CH619613A5 - Process for preparing a cosmetic composition for hair - Google Patents

Abstract

The composition is based on a polyamino-polyamide polymer crosslinked by means of 0.025 to 0.35 mol of crosslinking agent per amine group and optionally alkylated, the crosslinking being carried out by means of an epihalohydrin, a diepoxide, a dianhydride or a bisunsaturated derivative. This polymer is distinguished by good solubility at a concentration of 10% in water, by a viscosity in 10% solution in water at 25 DEG C of greater than 3 centipoises, by the absence of reactive groups and by good preservation during storage. The cosmetic composition is compatible with anionic shampoos, provides for easy untangling of the hair and may be applied at room temperature.

Description

The present invention relates to a process for the preparation of a cosmetic composition which makes it possible to improve the condition of the hair as well as the appearance of the hair.

It is known in fact that the hair of many people, as a result of the general condition or degradations consecutive to the action of atmospheric agents or to the action of treatments such as bleaching, perms or dyes, are often difficult to detangle and style, especially with abundant hair. They are generally, and to varying degrees, dry, dull and rough or lack vigor and nervousness.

We have tried to limit or correct these defects by applying to the hair a hair conditioning composition intended to improve the condition of wet hair and dry hair as well as combing and shaping operations.

The term “conditioning of the hair” is understood to mean the operation which, while facilitating the disentangling and combing of wet hair, communicates to the dry hair the plumpness and elasticity, which ensures good maintenance of the hairstyle. The agents which condition the hair are called conditioners.

Synthetic polymers such as polyethyleneimines, polyvinylpyridines, polyvinylbenzyltrimethylammonium polychloride and diallyldimethylammonium polychloride have already been used for conditioning the hair. These polymers have the drawback of not being compatible with anionic shampoos.

Polyaminoamide polymers (obtained by the polycondensation of a dicarboxylic acid and of a polyalkylene polyamine) have also been used in hair compositions, polyamino-ureylene polymers and alkylene-polyamine polymers modified, in particular by epichlorohydrin in amounts close to the stoichiometric proportions relative to the amine groups of the polyaminoamide. The addition of these large quantities of epichlorohydrin results in the presence, in the molecules of the crosslinked polymer, of reactive groups. These polymers indeed contain alkylating groups capable of reacting on nucleophilic groups such as amines, thiols, sulphites, etc. By way of example of such alkylating groups, mention may be made of azetidinium rings.

The first consequence of the existence of such reactive groups is a lack of stability of these compounds which can degrade when they are left in solution.

Furthermore, the existence of such alkylating groups makes these products eminently suspect for their application to human skin.

The use of thermosetting polymers to be crosslinked by heat has also been recommended as a hair conditioner.

The present invention aims to overcome these drawbacks, thanks to a crosslinked polyaminopolyamide having no reactive groups and chemically stable.

The present invention therefore relates to a process for the preparation of a cosmetic composition for hair by mixing with the other components of the composition of at least one crosslinked water-soluble polymer obtained by the crosslinking of a polyaminopolyamide prepared by polycondensation. at least one

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acid chosen from a) dicarboxylic acids free from ethylenic unsaturation and b) aliphatic mono- and dicarboxylic acids with ethylene double bonds and / or at least one ester of the above acids, on at least one polyamine of which at least 50 mol % are chosen from polyalkylene polyamines bis-primary and mono- or disecondary; the crosslinking being carried out by means of a crosslinking agent chosen from epihalohydrins, diepoxides, dianhydrides, and bis-unsaturated compounds; process characterized in that the proportion of crosslinking agent used for crosslinking is from 0.025 to 0.35 mol of crosslinking agent per amine group of the polyaminoamide, this proportion being such that the crosslinked polymer has all of the properties following:

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 an alkyl group.

The acids which can be used for the preparation of the polyamino-polyamides (A) are chosen from:

saturated organic dicarboxylic acids having 6 to 10 carbon atoms, for example adipic, trimethyl-2,2,4 and -2,4,4 adipic, terephthalic, aliphatic mono- and dicarboxylic acids with ethylene 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 or their esters.

The polyamines which can be used for the preparation of the polyamino polyamides (A) are chosen from polyalkylene polyamines bis-primary mono- or disecondary, 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 h to 1 h, 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 equimolecular proportions relative to the primary amino groups of the polyalkylene polyamines.

According to a preferred preparation method, 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 dimethyl ester, or (ii) on the intermediate product of the addition of one molecule of ethylenediamine and two molecules of methyl ester of an ethylenically unsaturated acid such as acrylate, methacrylate or methyl 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 minutes 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 25 ° C of less than 3 cPo.

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

£ OC — R — CO —Z} (I)

where R represents a bivalent radical which derives from the acid used or from the adduct of the acid with the bis-primary or bis-secondary amine.

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

- (ch2) * -

- ch2 - ch2 - nh - ch2 -ch2 - nh - ch2 - ch2 -

- ch — ch2 — nh — ch2 — ch2 — nh — ch2 — ch— I • I ch3 ch3

CH - CH_ CH_ - CH -

\ ^

N - CH0 - CH „- N

/ 2 2 \

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

-NH - [(CH2) X — NH} „(II)

where x = 2 and n = 2 or 3 or else x = 3 and n = 2 this radical deriving from diethylenetriamine, triethylenetetramine or dipropylenetriamine;

2) in the proportions of 0 to 40 mol%, the radical (II), in which x = 2 and n = let which derives from ethylenediamine, or the radical

\ / N — derived from piperazine;

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

The polyaminopolyamides thus obtained are then crosslinked by adding a crosslinking agent. A bifunctional compound chosen from (a) epihalohydrins, for example epichlorohydrin, is used as crosslinking agent; (b) diepoxides, for example diglycidyl ether, N, N'-bisepoxypropylpiperazine;

(c) dianhydrides, for example the dianhydride of butane-tetracarboxylic acid, the dianhydride of pyromellitic acid;

(d) bis-unsaturated derivatives, for example divinylsulfone, methylenebisacrylamide.

A crosslinking agent of advantageous use is epichlorohydrin. Other preferred crosslinking agents are divinylsulfone, methylenebisacrylamide, diglycidylether and N, N'-bisepoxy-propylpiperazine.

These crosslinking agents give rise respectively to the following radicals:

-CH2-CHOH-CH2-

O

II

-ch2-ch2- s-ch2-ch2-

II

O

- CH2 - CH2 - CONH - CH2 - NHCO - CH2 - CH2 -

- CH2 - CHOH — CH2-0-CH2 — CHOH - CH2 -

- CH2 - CHOH - CH2 - N <> N - CH2 - CHOH - CH2 -

Crosslinking reactions are carried out between 20 and 90 ° C, using aqueous solutions of 20 to 30% of polyaminopolyamide

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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 an essential characteristic of the invention, polyaminopolyamide polymers of 0.025 to 0.35 mol of crosslinking agent are used for crosslinking by amine group of polyaminopolyamide. An interesting category of these crosslinked polymers is obtained by using from 0.025 to less than 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 less than 0.1 mol of crosslinking agent per amine group of the polyaminopolyamide.

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.

Exceeding the proportions of crosslinking agent indicated above results in the formation of a gel which cannot be diluted with water, as a result of excessive crosslinking. By further increasing the amount of crosslinking agent, polymers are again obtained which are soluble in water, but which have an evolving character as a function of time and temperature. This evolutionary character is due to the presence in the crosslinked polymer of reactive substituents with respect to nucleophilic groups. When epichlorohydrin is used as crosslinking agent in amounts close to the stoichiometric proportions, the reactive substituents consist mainly of azetidinium rings.

® / n

H9c CH,

I

OH

The crosslinked polymers obtained from polyaminopolyamides known in the art and used in compositions for the hair contain reactive groups and therefore do not keep well.

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 solubility in water of crosslinked polyaminoamides, in the presence of anionic surfactants.

The following can be used as an alkylating agent:

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 alkanesultone, for example propanesultone or butane-sultone.

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 rate of alkylation relative to total basicity, that is to say say the number of moles of alkylating agent fixed relative to the total number of amine groups varies from 0 to 80%. The basicity index of the polymer expressed in milli-equivalents per gram indicates the total number of milliequivalents of basic nitrogen per gram.

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The crosslinked polymers according to the invention can be used in various 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 shampoo, such as anionic, cationic, nonionic, amphoteric or zwitterionic shampoo, coloring shampoo, dye, styling gel, styling lotion, brushing lotion, styling lotion, rinsed lotion , non-rinsing reinforcing strengthening lotion, in restructuring compositions, in more specific cosmetic compositions such as anti-dandruff, antiseborrhoeic compositions.

By rinsed lotion is meant a lotion which is applied after shampooing to obtain a conditioning effect for the hair and which is rinsed after a pause.

By brushing lotion or shaping 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, during the drying the hair using a hand dryer. This technique is suitable for relatively short hair.

By reinforcing lotion which is not rinsed, is meant a lotion applied after shampooing and before styling, which is not rinsed and which facilitates styling and improves its shape and duration.

By restructuring lotion is meant a lotion which contains products which strengthen the keratin chain of the hair. To this class of products belong methylol derivatives such as those described in French patents NM 1527085 and 1519979 of the holder.

These restructuring agents are generally used in combination with cationic compounds which facilitate the disentangling of the hair in the wet state, but have the disadvantage of giving the hair a tacky appearance in the dry state.

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.

They can be in the various usual forms, that is to say: aqueous or hydroalcoholic solutions, gels, creams, dispersions or in the form of aerosols.

They can contain, in addition to the crosslinked polymer, all the components used in hair compositions, in particular anionic, cationic, amphoteric, zwitterionic or nonionic surfactants, synergists, stabilizers, thickeners, emulsifiers, softeners, preservatives, dyes, perfumes, etc. These compositions can also comprise other cosmetic resins, in particular nonionic, cationic or anionic.

The combination of the conditioners of the present invention with non-ionic surfactants provides particularly advantageous shampoos, in particular for the easier disentangling of the hair.

Among the preferred cosmetic polymers or resins which can be used in combination with the crosslinked polymers, mention may be made of 10% crotonic acid / 90% vinyl acetate copolymers with a molecular weight of 10,000 to 70,000, the vinyl-pyrrolidone copolymer (VP) / vinyl acetate (AV) having a molecular weight of 30,000 to 360,000, the PV / AV ratio being between 30:70 and 70:30, the quaternary polyvinylpyrrolidone copolymers having a molecular weight of the order of 1000000, such, for example, that the polymer sold under the brand name Gafquat 755 by GAF Corporation, the cationic polymers resulting from the condensation of piperazine or its derivatives (1) on bifunctional compounds such as alkyl or alkylaryl dihalides , bisepoxides, epihalohydrins, bis-unsaturated derivatives and / or (2) on a primary amine with two hydrogen atoms5

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can be substituted and which behaves like a two-function 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.

Among the surfactants which can be used in combination with the crosslinked polymers, mention may be made of: (a) anionic surfactants such as the alkali or alkanolamine salts of alkanesulfonates, alkyl sulfates and alkyl ether sulfates and their condensation products with ethylene oxide, for example lauryl and sodium or triethanolamine myristylethersulfate, the alkanolamide semi-estersulfosuccinatedisodium, (b) non-ionic surfactants such as: (i) the condensation products of a monoalcohol, of an α-diol or of an alkylphenol with glycidol, for example the compounds of formula R — CHOH — CH2— 0- [CH2 — CHOH — CH2 —0} nH 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 ins 10; (ii) the compounds of formula R0 C2 C2H30 (CH20H)] nH in which R denotes an alkyl, alkenyl or alkylaryl radical and n 10; (c) cationic surfactants such as (i) dimethylhydroxymethyl ketyl ammonium chloride or (ii) tetradecyltrimethylammonium bromide; (d) amphoteric surfactants such as carboxylic derivatives of imidazole.

The cosmetic compositions for hair according to the invention must be applied to sensitized hair advantageously contains 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 sodium, potassium, ammonium and calcium chlorides and acetates. The amount of electrolyte is not critical. It is preferably between 0.01 to 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 polyaminoamide polymers (I) crosslinked with the above crosslinking agents and alkylated with an alkylating agent chosen from acrylamide and glycidol are new compounds.

During the alkylation of a polyaminoamide crosslinked with the acrylamide of formula CH2 = CH — CONH2, the latter condenses on the primary and / or secondary amine groups, giving chains of formula

I

- N - CH2 - CH2 - CONH2;

glycidol under the same conditions leads to chains of formula |

- N- CH2 - CHOH - CH2OH.

Example 1

Polycondensation of adipic acid and diethylenetriamine

The constitution of the polymer obtained can be characterized by the following motif:

£ OC - (CH2) 4 - CONH - (CH2 - CH2 - NH) 2 •}

To 619 g (6 mol) of diethylenetriamine, 876 g (6 mol) of adipic acid are added, with stirring and under a nitrogen atmosphere, over 15 min. 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

Crosslinking of the polymer obtained according to Example 1 with epichlorohydrin s To 200 g of resin, obtained according to the process described in Example 1, dissolved in 800 g of water, 9 g of epichlorohydrin are added, with stirring . The mixture is heated to 90 ° C., then 1.8 g of epichlorohydrin are added in very small fractions and at intervals of 5 to 10 minutes until a viscosity greater than 50 is obtained. cPo at 65 ° C.

The solution is then immediately diluted to a concentration of 10% of dry extract by adding 1098 g of water.

The apparent viscosity measured after 24 h and at 25 ° C is 31 cPo at the speed gradient of 26.3 s-1.

The amount of crosslinker used is 11 mol of epichlorohydrin per 100 amine groups.

Example lb

Crosslinking of the polymer obtained according to Example 1 with methylenebisacrylamide

20 To 70 g of resin prepared according to the method described in Example 1 and dissolved in 280 g of water, 7 g of methylenebisacrylamide are added at room temperature with stirring, then the mixture is heated to 80-90 ° C. After 1 h of heating, a significant increase in viscosity is observed. The mixture is then diluted to 10% of dry extract by adding 413 g of water.

A clear solution is obtained having an apparent viscosity of 32 cPo, measured after 24 h at 25 ° C and under a speed gradient of 26.3 s-1.

3o The amount of crosslinker used is 12.1 mol of methylenebisacrylamide per 100 amine groups of the polyaminopolyamide.

Example the

3J Cross-linking of the polymer obtained according to Example 1 with N, N'-bisepoxypropylpiperazine

To 20 g of polymer prepared according to the method described in Example 1 and dissolved in 80 g of water, 1.50 g of N, N'-bisepoxypropylpiperazine, is added at ordinary temperature and with stirring,

40 then the mixture is heated to 70-80 ° C. After 15 minutes of heating, a gel is obtained which is immediately diluted to 10% of dry extract by the addition of 113.5 g of water.

A clear solution is obtained having a viscosity of 32 cPo measured after 24 h at 25 ° C and under a speed gradient of 26.3 s ~ 1.

The amount of crosslinker used is 7.3 mol of N, N'-bisepoxy-propylpiperazine per 100 amine groups of the polyaminopolyamide.

Example ld

50 Crosslinking of the Polymer Obtained According to Example 1 with Divinyl Sulfone

To 20 g of polymer prepared according to Example 1 and dissolved in 80 g of water is added, drop by drop, at room temperature, until a gelling begins, 1.7 g of divinylsulfone.

55 Then diluted quickly with 100 ml of water.

The apparent viscosity of a 10% solution, measured after 24 h, at 25 ° C and at the speed gradient of 26.3 s-1 is 27 cPo.

The amount of crosslinker used is 13.9 mol of divinylsulfone per 100 amine groups of the polyaminopolyamide.

60 Example 2

Polycondensation of adipic acid and of the diethylene-triamine-piperazine mixture

The constitution of the prepared polymer can be represented by

65 the two reasons below distributed statistically in the proportions of 2: 1.

- [OC - (CH2) 4 - CONH - (CH2 - CH2 - NH) 2}

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- [oc -

and

(ch2) 4

- CO

not

The mixture of 438 g (3 mol) of adipic acid and 86 g (1 mol) of piperazine is heated, with stirring, and in a nitrogen atmosphere for 2 h at 120-135 ° C. The following is then added to this temperature and in the space of 90 min, 206 g (2 mol) of diethylenetriamine. The water formed is distilled for 1 h at 140-170 ° C at ordinary pressure, then 1 h at 170-175 ° C under 15 mm of Hg.

The product thus obtained is in the form of a hard, brittle, transparent resin with a yellow-green color.

Example 2a

Crosslinking of the polymer obtained according to Example 2 with epichlorohydrin

To 200 g of resin, obtained according to Example 2 and dissolved in 800 g of water, 9 g of epichlorohydrin are added, with stirring, at ordinary temperature. The mixture is then heated to 90 ° C. and a further 1.1 g of epichlorohydrin is added in small fractions at 5 or 10 min intervals, until a viscosity of 50 cPo is obtained.

The solution is then quickly diluted with 1091 g of water to obtain a concentration of 10%.

The solution thus obtained is clear and its viscosity, measured after 24 h at 25 ° C, and at a speed gradient of 26.3 s-1 is 52 cPo.

The amount of crosslinker used is 13.2 mol of epichlorohydrin per 100 amine groups of the polyaminopolyamide.

Example 3

Polycondensation of adipic acid and triethylenetetramine

The constitution of the polymer prepared in this example can be represented by the motif:

f OC - (CH2) 4 - CONH - (CH2 - CH2 - NH) 3 ■}

To 292 g (2 mol) of triethylenetetramine, 292 g (2 mol) of adipic acid are added, under small nitrogen and with stirring, under a nitrogen atmosphere, within 20 minutes. The mixture is then heated at total reflux at 145 ° C for 1 h. The water formed is removed by distillation at ordinary pressure for 3 h and under reduced pressure of 15 mm of mercury for 1 h, gradually raising the temperature to 170-175 ° C.

A transparent yellow resin is thus obtained, a 10% solution of which has a viscosity, at 25 ° C., of less than 2 cPo.

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Example 3a

Crosslinking of the polymer obtained according to Example 3 with epichlorohydrin

To 200 g of a 20% aqueous solution of polymer obtained according to the process described in Example 3, 1.8 g of epichlorohydrin are added quickly and with stirring and the mixture is heated to 90-95 ° C. for 30 mins. 0.4 g of epichlorohydrin is then added, at the same temperature, very slowly, until a viscosity greater than 50 cPo is obtained, measured at 65 ° C.

The solution is then immediately diluted to a concentration of 10% of dry extract, by adding 220 g of water. The solution obtained is clear. Its viscosity at 25 ° C and at a speed gradient of 26.3 s "1 is 24 cPo.

The total amount of epichlorohydrin added is 0.0242 mol, which corresponds to 7.8 mol of crosslinker per 100 amine groups of the polyaminopolyamide.

Example 3b

2s Crosslinking of the polymer obtained according to Example 3 with methylenebisacrylamide

To 100 g of aqueous 20% polymer solution, obtained according to the process described in Example 3, 0.8 g of methylenebisacrylamide is added, then the mixture is heated to 70-80 ° C for 25 min. A soft gel is then obtained which is immediately diluted to a concentration of 10% of dry extract, by adding 108 g of water. The solution obtained is clear. Its viscosity, measured after 24 h at 25 ° C and at a speed gradient of 26.3 s -1 is 43 cPo. The amount of methylenebisacrylamide added is equivalent to 3.4 mol of crosslinker per 100 amine groups of the polyaminopolyamide.

Example 4

40 Polycondensation of the reaction product of 2 mol of methyl itaconate and 1 mol of ethylenediamine with diethylenetriamine The composition of the polymer prepared in this example can be represented by the motif:

OC - CH - CH

N - CH2-CH2-N ^

First stage

To 620 g (3.9 mol) of methyl itaconate, 118 g (1.95 mol) of ethylenediamine are added over 1 hour, with stirring and under a nitrogen atmosphere, while maintaining the temperature at 30 ° C.

After one night, at room temperature, the mixture is heated to 80 ° C., to remove the methanol, first at ordinary pressure, then under reduced pressure of 15 mm Hg. The appearance of a precipitate is then noted. The reaction mixture is taken up in 500 ml of benzene and the methanol / benzene azeotrope is distilled.

Concentrate and take up the residue with acetone. In this way, with a yield of 82%, N, N'-ethylenebis- [methyl 4-carboxylate 2-pyrrolidone], in the form of a white powder having a melting point of 141-142 ° C and a saponification index 6.35 mEq / g.

Second stage

To 198 g (0.63 mol) of diester thus obtained, 65.5 g (0.63 mol) of diethylenetriamine are added at room temperature and distillation is carried out.

-CH.

1

0

ÇH - CONH - (CH2-CH2-NHt2j-

CH „

the methanol formed by heating to 120-130 ° C, first at ordinary pressure for 90 min, then under reduced pressure of 15 mm Hg for 30 min.

55 This gives a transparent, hard and brittle yellow-green resin, perfectly soluble in water.

Example 4a

Crosslinking of the polymer obtained according to Example 4 with epi-60 hydrochloride

To 200 g of resin dissolved in 800 g of water, 13 g of epichlorohydrin are added, with stirring, at room temperature. The mixture is heated to 90 ° C. and 2 g of epichlorohydrin are added in small portions, 5 or 10 minutes apart, until a start of gelation is obtained. Then diluted quickly with 1135 g of cold water to bring the solution to 10% of dry extract.

A clear solution is thus obtained, the viscosity of which, measured after 24 h at 25 ° C and at a speed gradient of 26.3 s "1 is 49 cPo.

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The amount of epichlorohydrin used corresponds to 22 mol per 100 amine groups of the polyaminopolyamide.

Example 4b

Crosslinking of the polymer obtained according to Example 4 with methylenebisacrylamide

To 50 g of polymer obtained in Example 4 and dissolved in 200 g of water, 1.5 g of methylenebisacrylamide are added at room temperature with stirring, then the mixture is heated to 85-90 ° C. The crosslinker is then added gradually until a viscosity greater than 50 cPo is obtained at 65 ° C. The concentration of the mixture is then reduced to 10% of dry extract, by the addition of 285 g of water.

A clear solution is obtained, having a viscosity of 54 cPo at 25 ° C and at a speed gradient of 26.3 s-1.

The amount of methylenebisacrylamide added is 3.9 g and it corresponds to 16 mol per 100 amine groups of the polyaminopolyamide.

Example 5

Polycondensation of a mixture of 2 mol of methyl acrylate and 1 mol of ethylenediamine with diethylenetriamine The constitution of the polymer prepared in this example can be represented by the motif:

- [OC - CH2 - CH2 - NH - CH2 - CH2 - NH - CH2 - CH2 -CONH - (CH2 - CH2 - NH ^ rJ-

To 240 g (4 mol) of ethylenediamine, 689 g (8 mol) of sodium hydroxide are added over 2 hours at a temperature between 10 and 20 ° C., with stirring and in a nitrogen atmosphere. methyl acrylate. After 1 h of stirring at room temperature, 413 g (4 mol) of diethylenetriamine are added. The methanol formed is then distilled by heating at 120-140 ° C for 2 h at ordinary pressure and for 2 h under a reduced pressure of 15 mm Hg.

A transparent yellow-orange resin is thus obtained, which in a 10% solution of dry extract, has a viscosity of less than 2 cPo.

Example 5a

Crosslinking of the polymer obtained according to Example 5 with epichlorohydrin

To 200 g of polymer, obtained according to the process of Example 5, dissolved in 800 g of water, 45 g of epichlorohydrin are added, with stirring, at room temperature. It is gradually heated to 90 ° C., then 11 g of epichlorohydrin are added in small fractions, 5 or 10 minutes apart, until the onset of gelling. The concentration is then rapidly diluted to 10% of dry extract, by adding 1504 g of cold water.

A clear solution is thus obtained having a viscosity of 25 cPo, measured after 24 h at 25 ° C and at a speed gradient of 26.3 s "1.

Example 6

Polycondensation of a mixture of 2 mol of methyl methacrylate and 1 mol of ethylenediamine with diethylenetriamine The constitution of the polymer prepared in this example can be represented by the motif:

-E

OC-CH - CE,

NH - CH,

CH „- NH

CH,

-CONH - (CH2 -CH2 -NH ^ -

- ch2-ch QH ^

To 180 g (3 mol) of ethylenediamine, 600 g of methyl methacrylate (6 mol) are added at room temperature. The mixture is left for 3 days, then heated to 80 ° C for 3 hours. 309 g of diethylenetriamine (3 mol) are then added and the mixture is heated at 120-125 ° C for 4 h at ordinary pressure and for 90 min under a reduced pressure of 15 mm of Hg. The polycondensate thus obtained is in the form a bronze-green resin.

Example 6a

Crosslinking of the polymer obtained according to Example 6 with methylenebisacrylamide

To 84.6 g of polymer prepared according to the process described in Example 6 and dissolved in 338.4 g of water, 27.3 g of methylenebisacrylamide are added at ambient temperature and with stirring. The mixture is then heated to 85-90 ° C for 15 min. A gel is then obtained which is immediately diluted to a concentration of 10% of dry extract, by the addition of 669 g of water. A clear solution is obtained having, at 25 ° C and at the speed gradient of 26.3 s-1, a viscosity of 53 cPo.

The amount of crosslinker added corresponds to 21.4 mol per 100 amine groups of the polyaminopolyamide.

20 Example 7

Propanesultone alkylation of the crosslinked polymer according to example la

With 3000 g of aqueous solution at 10% of crosslinked polyaminoamide and prepared according to example la and having a basicity index 25 0.45 mEq / g (1 g of polymer contains 0.45-10-3 amine groups), 113.5 g (0.93 mol) of propanesultone is added with stirring and a nitrogen atmosphere. The reaction mass is then heated to 60 ° C for 4 h. Diluted with 1020 g of water to bring the concentration to 10% of dry extract. The solution thus obtained is yellow in color and has a viscosity of 12.6 cPo at 25 ° C.

Example 8

Alkylation with sodium chloracetate of the crosslinked polymer according to Example 1a

To 2000 g of solution obtained according to example la, 70 g (0.6 mol) of sodium chloroacetate are added with stirring and at ambient temperature, and the reaction mass is then heated to 90 ° C. for 10 h. 270 g of water are then added to bring the concentration to 40% of dry extract. This gives a clear solution, straw yellow in color and whose viscosity at 25 ° C is 21 cPo.

Example 9

Alkylation with glycidol of the crosslinked polymer according to example la 45 A 1000 g of 10% solution of cationic polymer prepared according to example la, 27 g (0.36 mol) are added over 2 h, with stirring. ) of glycidol. Stirring is continued for 5 h and then diluted with 265 g of water to bring the concentration to 10% of dry extract. A clear, slightly colored solution 50 is thus obtained, the viscosity of which, measured at 25 ° C., is 13.8 cPo.

Example 10

Alkylation to the acrylamide of the crosslinked polymer according to Example 55

To 1000 g of 10% aqueous polyaminoamide solution prepared according to example la, 20 g (0.28 mol) of acrylamide are added at room temperature, in the presence of a trace of sodium nitrite. The reaction medium is then heated for 10 h, at 60 ° C. By 60 addition of 180 g of water, a clear polymer solution containing 10% of active material and with a viscosity equal to 11.2 cPo at 25 ° C. is obtained. .

Application examples 65 Example A1

Anionic shampoo

Triethanolamine lauryl sulfate 15 g

Coconut fatty acid diethanolamides 3 g

9

619,613

Polymer prepared according to the example 1.5 g

Water qs 100 g pH = 7

About 10 cm3 of this solution is applied to previously wet hair. We massage lightly. Rinse with water and make a second application. It is massed vigorously to obtain an abundant foam, it is left to stand for 1 min to ensure the fixing of the polymer on the hair, then it is rinsed.

There is a great ease of disentangling wet hair (the comb slides easily in the hair), the hair is very soft, flexible, malleable, the styling is mounted with great ease. After drying and when styling dry hair, there is also an ease of disentangling. The hair is nervous and disciplined.

Example A2 Anionic Shampoo

Modified alkanolamide semi-estersulfosuccinatedisodium (sold under the brand name Monomate

DHL 50 15 g

Sodium lauryl ether sulfate condensed with 2.2 mol of ethylene oxide 15 g

Polymer prepared according to example la 1 g

Water qs 100 g pH = 7.8

EXAMPLE A3 Anionic Shampoo

Sodium lauryl ether sulfate condensed with 2.2 mol of ethylene oxide 12 g

Coconut fatty acid diethanolamides 4 g

Polymer according to Example 5a 1.5 g

Quaternary polyvinylpyrrolidone copolymers having a molecular weight of the order of 1,000,000, sold under the brand name Gafquat 755 by

General Aniline and Film Corp 0.3 g

Water qs 100 g pH = 7.5

Example A4

Anionic shampoo sodium Myristylethersulfate condensed with

2.5 mol of ethylene oxide 5 g

Sodium lauryl ether sulfate condensed with 2.2 mol of ethylene oxide 1 g

Polymer according to Example 4a 1 g

Water qs 100 g pH = 8

Example A5 Anionic shampoo

Triethanolamine lauryl sulfate 10 g

Coconut fatty acid monoethanolamides 1.5 g

Protein hydrolyzate derived from collagen with 80% active ingredients, sold under the brand

Hydropo 220 by Stepan Chemicals 5 g

Polymer according to example 2a 2 g

Water qs 100 g pH = 4

The action of shampoos A2 to A4 is similar to that of shampoo Al. Shampoo A5 also improves the condition of damaged hair by giving more resistance to the fibers and more hardness to the hair.

Example A6

Non-ionic shampoo

R-CHOH-CH2-OfCH2-CHOH-

CH2 - 0} 3.5 H 14 g r = mixture of nonyl to dodecyl radicals

Polymer according to the example la 2,5 g

Lactic acid qs pH = 5

Water qs 100 g

Example Al

Non-ionic shampoo r — CHOH — CH2—0 £ CH2 —CHOH—

ch2 —09-3, îhr = nonyl to dodecyl 12 g

Dimethylhydroxyethylketylammonium chloride 1.5 g

Polymer prepared according to the example 1.5 g

Quaternary polyvinylpyrrolidone copolymers having a molecular weight of the order of 1,000,000 sold under the brand name Gafquat 755 by

General Anilin and Film Corp 0.2 g

Lactic acid qs pH 3

Water qs 100 g

Example A8

Non-ionic shampoo r-choh-ch2-o [ch2-choh-

ch2-0} 3.5h 5 g r = mixture of nonyl to dodecyl radicals

Dimethylhydroxyethylketylammonium chloride. 1 g

C12H250- [CH2-CH-044H 5 g

CH2OH

Polymer of Example 5a 3 g

Lactic acid qs pH 5

Water qs 100 g

Example A9

Non-ionic shampoo

Laury alcohol oxyethylenated with 12 mol of ethylene oxide 7 g

Diethanolamide lauric 3 g

Polymer according to example la 0.5 g

Polymer according to Example 2a 0.8 g

Lactic acid qs pH 4.5

Water qs 100 g

AIO example

Non-ionic shampoo

Laury alcohol oxyethylenated with 12 mol of ethylene oxide 6 g

C12H250- [CH2-CH-044H 4 g

I

ch2oh

Lauric diethanolamide 1.5 g

Polymer according to example 4a 2 g

Lactic acid qs pH 3

Water qs 100 g

The nonionic shampoos of examples AIO apply as the anionic shampoos of examples A1-A5. There is a very great ease of disentangling wet hair and dry hair. The detangling is excellent and the hair retains suppleness and great lightness. The hair has volume and the styling is easy to assemble.

Garlic Example

Styling enhancer

The following lotion is prepared:

90/10 vinyl acetate / crotonic acid copolymer

PM (molecular weight) = 10,000 2.5 g

Polymer according to example la 0.3 g

2-amino 2-methylpropane 1,3-diol qs pH 7 Ethanol qs 50 °

5

10

15

20

25

30

35

40

45

50

55

60

65

619,613

10

Dye 0.01 g

Perfume 0.2 g

Water qs 100 ml

Example Al2

Styling enhancer for oily hair The following lotion is prepared:

Polymer according to example la 0.3 g

90/10 vinyl acetate / crotonic acid copolymer

MW = 50,000 2.5 g

Polyvinylpyrrolidone / vinyl acetate / copolymer having a viscosity of 3.3 cPo (measured at 25 ° C

in 5% solution in ethanol) 0.5 g

2-amino 2-methylpropane 1,3-diol qs pH 7 Ethanol qs 50 °

Dye 0.01 g

Perfume 0.2 g

S-carboxymethylcysteine (antiseborrheic) 0.7 g

Water qs 100 ml

The lotions of Examples All and A12 are applied to wet hair and towel-dried after shampooing and before winding the setting.

We notice on wet hair an easy disentangling. After winding the styling, we see that the hair is more nervous, softer and slightly more shiny. The holding of styling is considerably prolonged.

Example Al3

Brushing lotion (shaping)

The following lotion is prepared:

Polymer according to example la 0.5 g

Ethanol qs 50 °

Dye 0.01 g

Perfume 0.2 g

Water qs 100 ml

This lotion is 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 shinier and softer.

Example Al4

Rinse (rinsed lotion) for fine and soft hair

The following lotion is prepared:

Cetyl / stearyl alcohol 30/70% oxyethylenated at 33% marketed under the brand Cire de Sipol A0 by

Sinnova 1.5 g

Dimethyldistearylammonium chloride, sold under the brand Arquad2HT 75 by Armor ... 1.5 g R-CHOH-ch2-O- [ch2-CHOH-

ch2-o} 3,5h 1 g

R = mixture of nonyl to dodecyl

Polymer according to example 2a 2 g

Quaternary polyvinylpyrrolidone copolymers having a molecular weight of the order of 1,000,000 sold under the brand name Gafquat 755 by

General Anilin and Film Corp 0.5 g

Hydroxyethylcellulose 0.9 g

Maleic acid qs pH 8

Water qs 100 g

This lotion is applied to wet hair and towel-dried after shampooing, it is left to stand for 5 minutes, then it is rinsed.

There is a very good disentangling of wet hair. After styling and drying, the hair is nervous, easy to style and shiny.

Example A15

Styling lotion

The following lotion is prepared:

Polymer according to Example 5a 0.5 g

0.1 g silicone oil

Hydroxyethylcellulose 0.2 g

Ethanol 50 ml

Perfume 0.2 g

Water qs 100 ml

This men's lotion is applied to wet hair. The hair is styled and then dried. We see that the hair is nervous, slightly hardened and stays perfectly in place.

15

65

Example A16

Styling gel

Polymer according to the example la 1 g

Hydroxyethylcellulose 2 g

0.5 g silicone oil

20

Ethanol 40 ml

Perfume 0.02 g

Water qs 100 g

A small amount of this gel, applied to dry hair, ensures good hold of the hairstyle while imparting shine to the hair.

Example A1 7

Structuring lotion without rinsing. 30 Dimethylolethylenethio-urea of formula:

^, CH2OH

ch2-N

\ /

CS

0.5 g ch2-N

ch2oh

Polymer according to example la 0.5 g

40 Phosphoric acid qs pH 3

Water qs 100 ml

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 has a silky feel. 45 After styling and drying, the hair is shiny and nervous, it has body and volume and its feel is soft.

Example A18

A similar result is obtained by replacing the ready-made polymer according to Example 1a with the polymer prepared according to Example 2a.

Example A 19

Structuring lotion, applied with rinsing. Dimethylolethylenethiourea of formula 55 ch2oh

ÇH2-N

\ /

CS

1 g

60 ch2-N

NOT

CH2OH

Polymer according to the example la 1 g

Phosphoric acid qs pH 3

Water qs 100 ml

We apply this lotion to wet and clean hair. Leave to pause for 10 minutes, then rinse.

Hair has a soft feel and is easily detangled.

11

619,613

After styling and drying, the comb passes easily through hair which is shiny, nervous and has volume.

Example A20

By replacing, in the above lotion, the polymer according to Example 1a with the polymer according to Example 2a, an equally good result is obtained.

Examples A21-A22

Styling lotion for sensitized hair. A21 An aqueous solution containing 1% of active material of the compound prepared in Example 1d and 0.5% NaCl is prepared, adjusted with citric acid to pH 7.

Apply to bleached hair. We do the setting and dry.

The hair is hardened and nervous; the touch is silky and the disentangling easy.

A22 An aqueous solution is prepared at 1% of active material of the compound prepared in example le and 1.5% nh4ci, adjusted to pH 5 with lactic acid.

Apply to bleached hair. We do the setting and dry. The hair is hardened. They are elastic and shiny. The touch is silky and the disentangling easy.

Example A23

Treatment lotion applied with rinsing.

25 ml of the following solution is applied to wet and clean hair:

Polymer according to example lb 1.5 g

Citric acid qs pH 5

Water qs 100 g

Leave to stand for 5 minutes and rinse. Hair has a soft feel and is easily detangled. We do the setting and dry. Dry hair is easily disentangled. They are bright and nervous.

Example A24

The same result is obtained by replacing 1.5 g of polymer according to Example 1b with 1 g of polymer according to Example 3a.

Example A25

Structuring lotion applied without rinsing. Dimethylolethylenethiourea of formula

^ ch2OH ch2-n

0.6 g ch2-n

^ CHzOH

Polymer according to Example 3b 0.5 g

Phosphoric acid qs pH 3

Water qs 100 g

The mixture is applied to washed and towel-dried hair before styling. Hair is disentangled easily, the touch is silky. We do the setting and dry.

The hair is shiny, nervous, elastic and has volume. The touch is silky, the disentangling easy.

Example A26

The same result is obtained if the polymer according to Example 3b is replaced by the polymer according to Example 4b.

Example A27

Structuring lotion applied with rinsing Dimethylolethylenethio-urea of formula chjoh ch2-n

/ CS

ch2-n

\

ch2oh

Polymer according to Example 6a

1.5g

1 g

Hydrochloric acid qs pH 3

Water qs 100 g

The mixture is applied to washed and towel-dried hair. Leave to pause for 10 minutes and rinse. Detangling is easy, the hair has a soft, silky feel. We do the styling and dry under 20 helmet.

Dry hair is easily disentangled; they are bright, nervous and have volume.

Example A28

25 Anionic shampoo

Monoethanolamine lauryl sulfate 10 g

Coconut fatty acid monoethanolamides 1.5 g

Polymer according to the example le 1 g

Lactic acid qs pH 7.2 30 Water qs 100 g

Example A29

Anionic shampoo

Sodium lauryl ether sulfate oxyethylenated with

35 2.2 mol of ethylene oxide 6 g

Triethanolamine lauryl sulfate 6 g

Coconut fatty acid diethanolamides 3 g

Polymer according to Example 3a 1.5 g

Lactic acid qs pH 7.6 io Water qs 100 g

Example A30

Anionic shampoo

Same composition as the shampoo of example A29, except that the polymer according to example 3a is replaced by the polymer according to example 3b.

Example A31

Anionic shampoo 50 Sodium Myristylethersulfate, oxyethylenated with

2.5 mol of ethylene oxide 6 g

Monoethanolamine lauryl ether sulfate, oxyethylenated with 2 mol of ethylene oxide 9 g

Coconut fatty acid diethanolamides 3.5 g

55 Protein hydrolyzate derived from collagen, 80%

active ingredients, sold under the brand

Hydropo 220 by Stepan chemicals 3 g

Polymer according to example 4b 1 g

Lactic acid qs pH 7.5 60 Water qs 100 g

Example A32

Anionic shampoo

Same composition as the shampoo of example A31, except that the polymer according to example 4b is replaced by the polymer according to example 6a.

The action of the shampoos of Examples A28 to A30 is similar to that of the shampoo of Example A1. The shampoos of

619,613

12

Examples A 31 and A32 further improve the condition of damaged hair by giving more resistance to the fibers and more hardness to the hair.

Example A33

Non-ionic shampoo ci2h250- [c2h30 (ch20h9-nh 6 g n represents an average statistical value of about 4 Laury alcohol oxyethylenated with 12 mol of ethylene oxide 6 g

Carboxylic derivative of imidazole of formula c11h23c

Example A40

No-rinse structuring lotion Dimethylolethylenethiourea of formula ch2oh ch2-n

\

^ CS 0.5 g ch2-n

^ CHÎOH

OH

I CH.-COONa

L

_ CH „-CH„ -0-CH „-COONa 4 g

Polymer according to Example 3b 1 g

Lactic acid qs pH 5

Water qs 100 g

Example A34

Same composition as the shampoo of example A33, except that the polymer Illb is replaced by the polymer le.

Example A35

Same composition as shampoo A33, except that the polymer Illb is replaced by the polymer Illa.

Example A36

Non-ionic shampoo

Laury alcohol oxyethylenated with 12 mol of ethylene oxide 10 g

Coconut fatty acid monoethanolamides 1.5 g

Lauryldimethylamine oxide 3 g

Polymer according to Example 6a 0.5 g

Lactic acid qs pH 3.3

Water qs 100 g

Example A3 7

Same composition as shampoo A36, except that the polymer according to Example 6a is replaced by the polymer according to Example 4b.

Example A38

ci2h250- [c2h30 (ch20h)} nh 5 g n represents an average statistical value of around 4.

r-choh-ch2-o- [ch2-choh - ch2-o} „h 10 g

R = mixture of cg-ci2 alkyl radicals n represents an average statistical value of approximately 3.5

Polymer according to Example 3b 1.5 g

Lactic acid qs pH 5

Water qs 100 g

Example A39

Same composition as the shampoo of example A38, except that the polymer according to example 3b is replaced by the polymer according to example 4b.

The action of the shampoos according to Examples A33-A39 is similar to that of the shampoos according to Examples A6-A10.

Polymer prepared according to Example 7 0.6 g

Phosphoric acid qs pH 3

15 Water qs 100 cm3

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 has a silky feel. After styling and drying, the hair is shiny and ner-20 want, they have body and volume and their touch is soft.

30

Example A41

Lotion increasing the volume of sensitized hair applied with rinsing

Calcium acetate 2 g

Polymer prepared according to Example 9 2 g

Phosphoric acid qs pH 8

Water qs 100 cm3

We apply this lotion to wet and clean hair. Hair has a soft feel and is easily detangled. After styling and drying, the comb passes easily through hair which is shiny, nervous and has volume.

Example A42

Structuring lotion, applied with Dimethylolethylenethio-urea rinse of formula:

^ ch2OH

ch2-n

\ /

CS

1 g ch2-n

ch2oh

Polymer prepared according to Example 7 0.5 g

Polymer prepared according to Example 8 0.4 g

Phosphoric acid qs pH3

Water qs 100 cm3

50 Apply this lotion to wet and clean hair. Leave to pause for 10 minutes, then rinse.

Hair has a soft feel and is easily detangled. After styling and drying, the comb passes easily through hair which is shiny, nervous and has volume.

55

Example A43

Non-ionic shampoo

R- CHOH - CH2 - O - [CH2 - CHOH—

ch2—093, sh 15 g

60 R = Cs to C12 alkyl

Polymer prepared according to the example 1.5 g

NaCl 1 g

Lactic acid qs pH 3

Water qs 100 ml

65 Applied to sensitized hair, this limpid-looking shampoo provides abundant and fairly soft lather.

It very clearly improves the disentangling of damp hair. After drying, the hair is nervous, light and shiny.

13

619,613

Example A44

Non-ionic shampoo for sensitized hair R - CHOH - CH2 - O - [CH2 - CHOH -

CH2-0} 3.5H

R = C9 to Ci 2 alkyl

Polymer prepared according to example la

Polymer with motif

17 g 0.8 g

/ \ [- CH2 -CH2 -XN

/

CH 2 - CH 2 "

prepared by the condensation of piperazine and piperazine bisacrylamide (preparation described in the Luxembourg patent N ° 64371 of the holder) 3 g

NH- (CH2-CH2-0) x-H

C18H37 ^ 1.5 g

NH— (CH2 — CH2 —0) y — H

x + y = 5

NH * C1 1.2 g

Lactic acid qs pH 3.5

Water qs 100 ml

Applied to sensitized hair, this limpid-looking shampoo provides an abundant and soft lather that is easily removed on rinsing.

The hair disentangles without difficulty and, after drying, has bulk and nervousness, while remaining soft and docile to styling.

Example A45

Non-ionic shampoo for sensitized hair

Cl2H2S0- [C2H30 (CH20H)} 4H 17 g

Polymer prepared according to Example 4a 1.8 g

Diethanolamide lauric 3 g

0.8 g NaCl

Lactic acid qs pH 5

Water qs 100 ml

Applied to sensitized hair, this limpid-looking shampoo provides abundant and pleasant lather and improves the disentangling of wet hair.

After drying, the hair is soft, shiny and very nervous while remaining disciplined.

Example A46

Styling enhancer for oily hair Vinyl acetate / crotonic acid copolymer 90/10

Molecular Weight 25,000 2.5 g

Polyvinylpyrrolidone / vinyl acetate 60/40 copolymer (viscosity 3.3 c Po, 5% in ethanolet at 25 ° C) 0.5 g

Polymer prepared according to Example 7 0.3 g

S-carboxymethylcysteine (antiseborrheic agent) .. 0.7 g Triethanolamine qs pH 8.6

Ethyl alcohol 10 ml

Water qs 100 ml

This lotion is applied to wet and towel-dried hair after shampooing and before winding the styling.

We notice on wet hair an easy disentangling. After winding the styling, we see that the hair is more nervous, softer and slightly more shiny. The holding of styling is considerably prolonged.

Example A47

Styling enhancer for oily hair Vinyl acetate / crotonic acid copolymer 90/10 molecular weight 70,000 2.5 g

Polyvinylpyrrolidone / vinyl acetate copolymer

60/40 (viscosity 4 cPo at 5% in ethanol and at 25 ° C) 0.5 g

Polymer prepared according to Example 7 0.3 g

Triethanolamine qs pH 7

s Ethyl alcohol 10 ml

Water qs 100 ml

This lotion is applied to wet and towel-dried hair after shampooing and before winding the styling.

We notice on wet hair an easy disentangling. 10 After winding the styling, we see that the hair is more nervous, softer and slightly more shiny. The holding of styling is considerably prolonged.

Example A48

15

Styling enhancer for oily hair

90/10 vinyl acetate / crotonic acid copolymer

molecular weight 50,000 2.5 g

Polyvinylpyrrolidone / vinyl acetate 20 60/40 copolymer (viscosity 3.5 cPo at 5% in ethanol and at 25 ° C) 0.5 g

Polymer prepared according to Example 9 0.3 g

Triethanolamine qs pH 7

Ethyl alcohol 10 ml

Water qs 100 ml

25 This lotion is applied to wet and towel-dried hair after shampooing and before winding the styling.

We notice on wet hair an easy disentangling. After winding the styling, we see that the hair is more nervous, softer and slightly more shiny. The holding of 3 "styling is considerably extended.

Example A 49 Styling enhancer for colored oily hair Vinyl acetate / crotonic acid copolymer 90/10

molecular weight 50,000 2.5 g

Polyvinylpyrrolidone copolymer neutralized with triethanolamine vinyl acetate 60/40 (viscosity

3.7 cPo at 5% in ethanol and at 25 ° c) 0.5 g

40 Polymer prepared according to example la 0.5 g

Dimethylhydroxymethylketylammonium chloride 0.1 g

0.5 g NaCl

Hydrochloric acid qs pH 8

Ethyl alcohol 50 ml

45 Water qs 100 ml

This lotion is 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 a pro-50 holding along the hairstyle. We also find that the hair is shinier and softer.

Example A50

No-rinse structuring lotion 55 Dimethylolethylenethiourea of formula ^, CH2OH

ch2-n

^ CS 0.5 g

CH2-N

^ CHjOH

Polymer prepared according to Example 10 0.6 g

"Phosphoric acid qs pH 3

Water qs 100 ml

This lotion is applied to hair washed and towel-dried after shampooing and before styling.

619,613

14

It is found that in the wet state the hair is disentangled easily and that it has a silky touch.

After styling and drying, the hair is shiny and nervous. They have body and volume and their touch is soft.

Example A51

Rinse (rinsed lotion) for fine and soft hair

Vaseline oil 7.5 g

Dimethyldistearylammonium chloride 1 g

R-0- [C2H30 (CH20H) ^ H (R = Cis to Cis alkyl) 3.75 g

C12H250- [C2H30 (CH20H)} 4H 3.75 g

Polymer prepared according to Example 9 2 g

Polyvinylpyrrolidone quaternary copolymers having a molecular weight of the order of 1,000,000, sold under the brand name Gafquat 755 by

General Aniline and Film Corporation 2.5 g

Citric acid qs pH 3

Water qs 100 g

This lotion is applied to wet hair and towel-dried after shampooing, it is left to stand for 5 minutes, then it is rinsed.

There is a very good disentangling of wet hair. After styling and drying, the hair is nervous, easy to style and shiny.

Example A52

Anionic shampoo

Triethanolamine lauryl sulfate 40% active ingredient 30 g

Coconut fatty acid diethanolamides 1.5 g

Polymer prepared according to example la (100% active ingredient) 1 g

Polymer with the motif Y — CH2 — CHOH—

CH2} 0.5 g where Y denotes

-N <^ ^> N-

or - N—

ch2 I

ch2-o-ch2oh these two groupings being statistically distributed

Distilled water qs 100 g ph = 7.5.

About 10 cm 3 of this clear solution are applied to previously wet hair. We massage lightly. Rinse with water and make a second application. It is massed vigorously to obtain an abundant foam, it is left to stand for 1 minute to ensure the fixing of the polymer on the hair, then it is rinsed.

There is a great ease of disentangling wet hair (the comb passes easily through the hair), the hair is very soft, flexible, malleable, the styling is assembled with great ease. After drying and when styling dry hair, there is also an ease of disentangling. The hair is nervous and disciplined.

15 Example A53

Cationic shampoo

Tetradecyltrimethylammonium bromide 75 g

Polyoxyethylenated lauryl alcohol with 12 mol of oxide

20 ethylene 50 g

Polymer prepared according to example la 5 g

Polymer with the motif {-Y — CH2 — CHOH— CH2} 0.5 g

25 where Y denotes - N <^ ^> N— or —N—

CHz I

ch2-o-ch2-ch2oh

30 these two groups being distributed statistically.

Lactic acid qs pH 5-5.5

Distilled water qs 1000 g

This clear-looking solution is applied to dyed hair. After massage, it is rinsed with water, then a second application is made. Massage vigorously to obtain an abundant foam, then rinse.

There is a great ease of disentangling wet hair (the comb slides easily into the hair), the hair is very soft, flexible, malleable, the styling is assembled with great ease. After drying and when styling dry hair, there is also an ease of disentangling. The hair is nervous and disciplined.

R

Claims (35)

619,613 2 1. Process for the preparation of a cosmetic composition for hair by mixing with the other components of the composition of at least one crosslinked polymer soluble in water obtained by the crosslinking of a polyaminopolyamide prepared by polycondenation of at least an acid chosen from a) dicarboxylic acids free from ethylenic unsaturation and b) aliphatic mono- and dicarboxylic acids with ethylenic double bonds and / or at least one ester of the abovementioned acids, on at least one polyamine of which at at least 50 mol% are chosen from polyalkylene polyamines bis-primary and mono- or secondary; the crosslinking being carried out by means of a crosslinking agent chosen from epi-halohydrins, diepoxides, dianhydrides, and bis-unsaturated compounds; process characterized in that the proportion of crosslinking agent used for crosslinking is from 0.025 to 0.35 mol of crosslinking agent per amine group of the polyaminoamide, this proportion being such that the crosslinked polymer has all of the properties following: 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 an alkyl group. 2. Method according to claim 1, characterized in that one uses for the polycondensation an ester which is an addition product of one molecule of ethylenediamine and two molecules of methyl ester of an ethylenically unsaturated acid . 3. Method according to one of claims 1 or 2, characterized in that the crosslinked polymer is reacted additionally with an alkylating agent chosen from a) epoxides, b) ethylenically unsaturated compounds, c) acid chloracetic, d) pro-panesultone or butanesultone. 4. Method according to one of claims 1 to 3, characterized in that the polyamine comprises up to 20 mol% of hexamethylene diamine. 5. Method according to one of claims 1 to 3, characterized in that the polyamine comprises up to 50 mol% of a bis-primary alkylene diamine such as ethylenediamine or of a bis-secondary dialkoylenediamine such as piperazine. 6. Method according to one of claims 1 to 5, characterized in that the acid compound or the ester 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 acrylic, methacrylic, ita-conic acids or their esters. 7. Method according to claim 1, characterized in that the polyalkylene polyamine used for the preparation of the polyaminopolyamide is chosen from diethylenetriamine, dipropylene triamine, triethylenetetramine and their mixtures with ethylenediamine, hexamethylenediamine and piperazine. 8. Method according to one of claims 1 to 7, characterized in that the crosslinking agent is chosen from divinylsulfone, methylenebisacrylamide, diglycidylether and N, N'-bisepoxy-propylpiperazine. 9. Method according to claim 1, characterized in that epichlorohydrin is used as crosslinking agent. 10. Method according to one of claims 1 to 9, characterized in that less than 0.2 mol of crosslinking agent is used per amine group of the polyaminopolyamide. 11. Method according to one of claims 1 to 9, characterized in that the crosslinked polymer is obtained using 0.025 to less than 0.1 mol of crosslinking agent by amine group of the polyaminopolyamide. 12. Method according to one of claims 1 to 9, characterized in that the proportion of crosslinking agent is such that the 10% solution in water and at 25 ° C of the crosslinked polymer has a viscosity between 3 and 200 cPo, preferably between 20 and 50 cPo. 13. Method according to claim 1, characterized in that a polyaminoamide is prepared consisting of units of formula -OC-R-CO-Z 5 where R represents: (CH2) 4- 10 -ch2-ch2-nh-ch2-ch2-nh-ch2-ch2- -ch-ch2-nh-ch2-ch2-nh-ch2-ch- CHÎ 15 - CH - CH ch3 55 25 Z represents: in the proportions of 50 to 100 mol%, the radical —NH - [(CH2) x — NH ■} „(II) where x = 2 and n = 2 or 3, or x = 3 and n = 2 in the proportions of 0 to 20 mol%, the radical -NH- (CH2) 6-NH-; 30 in the proportions of 0 to 50 mol%, the radical (II) in which x = 2 and n = 1, or the radical / \ NOT- -v 14. Method according to claim 1, characterized in that the crosslinked polymer is prepared by polycondensation of adipic acid and of diethylenetriamine and then crosslinked using a crosslinker chosen from the group formed by epichlorohydrin, methylenebisacrylamide, N, N'-bisepoxypropylpiperazine, 40 divinylsulfone and diglycidylether. 15. Method according to claim 1, characterized in that the crosslinked polymer is prepared by polycondensation of adipic acid and of a mixture of diethylenetriamine and piperazine, 45 then crosslinking using a crosslinker chosen from the group formed by epichlorohydrin, methylenebisacrylamide, N, N'-bisepoxypropylpiperazine, divinylsulfone and diglycidylether. 16. Method according to claim 1, characterized in that the crosslinked polymer is prepared by polycondensation of the acid adi- 50 spike and triethylenetetramine, then crosslinking using a crosslinker selected from the group formed by epichlorohydrin, methylenebisacrylamide, N, N'-bisepoxypropylpiperazine, divinylsulfone and diglycidylether. 17. The method of claim 2, characterized in that the crosslinked polymer is prepared by polycondensation of the reaction product of 2 mol of methyl itaconate and 1 mol of ethylenediamine with diethylenetriamine, then by crosslinking using a crosslinker chosen from the group formed by epichlorohydrin, methylenebisacrylamide, N, N'-bisepoxypropylpiperazine, divinylsulfone and diglycidylether. 18. The method of claim 2, characterized in that the crosslinked polymer is prepared by polycondensation of the reaction product of 2 mol of methyl acrylate and 1 mol of ethylene- 65 diamine with diethylenetriamine, then crosslinking using a crosslinker chosen from the group formed by epichlorohydrin, methylenebisacrylamide, N, N'-bisepoxypropylpiperazine, divinylsulfone and diglycidylether. 19. The method of claim 2, characterized in that the crosslinked polymer is prepared by polycondensation of the reaction product of 2 mol of methyl methacrylate and 1 mol of ethylene diamine with diethylenetriamine, then by crosslinking with using a crosslinker chosen from the group formed by epichlorohydrin, methylenebisacrylamide, N, N'-bisepoxypropylpiperazine, divinylsulfone and diglycidylether. 20. The method of claim 3, characterized in that the crosslinked polymer is alkylated by an epoxide. 21. The method of claim 20, characterized in that the epoxide is chosen from glycidol, ethylene oxide and propylene oxide. > 22. Method according to claim 3, characterized in that the crosslinked polymer is alkylated with an ethylenically unsaturated compound. 23. The method of claim 22, characterized in that the compound with ethylenic double bond is chosen from acrylic acid and acrylamide. 24. Method according to one of claims 1 to 23, for the preparation of a shampoo, characterized in that the crosslinked polymer or the crosslinked alkylated polymer is combined with a nonionic, anionic, cationic, amphoteric surfactant. or zwitterionic. 25. Method according to one of claims 1 to 23, characterized in that the crosslinked polymer or the crosslinked and alkylated polymer is combined with a restructuring agent. 26. Method according to one of claims 1 to 25, characterized in that the pH of the composition is adjusted to a value between 2 and 11, preferably between 3 and 8. 27. Method according to one of claims 1 to 26, characterized in that the crosslinked polymer or the crosslinked and alkylated polymer is incorporated into the composition in a proportion of 0.1 to 5% by weight of the total weight of the composition. 28. Method according to one of claims 1 to 27, characterized in that the crosslinked polymer or the crosslinked and alkylated polymer is combined with a water-soluble electrolyte. 29. The method of claim 28, characterized in that the electrolyte is a chloride or acetate of sodium, potassium, ammonium or calcium. 30. The method of claim 28, characterized in that the electrolyte / polymer ratio is between 0: 1 and 1.5: 1. 31. Process according to claim 1, characterized in that the polyaminopolyamide is prepared by polycondensation of a polyalkylene polyamine chosen from diethylenetriamine, triethylenetetramine, dipropylenetriamine and their mixtures on a compound chosen from adipic acid, its dimethyl ester and the addition product of one molecule of ethylenediamine on two molecules of methyl acrylate, methacrylate or itaconate. 32. Method according to one of claims 1 to 23, characterized in that the crosslinked polymer or the crosslinked and alkylated polymer is combined with at least one cosmetic resin. 33. Method according to one of claims 1 to 23, characterized in that the crosslinked polymer or the crosslinked and alkylated polymer is combined with a protein hydrolyzate. 34. Method according to one of claims 1 to 23, characterized in that the crosslinked polymer or the crosslinked polymer is combined and alkylated with one or more cosmetic adjuvant (s) chosen from anionic, amphoteric, zwitterionic or nonionic surfactants, foam synergists, stabilizers, thickeners, emulsifiers, softeners, dyes, perfumes, nonionic, cationic or anionic cosmetic resins, antiseborrheics. 35. Method according to one of claims 1 to 23, for the preparation of a lotion, characterized in that the crosslinked polymer or the crosslinked and alkylated polymer is combined with one or more cosmetic adjuvant (s) chosen from the group formed by ethanol, silicone oil, petrolatum oil, hydroxyethyl-cellulose, dimethylolethylenethio-urea, S-carboxymethyl- 619,613 cysteine, a vinyl acetate / crotonic acid copolymer, a vinylpyrrolidone / vinyl acetate copolymer, a quaternary polyvinylpyrrolidone copolymer, dimethylhydroxy-methyl ketylammonium chloride, dimethyldistearyl ammonium chloride, tetradecylammonium bromide, cetyl alcohol bromide oxyethylenated, sodium chloride, calcium acetate. 36. Cosmetic composition obtained in accordance with the process according to claim 1.