamine sulfate 15 g

- Hydroxypropylmethylcellulose 0.2 g

- Lauric diethanolamide 3 g

- Compound of Example IXb 1 g

- Perfume 0.2 g

- Dyes 0.01 g

- Eauq.s.p 100 g

The pH is 7.7, spontaneous.

Example 4q

A shampoo of the following composition is prepared:

- Alcoyl C12-C14 triethanolamine sulfate 10 g

- Hydroxypropylmethylcellulose 0.3 g

- Compound of example Xb 1 g

- Perfume 0.1 g

5 - Dyes 0.015 g

- Eauq.s.p 100 g

The pH is 7.7, spontaneous.

Example 5 a

10 Deep care cream after shampoo:

• - Cetyl alcohol 20 g

- Cetyl alcohol oxyethylenated with 10 mol of ethylene oxide, sold under the name of

. 15 Brij 50 by Atlas 12 g ch-,

i 5

N ©

i ch,

(gh2> 3

Cl

0

ch-,

I

N0

I

ch,

(ch-)

2y6

Cl

0

1.5 g active ingredient

- Compound of example Vllb 0.5 g active ingredient

- Acid phosphoric ester of ethoxylated oleic alcohol, sold under the name Di-valin SO by the company Zschimmer and

Schwarz lg

- Eauq.s.p 100 g

Example 5b

Deep care cream after shampoo:

- Cetyl alcohol 22 g

- Cetyl alcohol oxyethylenated with 10 mol of ethylene oxide, sold under the name of

Brij 56 by Atlas 10 g

- Compound of Example IVb 0.5 g active ingredient

- Acid phosphoric ester of ethoxylated oleic alcohol, sold under the name Di-valin SO by the company Zschimmer et ch,

35

45

Schwarz 1.2 g

- Eauq.s.p 100 g

The care cream of Example 5a or of Example 5b is applied to clean, damp and towel-dried hair, in sufficient quantity (60 to 80 g) to thoroughly impregnate and cover the hair. Leave to stand for 30 to 40 min and rinse. Wet hair is very soft and easy to untangle. We do the styling and dry under helmet. Dried hair is easily detangled and has a silky feel; they are bright, nervous and have body and volume.

Example 5 c

Deep care cream after shampoo:

- 12g stearic acid

- Oxyethylenated cetylstearyl alcohol with

10 mol of ethylene oxide 4 g

- Monoethanolamine 2 g

- Glycerin 4 g ch-

no

CH,

Cl

(ch3) 2

0

2J6

- n® - (ch ,,)

I

ch,

ClO

1.2 g active ingredient

Compound of example VlIIb 0.5 g active ingredient

Perfumes - Dyes 0.5 g active ingredient

Eauq.s.p 100g

The pH is adjusted to 7.

Example 5d

Deep care cream before shampoo:

- Stearic acid 12 g

- Oxyethylenated cetylstearyl alcohol with

10 mol of ethylene oxide 6 g

632409

22

- Monoethanolamine 3 g

- Glycerin 3 g

- Compound of example Illb 0.8 g active ingredient

- Perfumes - Dyes-

- Eauq.s.p 100 g 5

The pH is adjusted to 7.

The care cream from Example 5c or 5d is applied at a rate of 60 g to dirty, damp hair. We permeate the hair well by kneading. Leave to pause for 30 min. We perform a shampoo. Wet hair is very soft and easy to untangle. After styling and drying, the hair has a particularly soft feel. They are bright, nervous and have body. This effect persists after several shampoos.

Example 6a 15

Structuring lotion applied without rinsing The following composition is prepared:

- Dimethylolethylenethio-urea of formula:

y ch2-n ^

ch2-n ch2oh c = s ch20h

0.5 g

- Quaternary polyvinylpyrrolidone copolymer having a molecular weight of approximately 35,000,000, sold under the name of

Gafquat 755 by General Aniline 0.5 g

- Compound of example Ib 0.4 g active material

- Polyvinylpyrrolidone / vinyl acetate copolymer (70:30) 0.8 g 40

- Phosphoric acid q.s.p. pH 3

- Eauq.s.p 100 g

This lotion is applied to hair washed and towel-dried after shampooing and before styling. It is found that in the wet state the hair is disentangled easily and that it has a silky touch. 45 After styling and drying, the hair is shiny and nervous.

Example 6b

This example is similar to Example 6a, with the difference that the compound of Example Ib is replaced by an equal amount of the compound of Example IVb.

Example 7a

Leave-in lotion ready to use before permanent:

- Trimethylketylammonium bromide. . . 0.1g

- Compound of Example IVb 1.5 g

- Perfume 0.1 g

- Dyes 0.1 g

- Citric acid q.s.p. pH 5

- Eauq.s.p 100 g

Applied on washed hair, this leave-in product facilitates detangling and allows easy application of the perm. It protects the hair and prolongs the hold of the crimp.

60

Example 7b

Leave-in lotion ready to use before permanent:

- Trimethylketylammonium bromide. . . 0.15 g

- Composed of example Vllb 2.2 g

- Perfume 0.2 g

- Dyes 0.01g

- Citric acid q.s.p. pH 4

- Eauq.s.p 100 g

Applied on washed hair, this leave-in product facilitates disentangling and allows easy application of the perm. It protects the hair and prolongs the hold of the crimp.

Example 8a

Permanent '

Reducing liquid:

- Thioglycolic acid 3 g

- Thiolactic acid 2 g

- Ammonia at 22 ° B 4 g

- Triethanolamine 3.5 g

- Compound of example VIb 1.4 g

- Perfume 0.2 g

- Dyes 0.05 g

- Eauq.s.p 100 g

Fixing liquid:

- Potassium bromate 9.5 g

- Cetylpyridinium chloride 1 g

- Tartaric acid q.s.p. pH 6.5

- Perfume 0.1 g

- Dyes 0.05 g

- Eauq.s.p 100 g

On sensitized hair, the reducing liquid is very easily applied and penetrates deeply into the hair. After rinsing and application of the fixing liquid, a very strong and very regular crimping is observed. The hair is in a very beautiful cosmetic condition. After drying, the hair is very soft and particularly shiny. The holding of the hairstyle is particularly good.

Example 8 b Reducing liquid:

- Thioglycolic acid 3.5 g

- Thiolactic acid 2 g

- Ammonia at 22 ° B 3.5 g

- Triethanolamine 4 g

- Composed of example VlIIb 2 g

- Perfume 0.2 g

- Dyes 0.01 g

- Eauq.s.p 100 g

Fixing liquid:

- Potassium bromate 8 g

- Cetylpyridinium chloride 0.8 g

- Tartaric acid q.s.p. pH 6.5

- Perfume 0.2 g

- Dyes 0.05 g

- Eauq.s.p 100 g

On sensitized hair, the reducing liquid is very easily applied and penetrates deeply into the hair. After rinsing and application of the fixing liquid, a very strong and very regular crimping is observed. The hair is in a very beautiful cosmetic condition. After drying, the hair is very soft and particularly shiny. The holding of the hairstyle is particularly good.

Claims (28)

632409 2 CLAIMS 1. Process for the preparation of a cosmetic composition for hair, by mixing a crosslinked polymer soluble in water with at least one diluent or a cosmetic vehicle, characterized in that the polymer is obtained by the crosslinking of a polyaminopolyamide prepared by polycondensation of an acidic compound chosen from: i) organic dicarboxylic acids, ii) aliphatic mono and dicarboxylic acids with ethylene double bonds, iii) esters of the abovementioned acids, iv) mixtures of these compounds, on a polyamine chosen from mono- or disecondary bisprimary polyalkylene polyamines, bisprimary amines and bissecondary amines, at least 60 mol% of said polyamine consisting of mono- or disecondary polyalkylene polyamines; I) the simple bifunctional compounds chosen from the group formed by: 1) bishalohydrins resulting from the reaction of an epihalohydrin with a primary amine, a bissecondary diamine, a bisphenol and / or a bismercaptan, 2) bisazetidiniums, 3) bis-haloacylediamines, 4) the alkyl bishalides represented by the general formula: x "" * 2> x <Z> Ï " CH- N / A, CH „ jîH N I CH 3 © , Q X r0 - (CVx- X (Fx) where X = Cl or Br, Z denotes C CH - CH -CH = CH S VS x = 1 to 3 m = o or 1, n = o or 1, m and n cannot at the same time denote 1; moreover, when m = 1, x = 1; Aj denotes a divalent saturated hydrocarbon radical in C2) C3, C4 or C6 or else the 2-hydroxypropylene radical; II) the oligomers obtained by reaction of a compound chosen from the group formed by compounds 1), 2), 3), 4) above, 5) epihalohydrins, 6) bisepoxides, 7) bisinsaturated derivatives ; with a compound b which is a bifunctional compound reactive with respect to the compound a and chosen from the group formed by primary amines, bissecondary diamines, bismercaptans and bisphenols; the molar ratio b: a being between 0.1 and 0.9; Ilbis) the oligomers obtained by reaction of a compound aj chosen from the group formed by compounds 1), 3), 4), 6) above with a bistertiary diamine b! which is a bifunctional compound reactive with respect to the compound aj; the molar ratio b1: a1 being between 0.1 and 0.9; III) the quaternization product of a compound a2 chosen from the group formed by: 1) bishalohydrins resulting from the reaction of an epihalohydrin with piperazine, a bisphenol and / or a bismercaptan, 2) bisazetidiniums, 3) bishaloacylediamines, 4) alkyl bishalides of formula F1 6) bisepoxides, 7) bisunsaturated derivatives, 8) oligomers II obtained by reaction of a compound a3 chosen from the group formed by compounds 1), 2), 3), 4), 6), 7) above with a compound b3 which is a bifunctional compound reactive with respect to the compound a3 and chosen from the group formed by primary amines, bissecondary diamines, bismercaptans and bisphenols, the molar ratio b3: a3 being between 0.1 and 0.9; 9) the oligomers obtained by reaction of an epihalohydrin (compound a4 with a bifunctional compound b4 chosen from piperazine, bismercaptans, bisphenols, piperazine bisepoxides; the molar ratio of compound b4: epihalohydrin being between 0.1 and 0 , 9; 10) the oligomers obtained by reaction of a compound as chosen from the group formed by: 1) bishalohydrins resulting from the reaction of an epihalohydrin with piperazine, a bisphenol and / or a bismercaptan, 2) bishaloacylediamines , 3) the alkyl bishalides of formula Fj, 4) the bisepoxides, with a compound b5 chosen from the group of bistertiary diamines, the molar ratio b5: a5 being between 0.1 and 0.9; comprising tertiary amine groups which can be alkylated with an alkylating agent c 30 35 40 chosen from the group formed by methyl or ethyl chlorides, bromides, iodides, sulfates, mesylates and tosylates, benzyl chloride or bromide, ethylene oxide, propylene oxide and glycidol, crosslinking being carried out using 0.025 to 0.35 mol of crosslinking agent per amine group of the polyaminoamide. 2. Method according to claim 1, characterized in that the acid compound used for the preparation of the polyaminopolyamide is chosen from adipic acid, terephthalic acid, the esters of these acids, the addition product of ethylenediamine on the acrylic, methacrylic, itaconic acids or their esters. 3. Method according to claim 1, characterized in that the polyalkylene / polyamine used for the preparation of the polyaminopolyamide is chosen from diethylenetriamine, dipropylenetriamine, triethylenetetramine and their mixtures with ethylenediamine, hexamethylenediamine and piperazine. 45 4. Method according to claim 1, characterized in that the polyaminopolyamide is obtained by condensation of adipic acid on diethylenetriamine. 5. Method according to one of claims 1 to 4, characterized in that 0.025 to 0.2 mol of crosslinking agent is used by 50 amine group of the polyaminopolyamide. 6. Method according to claims 1 to 4, characterized in that 0.025 to 0.1 mol of crosslinking agent is used per amine group of the polyaminopolyamide. ss 7. Method according to one of claims 1 to 6, characterized in that the bifunctional compound b according to claim 1 is selected from the group formed by primary amines, bissecondary diamines, bismercaptans. 8. Method according to one of claims 1 to 6, characterized in that the bifunctional compound b according to claim 1 is chosen from the group formed by piperazine and ethane dithiol-1,2. 9. Method according to one of claims 1 to 8, characterized in that the compound a is chosen from the group formed by: 1) bis- 65 halohydrins resulting from the reaction of an epihalohydrin with a primary amine, a bissecondary diamine, a bisphenol and / or a bismercaptan, 2) bisazetidiniums, 3) bishaloacylediamines, 4) alkyl bishalides of formula: 632409 X * (CVx (Z) m- CH, Have CH- - A - It & - " 1 1 CH3 CH, 10th X® (CH) - X 2 x y; CR - CHV ^ V where X = Cl or Br, Z denotes C C \ ch = ch ' x = 1 to 3 m = 0 or 1; n = 0 or 1, m and n not being able to simultaneously designate 1; moreover, when m = 1, x = 1; Aj denotes a divalent saturated hydrocarbon radical in C2, C3, C4, C6 or the 2-hydroxypropylene radical; 5) epihalohydrins, 6) bisepoxides; compound b is chosen from bisphenols. 10. Method according to claim 9, characterized in that the reactive bifunctional compound b is bisphenol A or (4,4'-dihydroxy-diphenyl) -2,2 propane. 11. Method according to claim 1, characterized in that the bifunctional compound bj is chosen from the group formed by bistertiary diamines. 12. Method according to claim 1, characterized in that the bifunctional compound bj is chosen from the group formed by the N, N, N ', N'-tetramethylethylene-, propylene-, butylene-, hexamethylenediamine. 13. Method according to claim 1, characterized in that The alkylating agent c used for the quaternization is dimethyl sulfate. 14. Method according to one of claims 1 to 13, characterized in that the modified bisazetidinium derives from bishalohydrins in which the halohydrin units are linked to the rest of the molecule 25 by tertiary nitrogen groups and comprises two azetidinium groups or an azetidinium group and a halohydrin group. 15. Method according to one of claims 1 to 6, characterized in that the crosslinking of the polymer is carried out by means of an agent 30 crosslinking agent chosen from the group formed by the following compounds: bishalohydrins of formulas: i) x-ch „-ch-ch„ H 21 2 oh n n-ou-ch-ch. S / 2 | 2 oh n = 1 to 4 2) x - ch2-choh-ch2 "n ^ / n-ch2-choh-ch2 ~ / \ -ch2 ~ ch0h-ch2 x 3) X-CH2-CHOH-CH2-N- (CH2) n-N-CH2-CHOH-CH2X n = 2 to 6 CH, CH, 4) X - CH2 - CHOH — CH2 — N — CH2 — CHOH - CH2X R R = C „H2n + 1 n = 1 to 18 or - (CH2 — CH2 —0) mH m = lou2 5) X - CH2 - CHOH - CH20 - [CH2 - CH2OLCH2 - CHOH -CH2X p = 0 to 25 fH3 6) x ch2-ch0h-ch2-0 ^ ^> - ^> - 0 - ch2-choh-ch2x ch3 7) X — CH2 - CHOH — CH2 — S— (CH2) q — S — CH2 — CHOH — CH2X q = 2 to 6 In the above formulas, X denotes Cl or Br; 632409 bisazetidinium of formula: 4 8) HO • o -ch2 ~ ch0h-ch2 Cl rVV Oh Cl labischloracetylethylenediamine, bischloracetylpiperazine, labisbromo-undecanoylethylenediamine, bisbromo-undecanoylpiperazine, bishaloacyldiamine of formula: 9) X— (CH2) n — CON — A — NCO— (CH2) nX ri r2 where X = Cl or Br A = -CH2-CH2-, -CH2-CH2-CH2 or-C- O n = therel0 Ri = R2 = H or R! and R2 are interconnected and together denote the ethylene radical; when A denotes - C—, R! and R2 denote hydrogen, O when A denotes - CH2 — CH2—, Rj and R2 can be linked together and denote together the ethylene radical, the group —N — A — N— denotes Ri R, then the radical piperazine; not N - derived from alkyl bishalides of formula: 10) x "(ch.) (Z) - 2 x m ch N I ch 3 Ê> CH NOT 3 © _ Xe cn3 xe J " <cVx " where X = ClouBr Z denotes xc ch = ch m = 0or 1, n = 0 or 1, 40 m and n cannot simultaneously designate 1; moreover, when m = 1, x = 1; Ax denotes a divalent hydrocarbon radical in C2, C3, x = 1 to 3 c4 or C6 or else the hydroxy-2-propylene radical. 16. Method according to one of claims 1 to 6, characterized in that the crosslinking is carried out by means of a crosslinking agent chosen from the group formed by the following compounds: 6} \ 1) ch0 - ch - ch2 ~ n ^ - ch2 - ch - ch „ \ o / ch, ch3SO4 © 2) ch „- ch - ch0 ~ 'n 2 CL ^ t / ■ ch, s0, o 3 4 ch, ch. iA-nJ 3 n - ch. © © ch, n / a £> 3 4 3) ch2 = ch - co n - co -ch -ch -n Z Z v n-ch "ch -cc ✓ 22 0 -— f n-c0-ch = ch „ 632409 4) Cl CH2 CH OH - CH2 -Your " d1 CH2 - CH OH <- CH2-hr cl n = 4 5) Cl CH2-CHOH-CH2- CH, K ~ \ • / N - CH2 - CHOH - CH, 9 CH-S0.Ö * —3 4 Cl n - 4 6) H ' - CH „- CHOH - CH, OH Cl <9 / \ 7) Cl CH „- CO R N CO CH. Cl 2 N / 2 8). Cl CH2 - CH OH - CH2 - N N - CH „- CH OH - CH_ s <- * z Cl 9) Cl CH2 - CH OH - CH2 / NOT \ "\ NOT CH2 - CH OH - CH2 " Cl 10) Br <CH2) 1o - CO - ^ y - CO - (CH2) l0 - Br 17. Method according to one of claims 1 to 16, characterized in that the crosslinked polymer is combined with a nonionic, anionic, cationic, amphoteric or zwitterionic surfactant for the preparation of a shampoo. 18. Method according to one of claims 1 to 16, characterized in that the crosslinked polymer is combined with a restructuring agent. 19. Method according to one of claims 1 to 18, characterized in that the composition is given a pH between 2 and 11. 20. The method of claim 19, characterized in that the pH is between 3 and 8. 21. Method according to one of claims 1 to 20, characterized in that the crosslinked polymer is incorporated in a proportion of 0.1 to 5% by weight of the total weight of the composition. 22. Method according to one of claims 1 to 21, characterized in that the crosslinked polymer is combined with a water-soluble electrolyte. 23. The method of claim 22, characterized in that the electrolyte is a chloride or acetate of sodium, potassium, ammonium or calcium. 24. The method of claim 22, characterized in that the electrolyte is incorporated in an amount between 0.01 and 5% of the total weight of the composition. 25. Method according to one of claims 1 to 24, characterized in that the crosslinked polymer is combined with another cosmetic polymer. n / a 26. Method according to one of claims 1 to 25, characterized in that the crosslinked polymer is associated with at least one cosmetic adjuvant chosen from perfumes, dyes, sequestering agents, thickening agents, anionic surfactants, cationic, amphoteric, zwitterionic, nonionic, synergists, foam stabilizers, 55 softeners, cosmetic polymers. 27. Method according to one of claims 1 to 26, characterized in that a composition is prepared which is in the form of an aqueous or hydroalcoholic solution, cream, gel, dispersion, emulsion or aerosol. m 28. Cosmetic composition obtained in accordance with the process according to one of claims 1 to 27. 65 In its patent CH No. 619613, the licensee described and claimed for water-soluble crosslinked polymers obtained by the crosslinking of a polyaminopolyamide A prepared by polycondensation of a 632409 chosen acid compound panni: i) organic dicarboxylic acids, ii) aliphatic mono- and dicarboxylic acids with ethylene double bond, iii) esters of the abovementioned acids, iv) mixtures of these compounds: on a polyamine chosen from polyalkylene / bisprimary and mono- or disecondary polyamines, 0 to 20 mol% of this polyamine which can be replaced by hexamethylenediamine or 0 to 40% of this polyamine which can be replaced by a bisprimary amine, preferably ethylenediamine or by an amine bissecondary, preferably piperazine; the crosslinking being carried out by means of a bifunctional crosslinking agent chosen from epihalohydrins, bisepoxides, dianhydrides, unsaturated anhydrides and bisunsaturated derivatives, as well as cosmetic compositions for hair containing at least one crosslinked polymer indicated above and characterized by the following characteristics of the polymer: the polymer is crosslinked using 0.025 to 0.35 mol of crosslinking agent by amine group of the polyaminoamide: the polymer is perfectly soluble in water at 10% without gel formation; it does not contain a reactive group and, in particular, it does not have alkylating properties and it is chemically stable. The viscosity of a 10% solution in water at 25 ° C is greater than 3 cPo and usually between 3 and 200 cPo. The cosmetic compositions for hair constitute hair conditioners compatible with anionic shampoos, while ensuring satisfactory disentangling of wet hair, and good elasticity of dry hair, so as to ensure good hold of the hairstyle. The licensee has discovered that, by reaction of certain crosslinking agents with polyaminopolyamide A, crosslinked polymers are obtained which lead to new cosmetic compositions for hair having, compared to the hair compositions described above, the advantage of ensuring that the hair has a better cosmetic condition, in particular the advantage of imparting more body and elasticity to dry hair and improving the maintenance of the hairstyle. This advantage is more important in the case of damaged hair having undergone successive bleaching and / or perms. The crosslinking agents which can be used in the present process can be classified into the following three groups: s I - Simple bifunctional compounds chosen from the group formed by: bishalohydrins bisazetidiniums bishaloacyldiamines io alkyl bishalides II - The oligomers obtained by reaction of a compound chosen from the groups formed by bifunctional compounds described in group I above and the bifunctional crosslinking agents described in the main application, namely epihalohydrins, bis- 15 epoxides and bisunsaturated derivatives, in particular epichlorohydrin, N, N'-bisepoxypropylpiperazine, diglycidylether, divinylsulfone, methylenebisacrylamide, on a compound b which is a bifunctional compound reactive with respect to compounds a. III - The quaternization product of a compound chosen from the group formed by compounds a (described in the preceding paragraph), and the oligomers described under II and comprising one or more tertiary amine groups which are totally or partially alkylatable with a known alkylating agent and, in particular, with an alkylating agent chosen from the group formed by methyl or ethyl chlorides, bromides, iodides, sulfates, mesylates and tosylates, benzyl chloride or bromide, ethylene oxide, propylene oxide and glycidol. More particularly preferred are the polymers obtained using the crosslinking agents classified in the following subgroups: I) the simple bifunctional compounds chosen from the group formed by: 1) the bishalohydrins resulting from the reaction of an epihalohydrin with a primary amine, a bisecondary diamine, a bisphenol and / or a bismercaptan, 2) bisazetidiniums, 3) bishaloacyldiamines, 4) alkyl bishalides represented by the general formula: X - (CH_) (Z) -2 x rn CH I NOT I CH 3 © 3 0 CH - A1 - N 3 0. CH „ .0 (CVx (F1} where X = Cl or Br Z denotes CH - CH V \ x = 1 to 3 CH = CH m = 0or 1, n = 0 or 1, m and n cannot at the same time denote 1; moreover, when m = 1, x = 1; Aj denotes a divalent saturated hydrocarbon radical in C2, C3, C4 or C6 or else the 2-hydroxypropylene radical; II) the oligomers obtained by reaction of a compound chosen from the group formed by compounds 1), 2), 3), 4) above, 5) epihalohydrins, 6) bisepoxides, 7) bisinsaturated derivatives , with a compound b which is a bifunctional compound reactive with respect to the compound a and chosen from the group formed by primary amines, bisecondary diamines, bismercaptans and bisphenols, the molar ratio b: a being between 0 , 1 and 0.9; Ilbis) the oligomers obtained by reaction of a compound a, chosen from the group formed by compounds 1), 3), 4), 6) above with a bistertiary diamine bt which is a bifunctional compound reactive with respect to screw of the compound at the molar ratio bi: ai being between 0.1 and 0.9; III) the quaternization product of a compound a2 chosen from the group formed by: 1) the bishalohydrins resulting from the reaction 55 of an epihalohydrin with piperazine, a bisphenol and / or a bismercaptan, 2) the bisazetidiniums, 3) bishaloacyldiamines, 4) alkyl bishalides of formula Fj, 6) bisepoxides, 7) bisinsaturated derivatives, 8) oligomers II obtained by reaction of a compound a3 chosen from the group formed by compounds 1), 2 ), 3), 60 4), 6), 7) above with a compound b3 which is a compound bifunctional reactive with respect to the compound a3 and chosen from the group formed by primary amines, bissecondary diamines, bismercaptans and bisphenols, the molar ratio b3: a3 being between 0.1 and 0.9.9) the oligomers obtained by reaction of an epihalo-65 hydrine (compound a4) with a bifunctional compound b4 chosen from piperazine, bismercaptans, bisphenols, piperazine bisepoxides, the molar ratio of compound b4: epihalohydrin being between 0.1 and 0.9; 10) the oligomers obtained by reaction of a 7 632409 compound a5 selected from the group formed by: 1) bishalohydrins resulting from the reaction of an epihalohydrin with piperazine, a bisphenol and / or a bismercaptan, 2) bishaloacylesdiamines, 3) alkyl bishalides of formula F1; 4) bisepoxides, with a compound b5 chosen from the group of bistertiary diamines, the molar ratio b5: as being between 0.1 and 0.9, comprising tertiary amine groups which can be alkylated, with an alkylating agent c chosen from the group formed by chlorides, bromides, iodides, sulfates, mesylates and tosylates of methyl or ethyl, benzyl chloride or bromide, ethylene oxide, propylene oxide and glycidol. The simple bifunctional compounds of group I are described below in more detail. Bishalohydrins obtained by reaction of an epihalohydrin, such as epichlorohydrin or epibromohydrin, with bifunctional compounds, such as bisecondary diamines, primary amines, diols, bisphenols or bismercaptans, form very popular cross-linkers. s Bishalohydrins resulting from the reaction of epichlorohydrin with piperazine are particularly preferred. Bishalohydrins can be direct intermediaries for the preparation of bisepoxides but, conversely, they can be derived therefrom by opening the oxirane ring with a hydracid such as hydrochloric or hydrobromic acid. In both cases, the halogen atom can be linked to the last or the penultimate carbon atom without its position being detrimental to the reactivity of the crosslinker or to the properties of the final product. By way of examples, the following bishalohydrins may be mentioned: X CH „- CH - CH0 2, 2 OH - \ _ CH. - CH - CH „+ - X 2 i OH n = 1 to 4 X - CH2 - CHOH - CH2 - - CH2 - CHOH - CH2 - - CHOH - CH2X X - CH2 - CHOH - CH2 - N - (CH2) n - N - CH2 - CHOH - CH2X n = 2 to 6 CH3 CH3 R R = CnH2n +! or again - (CH2 — CH2—0) mH n = l to 18, m = l ou2 X - CH2 - CHOH - CH20 - [CH2 - CH20] pCH2 - CHOH ~ CH2X p = 0 to 25 CH. -0 - CH2 - CHOH - CH2X X — CH2 — CHOH — CH2 — S— (CH2) q — S — CH2 — CHOH — CH2X q = 2 to 6 In the above formulas, X denotes Cl or Br; Bisazetidinium compounds are derived from N, N-dialkoylhaloohydroxypropylamines by cyclization. So, for example: X CH2 - CHOH - CH2 - Jï - CH2 - CHOH - CH2 - ^ \ - CH2-CHOH-CH2X -> HO - \ N N -CH.-CHOH-CH0-N Nx) OH \ / é "- / 2 2 s— '© V # .0 X denotes Cl or Br 632409 8 However, cyclization can be difficult for some sterically hindered amines. As the reactivity of the azetidinium groups is little different from that of the epihalohydrin groups, it is possible to use, for the purposes of the invention, the compounds derived from bishalohydrins for which the halohydrin units are linked to the rest of the molecule by nitrogen groups tertiary, and comprising two azetidinium groups or an azetidinium group and a halohydrin group. The bishaloacyldiamines which can be used as crosslinking agents can be represented by the following formula: X - (CH2) n - CON - A - NCO - (CH2) nX Ri Rz i5 where X = C1 or Br A = -CH2-CH2-, - CH2 — CH2 —CH2 or —C— O n denotes a number between 1 and 10, Rj = R2 = H or Ri and R2 are linked together and together denote the ethylene radical; when A - C—, Ri = R2 = H; II O when A denotes - CH2 - CH2 -, Rj and R2 can be linked together and together denote the ethylene radical, the group —N — A — N— 20 r. R, 30 - derivative designating the radical - N N piperazine,> v ' Of particular interest for the purposes of the invention are bis-chloroacetyls or bisbromo-undecanoyl of ethylenediamine or piperazine. Among the particularly interesting bisepoxides, mention may be made of piperazine bisepoxides. The oligomers which can be used in the spirit of the invention are statistical mixtures of compounds obtained by reaction of a compound 40 posed described in groups I and II or of a compound aj described in group Ilbis or of a compound a3, a4 or a5 described in group III with respectively a bifunctional compound b, bt, b3, b4, b5, reactive towards compounds a, a15 a3, a4, a5, that is to say generally the primary amines, the bissecondary diamines such as piperazine, the bistertiary diamines such as N, N, N ', N'-tetra-methylethylene-, propylene-, butylene-, or hexamethylenediamines, bismercaptans such as 1,2-ethanedithiol or bisphenols such as bisphenol A or (4,4'-dihydroxy-diphenyl) 2 , 2'-propane. The molar proportions of b, bls b3, b4, b5 with respect respectively to a, ai, a3) a4, as are between 0.1 and 0.9. The oligomerization reactions are generally carried out at temperatures between 0 and 95 ° C and preferably from 0 to 50 ° C in water, or in a solvent such as isopropanol, t-butanol, acetone, benzene, toluene, dimethylformamide, chloroform. The quaternization reactions leading to a quaternization product described above, under III, are carried out between 0 and 90 ° C in water or in a solvent such as methanol, ethanol, isopropanol, t-butanol , alkoxyethanols, acetone, benzene, toluene, dimethylformamide, chloroform.