CA1086652A - Hair conditionner - Google Patents

Abstract

Cosmetic composition for hair containing at least one crosslinked polymer soluble in water, chosen from (I) the crosslinked polymers obtained by the crosslinking of a polyaminopolyamide prepared by polycondensation of an acid compound chosen from (i) organic dicarboxylic acids, (ii) aliphatic mono- and dicarboxylic acids with an ethylenic double bond (iii) esters of the abovementioned acids, (iv) mixtures of these compounds; on a polyamine chosen from primary and mono- or dis-secondary polyalkylene polyamines. 0 to 20 mole% of this polyamine which can be replaced by hexamethylenediamine or 0 to 40% of this polyamine which can be replaced by a bis-primary amine, preferably ethylenediamine or by a bis-secondary amine, preferably piperazine ; the crosslinking being carried out by means of a crosslinking agent chosen from epihalohydrins, diepoxides, dianhydrides, and bis unsaturated derivatives; either from (II) the crosslinked polymers (I) alkylated with an alkylating agent chosen from (a) epoxides, (b) ethylenically unsaturated compounds, (c) chloracetic acid, (d) propane sultone or butane sultone; composition characterized in that the crosslinking is carried out using 0.025 to 0.35 mole of crosslinking agent per amine group of the polyamino-amide; 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 polymer solution at 10% in l water at 25.degree.C, is greater than 3 centipoise; (3) it does not contain a reactive group and in particular it does not have an alkylating property and it is chemically stable. Alkylation of crosslinked polyamino-amide polymers. Shampoo containing the cosmetic composition. Polyamino-polyamide polymer prepared by crosslinking.

Description

5 ~ ~
. . -The present invention relates to a composition cosmetic which improves the condition of the hair as well as the appearance of the hair We know that the hair of many people, : as a result of the general damage or of the degradations consecutive to the action of atmospheric agents or the action of treatments such as discoloration, perms or stains, are often difficult to unravel and style especially when it comes to `
abundant hair. They are generally, and to varying degrees various, dry, dull and ragged or lacking in "vigor" and "nervousness"
your ".
.
We tried to limit or correct these defects by applying a "conditioning" composition to the hair of hair "intended to improve the condition of damp hair and dry hair as well as combing and setting operations form.
"Hair conditioning" means the operation which, while facilitating the disentangling and combing of the hair wet, gives dry hair "bulk" and elasticity ~ 20 cited, which ensures good maintenance of the hairstyle. The agents : ensuring the "conditioning of the hair" are called "condition-`
nors ".
We have already used hair conditioning ; synthetic polymers such as polyethylene imines, i polyvinylpyridines, p-vinyl-benzyl trimethyl-chloride - -~ Lammonium, diallyldimethylammonium polychloride. These poly-. . .
~ mothers have the disadvantage of not being compatible with ..: ~
anionic shampoos.
We have also already used in compositions for polyamino amide polymer hair (obtained by polyconden-sation of a dicarboxylic acid and a polyalkylene polyamine), ~; -polyaminourylene polymers and alkylene polyamine polymers modified, in particular by epichlorohydrin in amounts 8 ~ 652 : `.

~ close to the stoichiometric proportions compared to the groups -. ~
amine of the poluamino-amide. The addition of these quantities of ~ pichlorhydrin results in the presence in molecules of the crosslinked polymer of reactive groups. These polymers indeed contain alkyl groups capable of reacting on nucleophilic groups such as amines, thiols, sulfites, etc. ~ As an example such alkyl groups, mention may be made of rings ~ azetidinium.
-. 10 The first consequence of the existence of such groupings . reagents is a lack of stability of these compounds which can degrade when abandoned in solution.
Furthermore, the existence of such al ~ oylants groups makes these products highly suspicious for application to the skin of man.
It has also been recommended for use as a "condition-neur for hair ". of thermosetting polymeric polymer to crosslink by the heat.
The subject of the present invention is a "conditioner for hair "which removes these i ~ conveniences, and which consists : 1 by a crosslinked polyamino-polyamide which does not have a group . . reactive and chemically stable.
The present invention also relates to a composition of hair conditioning, which can be applied to the ordinary temperature and which is in the form of a `~. ready-to-use composition.
The present invention also relates to a "condition-neur for hair "which is compatible with anio shampoos while ensuring satisfactory detangling of the hair:.:

. 30 wet, and good elasticity of dry hair, so . ensure good hold of the hairstyle. .
;. , . The present invention also relates to a .`
: ~ - 2 -:

, .............. . . ....

~ 136 ~ 52 cosmetic composition for hair ~ containing at least one water-soluble crosslinked polymer obtained by crosslinking of a polyamino-polyamide (~) prepared by polycondensation of a acid compound on a polyamine ~ The acid compound is chosen among (i) organic dicarboxylic acids, (ii) acids mono- and dicarboxylic aliphatics with an ethylenic double bond, (iii) esters of the abovementioned acids, preferably with the lower alkanols a ~ ant from 1 to 6 carbon atoms, (iv ~
mixtures of these compounds. The polyamine is chosen from polyalkylene-polyamines bis primary mono- or secondary.
0 to 40 mole% of this polyamine can be replaced by a primary bis amine preferably ethylenediamine or with an amine ~ -bis-secondary preferably piperazine and 0 to 20 mole%
can be replaced by hexamethylenediamine. The reticula-tion is carried out by means of a crosslinking agent (B) chosen among epihalohydrins, diepoxides, dianhydrides, unsaturated anhydrides, bis unsaturated derivatives; crosslinking is characterized by the fact that it is carried out by means of 0.025 . ~, ..
0.35 mol of a ~ ent crosslinking by amine group of the polyamino-polyamide (A) and generally from 0.025 to less than 0.2 and in part 0.025 to less than 0.1 mole of cross-linking agent per `
; amine group of the polyamino-polyamide (A);
In the composition according to the invention, the crosslinked polymer culé has all of the following characteristics:
(1) it is perfectly soluble in water at 10% without formation gel;

(2) the viscosity of a 10% solution in water at 25C is higher less than 3 centipoises and usually between 3 and 200 and more especially it is equal to or greater than 20 centipoises and less than 50 centipoise, (3) it does not include any grouping reactive and in particular it has no alkylating property and it is chemically stable.

- 3 -~ '. ,. ...............: ........... ... ~., ........,.:
:,. . ',''..,:,.

The acids usable for the preparation of polyamino-polyamides (A) are chosen from:
- saturated organic dicarboxylic acids having from 6 to 10 carbon atoms, for example adipic acids, trimethyl-2, 2.4 and -2.4.4 adipic, terephthalic, aliphatic acids mono and dicarboxylates with ethylenic double bond, for example acrylic, methacrylic, itaconic acids.
Among the preferred acids are adipigal acid and addition compounds of an alkylenediamine with acids unsaturated such as acrylic, methacrylic, itaconic.
Adipic acid is particularly preferred.
It is also possible to use the esters of the above acids.
above cited. It is also possible to use mixtures two or more carboxylic acids or their esters.
Polyamines usable for the preparation of poly-amino-polyamides (A) are chosen from polyalkylene-polyamines bis primary mono- or disecondary, for example the diethylene triamine, dipropylene triamine, triethylene tetra-mine and their mixtures.
Polycondensation is carried out by known methods, by mixing the reagents, then heating between 80 and 250C, and ; preferably between 100 and 180C for 1 to 8 ~ eures according to , ,,. : ~.
~ reagents used. After heating at full reflux for 1/2 , } 'l'. .
j hour by hour, the water or alcohol formed during j polycondensation, first at pressure or ~ inary then under pres-reduced sion.
The reactions take place under a stream of nitrogen to avoid excessive coloring and facilitate elimination of volatile substances.

In carrying out the reaction, preferably a ~ amount of dicarboxylic acid and amines in proportions -. ''''

4 ~

36 ~ 5 ~
. ~:
equimolecular with respect to primary amine groups polyalkylene polyamines.
According to a preferred method of preparation, ef ~ ectue la polycondensation of the pre-selected polyalkylene polyamine reference among diethylene triamine, triethylene tetramine, dipropylene triamine and their mixtures, either (i) on a diacid preferably carboxylic adipic acid or its dimethyl ester lique, that is (ii) on the intermediate product of addition of a molecule of ethylenediamine and two molecules of methyl ester of an ethylenically unsaturated acid such as acrylate, methacrylate or methyl itaconate.
Addition reactions of ethylenediamine on unsaturated esters are produced by mixing the reagents between

5 and 80C, and polycondensation reactions by heating for 30 to 60 minutes at reflux, then with elimination of alcohol methyl at 120-150C, or water at 140-175C, first at ordinary pressure then under a partial vacuum of 15 mm of mercury.
The polyamino polyamides (A) thus obtained have a viscosity in water at 10% and at 25C less than 3 centipoise.
The constitution of the preferred polyamino polyamides (A) can be represented by the general formula (I) ~ OC - R - C0 - Z ~ (I) where R represents a bivalent radical ~ ui derives from the acid used or the adduct of the acid with the bis-primary amine or bis-secondary.
Among the preferred meanings of R we can cite the following:

, (CH2) 4 .
CH ~ CH2 ~ NH _ CH2 2 - CH - CH

.

366SiZ

- TH - CH _ NH - CH2 - CH2 - NH - CH2 - fH

'",'.
- CH CH2 ~ ~ CH2 - CH -CH2-- I C__ 2 `:
o O ''' These radicals are respectively derived from acid terephthalic acid, adlpic acid, adduct of ~:
ethylenediamine on acrylic, methacrylic and ita-conical or their esters.

Z represents ~

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

- NH - ~ (CH2) X - NH ~ n (II) where x = 2 and n = 2 or 3 or else;
x = 3 and n = 2 this radical deriving from diethylene triamine, from triethylene ~ ~:
tetramine or dipropylene triamine,.
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 ethylene-diarnine, or the radical -N ~ - derived from piperazine;
. ~ '..,:
"
3) in the proportions of - to 20 mole% the radical - NH - (CH2) 6 ~ MH - derived from hexamethylenediamine.
The polyamino polyamides thus obtained are then crosslinked by adding a crosslinking agent. We use like, have crosslinking a bifunctional compound chosen from (a) ~. :
. epihalohydrins, for example epichlorohydrin; (b) diepoxides:.

: - 6 -:.
., ~
``

,. . . . . . ... ...

~ 36q ~ 5 ~
for example diglycidyl ether, N, N'-bis epoxy propyl piperazine, (c) dianhydrides, for example dianhydride butane tetracarboxylic acid, the acid dianhydride ; pyromellitic; (d) bis unsaturated derivatives, for example divinylsulfone, methylene bis acrylamide.
A crosslinking agent of advantageous use is epichlorohydrin. Other preferred crosslinking agents are divinylsulfone, methylene bis acrylamide, diglycidylether and N, N'-bis epoxy propyl piperazine.
`10 These crosslinking agents give birth respectively ~ -to the following radicals:
- CH2 - CHOH ~ CH2 ~
. : -2 CH2 - ~ - CH2 - CH2 ', / ~, - CH2 - CHOH - CH2 - N - CH - C ~ OH - CH2-Cross-linking reactions are carried out between 20C
20 and 90C, from aqueous solutions of 20 ~ 30% polyamino-polyamide to which the crosslinking agent is added by very small fractions until o ~ hold a significant increase in the screw-cosiness but without however reaching the gel which does not dissolve would be more in the water. Concentration is then quickly adjusted to 10% by addition of water and the reaction medium possibly cooled.
.
According to an essential characteristic of the invention, polyamino-polyamide polymers are used for crosslinking from 0.025 to 0.35 mole of crosslinking agent per amine group polyamino-polyamide. An interesting category of these - 7 - `

8 ~ i; 65Z

crosslinked polymers is obtained using 0.025 to less 0.2 mole of crosslinking agent per amine group of the poly-amino polyamide. Another advantageous category of polymers crosslinked is obtained using 0.025 to less than 0.1 mole of crosslinking agent by amine group of the polyamino-polyamide.
The proportions of crosslinker to be used, which vary, depending on the nature of the polyamino-polyamide and of the crosslinker, may be easily determined by adding the desired crosslinking agent to an aqueous solution of the polyamino polyamide until the viscosity of a 10% solution, i.e. at 25C, between 3 centipoises and the gel state while retaining solubility perfect in water.
Exceeding the proportions of crosslinker above ', indicated results in the formation of a gel that cannot be diluted with water as a result of too much crosslinking. Increasing again the amount of crosslinker we again obtain poly-mothers who are water soluble but have a character evolving as a function of time and temperature. This character ~ evolutionary is due to the presence, in the crosslinked polymer of sub-reactive stituents with respect to nucleophilic groups. When epichlorohydrin is used as crosslinking agent in quantities close to the stoichiometric proportions, the reactive substituents consist mainly of ~ ~, a2étidinium cycles. ~ 3 ' / N \ Cl ~
HC CH

CH ,, OH

Crosslinked polymers obtained from polyamino-polyamides known in the art and used in hair compositions contain reactive groups 8 - ~
~ J
~. ~. `. ... ... ... ... . .

., : `:
and therefore do not keep well.
The crosslinked polymers according to the present invention are keep well and are compatible with anio-surfactants while ensuring good detangling of damp hair.
This compatibility with anionic surfactants can still be improved by alkylation of secondary amine groups crosslinked polyaminoamides. Alkylation increases the water solubility of crosslinked polyaminoamides, in the presence anionic surfactants.
The alkylating agent can be used:
1) an epoxide, for example glycidol, ethylene oxide, propylene oxide;
2) a compound with an ethylenic double bond, for example acryl-lamide, acrylic acid, 3) chloracetic acid;
4) an alkane sultone, for example propane sultone or butane sultone ~
The alkylation of the crosslinked polyamino amides is carried out in aqu ~ use solution, at a concentration of 10 to 30%, at a temperature erasure between 10 and 95C. The alkylation rate by in relation to total basicity, i.e. the number of moles of alkylating agent ~ attached to the total number of groups amine ranges from 0 to 80%. The basicity index of the polymer expressed in meq / g indicates the total number of milliequivalents of nitrogen basic per gram.
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 sensitized hair. They can also be used for concentrations from 0.1 to 5%, pre ~ erence from 0d2 to 2.5% and before-suitably from 0.3 to 1.3% in cosmetic compositions for hair and more particularly in compositions of shampoo, such as anionic, cationic, nonionic shampoo, _ ~; amphoteric or zwitterionic, coloring shampoo, dye, ; styling gel, styling lotion, brushing lotion, styling lotion, rinse lotion, rinse leave-in styling enhancer, in compositions restructuring, in more specific cosmetic compositions such as anti-dandruff, antiseborrhoeic compositions.
We mean by rinsed lotion, a lotion that apply after shampooing to obtain an effect of "condition-hair "and rinse after a break.
We mean by "brushing lotion" or shaping, a lotion applied after shampooing and which promotes the shaping of the hair, this shaping being carried out on wet hair using a brush, while drying the hair using a hand dryer.
This technique is suitable for relatively short hair.
By reinforcing styling lotion is meant leave on, a lotion applied after shampooing and before styling, which is not rinsed and which facilitates the setting folds and improves its shape and duration.
By restructuring lotion is meant a lotion which contains products strengthening the keratin chain of hair. To this class of products belong the derivatives methylolés such as those described in French patents N
1,527,085 and 1,519,979 of the plaintiff.
These restructuring agents are generally used.
in combination with cationic compounds which facilitate the detangling of hair in the wet state but has the inconvenience deny giving hair a sticky appearance when dry.
Cosmetic compositions for hair containing a crosslinked polymer according to the invention may have a pH understood between 2 and 11 and preferably between 3 and 8.

~ '', ' :

i52 They can come in various forms . usual, that is to say: aqueous or hydroalcoholic solutions -ques, gels, creams, dispersions or in ~ aerosol form.
They may contain, in addition to the cross-linked polymer.
culé all the components used in the compositions for hair, in particular anionic, cationic surfactants, amphoteric, zwitterionic or non-ionic, synergistic,. .
stabilizers, thickeners, emulsifiers, softeners, agents preservatives, dyes, ~ ums, etc. These compositions may also contain other cosmetic resins, in particular particular non-ionic, cationic or anionic.
The association of conditioners of this invention with non-ionic surfactants provides particularly interesting shampoos especially for the easier detangling of hair.
Among the pref res resin cosmetic polymers:
can be used in combination with crosslinked polymers mention may be made of 10% crotonic acid-acetate copolymers : vinyl 90% with a molecular weight of 10,000 to 70,000, the copo-vinylpyrrolidone (VP) lymer -vinyl acetate ~ AV ~ having a molecular weight from 30,000 to 360,000, the VP: AV ratio being between 30:70 and 70:30, copolymers of polyvin ~ lpyrro-~ uaternary lidone having a molecular weight of the order of 1,000,000, such as for example the polymer sold under the brand: ~
"GAFQUAT 755" by GAF Corporation, polymers resulting from the condensation of piperazine or its derivatives (1) on bi ~ unctionnels compounds such as di ~ alkyl halides or alkyl aryls, bis-epo ~ Yydes, epihalohydrins, bis unsaturated derivatives and / or (2) on a primary amine in which the two hydrogen atoms may be sub-incorporated and which behaves like a bifunctional compound i6S; Z

(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 that can be used in combination with the crosslinked polymers, mention may be made of (a) the anionic surfactants such as alkali or alkali salts nolamines of alkanes sul ~ onates, alkyl sulphates and alkyl ether sulfates and their condensation products with ethylene xide does for example lauryl and myristyl bther sodium sulfate or triethanolamine, the disodium sulfosuccinate semi-ester alkanolamides, (b) non-ionic surfactants such as (i) the condensation products of a monoalcohol, of a ~ -diol or 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 alipha-ticks which may contain ether, thioether and ;, hydroxymethylene and 1 ~ n ~ 10, (ii) the compounds of formula R0 ~ C2H30 (C ~ 2oH) ~ n in which R denotes an alkyl, alkenyl or alkylaryl radical and n 10, (c) cationic surfactants such as (i) dimethyl hydroxymethyl cetyl ammonium chloride at tii) bromu-re of tetradecyl trimethylammonium; (d) surfactants amphoteric such as d ~ riv ~ s carboxylic imidazole.
The cosmetic compositions for hair are ~ on 'the invention to be applied to sensitized hair advantageously contain an electrolyte. The presence of the elect trolyte in the composition reduces or eliminates the tendency that have sensitized hair to permanently fix polymers.
As the electrolytes, alkaline salts or alkaline earth mineral or organic acids, soluble in preEerence water and sodium chlorides and acetates, from "~
.

, - ' ,,, ~. ;., '' .

8 ~; ~ 5Z
potassium, ammonium and calcium. The amount of electrolyte ~
is not critical. It is preferably between 0.01 to;
5/0 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.
Polyamino-amide polymers (I3 crosslinked with the crosslinking agents above indicated and alkylated with a alkylating agent chosen from acrylamide and glycidol are new compounds.
During the alkylation of a polyamino polymer amide crosslinked with acrylamide of ~ ormule CH2 = CH-CONH2 the latter condenses on primary and / or secondary amine groups giving formula strings glycidol under the same conditions leads to chains of formula '~ -cH2-cHoH-cH2orI.

`~ 86G ~ 2 EXAMPLE I
Polycondensation of adipic acid and diethylene triamine.
The constitution of the polymer obtained can be characterized by the following pattern:; ~

~ OC - (CH2) 4 CO ~ H - (CH2 C 2 2 619 g (6 moles) of diethylene triamine are added, : $ 0US stirring and in a nitrogen atmosphere, in 15 minutes, 876 g (6 - moles) of adipic acid. The reaction mixture is then heated at 145-150C, temperature at which water condensation is noted.
Mainti ~ nt reflux ~ for 45 minutes and then remove the water ~ -by distillation at ordinary pressure for 2 hours, then under reduced pressure (15 mm Hg) for 1 hour. The temperature . .., ~,.
~ heating temperature gradually increases to 170C.
; The product thus obtained is poured hot. he is, after cooling, in the form of a hard resin and brittle. It is transparent yellow-green in color and completely solubilizes in water. ! i EXAMPLE Ia ; Crosslinking of the polymer obtained according to Example I with epichloro-- 20 hydrins. ;
At 200 g of resin, obtained ~ the according to the method described in Example I, dissolved in 800 g of water, is added, with stirring t1on, 9 g of epichlo ~ hydrine. We heat the mixture up to 90C, then we add in very small fractions and at intervals ~ the from 5 to 10 minutes, 1.8 g of epichlorohydrin until obtaining with a viscosity greater than 50 centipoise at 65C.
The solution is then immediately diluted to a concentration of 10% of dry extract by addition of 1098 g of water.
The apparent viscosity measured after 24 hours and at 25C is 31 centipoise at a speed gradient of 26.3 sec 1.

~ The amount of crosslinker used is 11 moles ~
.,:

,. , .. ~,:

366 ~ 2 epichlorohydrin per 100 amine groups.

EXAMPLE Ib :.
Crosslinking of the polymer o ~ held according to Example I with methyl-lene bis acrylamide.
70 g of resin prepared according to the process described in example I and dissolved in 280 g of water we add to the room temperature and ~ or with stirring, 7 g of methylene bis acry-lamide, then the mixture is heated to 80-90C. After 1 hour of ~ - heating is observed ~ e a significant increase in viscosity.
The mixture is then diluted to 10% of dry extract by addition of 413 g of water.
A clear solution having a viscosity is obtained apparent of 32 centipoises, measured after 24 hours at 25C and under a speed gradient of 26.3 sec The amount of crosslinker used is 12.1 moles methylene bls acrylamide per 100 amine groups of the polyamino-polyamide.

EXAMPLE Ic - Crosslinking of the polymer obtained according to the example ~ with N, N'-bis ~ epoxy propyl piperazine.
20 g of polymer prepared according to the process described in example I and dissolved in 80 g of water, is added, at ordinary scratches and ~ or stirring, l, CtO g key N, N'-bis-epoxy propyl piperazine, then the mixture is heated to 70-80C. A ~ rès 15 minutes of heating, a gel is obtained which is immediately diluted.
10% of the dry extract by adding 113.5 g of water.
A clear solution having a viscosity is obtained of 32 centipoises measured after 24 hours at 25C and under a 26.3 sec speed gradient 1. The amount of crosslinker used is 7.3 moles of N, N'-bis-epoxy propyl piperazine per 100 amine groups of the polyamino-polyamide.

- 15 - ~

.

~ L ~ 136 ~ 5; ~ ~
.
XAMPLE Id Crosslinking of the polymer obtained according to Example I with divinyl sulfone. ``
20 g of polymer prepared according to Example I and ~ -dissolved in 80 g of water, drop by drop at temp ~ rature ambient, juice ~ u 'to obtain a d ~ gelling purpose, 1.7 g of divinyl sulfone. Then diluted quickly with 100 ml of water.
The apparent viscosity of a 10% solution, measured ~ e after 24 hours, at 25C and at a speed of 26.3 sec.
1 is 27 centipoise.
- The amount of crosslinker used ~ e is 13.9 mole ~
of divinyl sulfone per 100 groups ~ ine of polyamino-polyami ~ of EXAMPLE II
Polycondensation of adipic acid and melan ~ e di ~ thylène triamine-piperazine.
The constitution of the prepared polymer can be represented felt by the two reasons below distributed statistically in the ratio of 2: 1.

- [OC - (CH2) ~ - CONH - (CH2 - CH2 - NH) 2 - and _ ~ OC - (CH2) 4 - CO ~

The mixture of 438 g (3 moles) of adipi ~ ue acid and 86 g (1 mole) of pipereaine is heated, with stirring, and nitrogen atmosphere for 2 hours at 120-135C. We add then, at this temperature and within 90 minutes, 206 g (2 moles) of diethylene triamine. The water formed is distilled for 1 hour at 140-170C at ordinary pressure, then 1 hour `
at 170-175C under 15 mm Hg.
The product thus obtained is in the form a hard, brittle, transparent resin with a yellow-green color.
, ~ - 16 -... . . . . . ... . . . . .

866 ~; 2 EXAMPLE IIa Crosslinking of the polymer obtained according to Example II with epichlorohydrin.
A 200 g of resin obtained according to e ~ ample II and dissolved in 800 g of water, 9 g are added, with stirring:.
. of epichlorohydrin at room temperature. Then we heat ; the mixture at 90C and a further 1.1 g of epichlorohydrin are added small fractions 5 to 10 minutes apart, up to obtain a viscosity of 50 centipoise.
. 10 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 vis-cosity, measured after 24 hours at 25C and at the speed gradient 26.3 sec is 52 centipoise.
. The amount of crosslinking agent used is 13.2 . ~ moles of epichlorohydrin per 100 amine groups of the polyamino-polyamide EXAMPLE III ~.
Polycondensation of adipic acid and triethylene tetra-. .
mine.
,. , ; The constitution of polymer prepared in this example can be represented by the pattern: ~.

OC (CH2) 4 CO ~ H (CH2 CH2 - N ~ I) A 292 g (2 moles) of triethylene tetramine, ~ on ;; ~
~ '!
add, under a nitrogen atmosphere, in the course of 20 minutes, 292 g:
(2 moles) of adipic acid, in small fractions and under agitation-tion ~ The mixture is then heated to total reflux at 145C during for 1 hour. The uniform water is removed by distillation with. . ~::
ordinary pressure for 3 hours and under reduced pressure of 15 mm of mercury for 1 hour by raising the ~
temperature up to 170-175C.
: ' : ':, ~, 366 ~ iiZ

This gives a transparent colored resin yellow, of which a 10% solution has a viscosity, at 25C, less than 2 centipoises.

EXEMP1E IIIa Crosslinking of the polymer obtained according to Example III with the epi-chlorohydrin.
200 g of aqueous 20% mother solution obtained according to the process described in Example III, the following is added, quickly and with stirring, 1.8 g of epichlorohydrin and heating mixing at 90-95C for 30 ~ minutes. Then we add, to the same temperature, very slowly, 0.4 g of epichlorohydrin until obtaining a viscosity greater than 50 centipoise, measured at 65C.
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 25C and at gra-speed 26.3 sec 1 is 24 centipoise. ;
The total amount of epichlorohydrin added is 0.0242 mole, which corresponds to 7.8 moles of crosslinker for 100 amine groups of the polyamino-polyamide.
~.
EXAMPLE IIIb Crosslinking of the polymer obtained according to Example III with m ~ thy-lene-bis-acrylamide.
At 100 g of aqueous solution at 20% of polymer, obtained according to the method described in Example III, 0.8 is added g of methylene-bis-acrylamide, then the mixture is heated to 70-80C
for 25 minutes. We then obtain a soft gel which we ~ immediately dilutes to a concentration of 10% dry extract, ; by adding 108 g of water. ~ The solution obtained is clear.

Its viscosity, measured after 24 hours at 25C and at the gradient of speed of 26.3 sec is 43 centipoise.
', - 18 - ~ ~
.. ..

i52 The amount of methylene-bis-acrylamide added equivalent to 3.4 moles of crosslinker per 100 amine groups polyamino-polyamide, EXAMPLE IV
Polyconsen ~ ation of the reaction product of 2 moles of itaconate methyl and 1 mole of ethylenediamine with diethylene triamine. .:
The constitution of the polymer prepared in this ~ `
example can be represented by the pattern:

C - CH - CH2 CH2 - CH - CONH - (CH2 - CX2 - NH) I / -CH2 2 \ I ..

C ~ 2 ~~ ~ ~ CH2.:

First stage. ~ ~ -At 620 g (3.9 moles) of methyl itaconate, there is:
. add, in the space of an hour, with stirring and in an atmosphere ; nitrogen, 118 g (1.95 mole) of ethylene diamine while maintaining the temperature at 30C. ;
After one night, at room temperature, we heat -at 80C, to remove methanol, first at ordinary pressure, then under reduced pressure of 15 mm Hg. The apparatus is then noted . rition of a precipitate. We resume the reaction mixture with ~: ~
500 ml of benzene and the azeotrope methanolbenzene is distilled.
Concentrate and take up the residue with acé ~ tone. N, N'-ethylene is thus obtained with a yield of 82%
-bis- methyl C4-carboxylate 2-pyrrolidone], in the form of. ~:
. white powder with a melting point of 141-142C and an index : saponification of 6.35 milli e ~ uivalent / gram.

: Second stage : ~ At 19 ~ g (0.63 mole) of diester thus obtained, we add, at ambient temperature, 65.5 g (0.63 mole) of diethylene `-triamine and distilled methanol.formed by heating at 120-130C, ~.
first at ordinary pressure for 90 minutes, then under pressure '- 19 -~. :;. .

66 ~; i2 ,, --`

reduced by 15 mm Hg for 30 minutes.
This gives a transparent, hard and brittle yellow-green color, perfectly soluble in water.
"':
EXAMPLE IVa Crosslinking of the polymer obtained according to Example IV with epoxy chlorohydrin.

At 200 g of resin dissolved in 800 g of water, we add, with stirring, 13 g of epichlorohydrin at temperature - ambient. The mixture is heated to 90C and added again, in small ~ reactions, 5 or 10 minutes apart, 2 g `epichlorohydrin, until the start of gelling.

Then diluted quickly with 1135 g of cold water to bring , the 10% solids solution.
:
'' This gives a clear solution, the ; viscosity, measured after 24 hours at 25C and at the gradient of speed of 26.3 sec 1 is 49 centipoise.
The amount of epichlorohydrin used corresponds 22 moles per 100 amine groups of the polyamino-polyamide.

EXAMPLE IVb ; ~ 20 Crosslinking of the polymer obtained according to Example IV with the methylene-bis-acrylamide.
~, 'At 50 g of polymer obtained in Example IV and dissolved in 200 g of water, added at room temperature and , with stirring, 1.5 g of methylene-bis-acrylamide, then heating mixing at 85-90C. Then, gradually add 1 ~
crosslinking until a viscosity greater than 50 centi-poises at 65C. The concentration of the mixture is then reduced to 10%
dry extract, by adding 285 g of water. -A clear solution is obtained, having a viscosity from 54 centipoises at 25C and at a speed gradient of 26.3 sec The amount of methylene-bis-acrylamide added is ':
~ - - 20 -.

; of 3.9 g and it corresponds to 16 moles per 100 groupings polyamino-pol amine.

EXAMPLE V
Polycondensation of a mixture of 2 moles of methyl acrylate and 1 mole of ethylenediamine with diethylene triamine ~
The constitution of the polymer prepared in this example can be represented by the pattern:

2 2 ~ I CH2 CH2-NH-CH2-CH2-COMH- ~ CH2-CH -NH) To 240 g (4 moles) of ethylenediamine, the following is added, in the space of 2 hours, at a temperature between 10C
and 20C, with stirring and in a nitrogen atmosphere, 689 g (8 moles) methyl acrylate. After 1 hour of stirring at temperature `~`
ambient, 413 g (4 moles) of diethylene triamine are added. We then distills the methanol formed pa ~ heating to 120-140C
for 2 hours at ordinary pressure and for 2 hours under `
a reduced pressure of 15 mm Hg.
This gives a transparent resin of color ~ `
...
yellow-orange, which in 10% solution of dry extract, presents a viscosity of less than 2 centipoise. ;

EXAMPLE Go Crosslinking of the polymer obtained according to Example V with the epi-chlorohydrin.
~ 200 g of polymer, obtained according to the process of Example V, dissolved in 800 g of water, is added, with stirring, at room temperature, 45 g of epichlorohydrin. We heat progress-sively up to 90C, then add, in small fractions, to 5 or 10 minutes apart, 11 g epichlorohydrin until the rition of the beginning of gelling. We then quickly dilute the concentration at 10% of dry extract, by adding 1504 g of water cold.
... . .
This gives a clear solution having a .:.
... .

5z . '.' .

viscosity ~ of 25 centipoise, measured ~ e after 24 hours at 25C and at 26.3 sec speed gradient EXEMP ~ E VI; ~
Polycondensation of a mixture of 2 moles of methacrylate of m ~ thy-~ 'and 1 mol of ethylene diamine with diethylene triiamine.
The constitution of the polymer prepared in this example can be represented by the pattern:
OC-fH - CH - ~ H - CH2 - CH2 - NH - CH2 - ~ -CO ~ H (CH2 CH2 NH) 2 H CH3 t ' To 180 g (3 moles) of ethylene diamine, at room temperature, 600 g of methyl methacrylate (6 moles The mixture is left for 3 days, then heated to 80C
during 3 hours. Then added 309 g of diethylene triamine (3 moles ~ and heated to 120-125C for 4 hours at the press-ordinary and for 90 minutes under reduced pressure 15 ~ n Hg. The polycondensate thus obtained is present in ,, i the form of a worm-bronze colored resin.
EXAMPLE VIa Crosslinking of the polymer obtained according to Example VI with the methylene-bis-acrylamide ~ ', A 84.6 g of polymer pr ~ paxé according to the process `` describes dan8 Example VI and dissolved in 338.4 g of water, we add, ', at room temperature and with stirring, 27.3 g of methylene-bis-acrylamide. The mixture is then heated to 85-90C for 15 minutes. We then obtain a gel which is diluted immediately at a concentration of 10% dry extract, by adding 669 g of water. A clear solution is obtained having, at 25C and at gra-speed of Z6.3 ~ ec 1, a viscosity of 53 centipoise.
The amount of crosslinker added corresponds to 21.4 moles per 100 amine groups of the polyamino-polyamide.

1 ~ 52 . :
E ~ EMPLE VII
Alkylation with propane sultone of the crosslinked polymer according to Example Ia:
3000 g of 10% aqueous crosslinked polyaminoamide solution and prepared according to Example Ia and having a basicity index 0.45 meq / g (1 g of polymer ren ~ erme 0.45 10 3 amine group), ~
113.5 g (0.93 mole ~) are added with stirring and nitrogen atmosphere:
propane sultone. The reaction mass is then heated to 60C, for 4 hours. Diluted with 1020 g of water to bring back.
the concentration at 10% of dry extract. The solution thus obtained.
is yellow in color and has a viscosity of 12.6 cps at 25C.

EXAMPLE VIII
sodium chloracetate alkylation of the crosslinked polymer according to Example Ia::
: To 2000 g of solution obtained according to example Ia, we add under ~.
stirring and at room temperature 70 g (0.6 mole) of chloroacetate , 'of sodium hydroxide, and then the reaction mass is heated to 90C, for 10 hours. Coated 270 g of water are added to bring the concentration at 10% of dry extract. A solution is thus obtained.
. 20 limpid, straw-yellow in color and whose viscosity at 25C is 21 cps.

EXAMPLE IX.
Alcoylati_n au y ~ y ~ gL ~ crosslinked olymer according to Example Ia:
A 1000 g of 10% solution of cationic polymer prepared according to : example Ia is added in them hours, with stirring and at ambient saturation, 27 g (0.36 mole) of glycidol. Agitation is : maintained for 5 hours and then diluted with 265 g of water.
to reduce the concentration to 10% of dry extract. We obtain thus a clear solution, slightly colored, and whose vis-30 cosity measured at 25C, is 13.8 cps.
.

':, '' . ':.
... . . ,. . -.,. . ~ ... .

B6 ~

EXAMPLE X
Alkylate with acrylamide of the crosslinked polymer according to e ~ example _a To 1000 g of 10% aqueous polyamino amide solution prepared according to Example Ia, is added at room temperature, in the presence, of a trace of sodium nitrite, 20 g (0.28 mole) of acrylamide.
The reaction medium is then heated for 10 hours at 60 C.
By adding 180 g of water, a clear solution of polymer with 10% active material and viscosity equal to 11.2 cps - at 25C.

APPLICATION EXAMPLES

Anionic shampoo - Triethanolamine lauryl sulfate ......................... 15 g - Diethanolamides of coconut yras acids .................. 3 g - Polymer prepared according to Example Ia ...................... 1.5 g - ~ at qsp .... ..... ~ .................................... 100 g ,, pH ~ 7 We apply approximately 10 cm3 of this solution to hair previously wet. We massage lightly. We rinse with water and make a second application. We massage vigorously to obtain an abundant foam, let it pause one minute to ensure ~ fixing the polymer on the hair then we rinse.
There is a great ease of disentangling the - ~ wet hair (the comb slides easily through the hair), the hair is very soft, flexible, malleable, the styling is mounts with great ease. After drying and during styling dry hair, there is also an ease of disentangling.
The hair is nervous and disciplined.

Anionic shampoo - Modified alkanolamide disodium sulfosuccinate semi-ester..15 g .

6 ~

(marketed under the trademark "Monomate DHL 50" ~ `
- Sodium lauryl ether sulfate condensed with 2.2 moles ethylene oxide ... ~ ............................ 15 g - Polymer prepared according to Example I a ....................... 1 g - Water q.s.p ............ ... ............ 100 g pH = 7.8 Anionic shampoo - Sodium lauryl ether sulfate condensed with 2.2 moles ethylene oxide ... ......... `............................ 12 g - Diethanolamides of coconut fatty acids ................... 4 g - Polymer according to the example Va ..... ~ .. ......... ~ .............. 1.5 g - Quaternary polyvinylpyrrolidone copolymers having a molecular weight of the order of 1,000,000, marketed under the trademark "GAFQUAT 755" by General ~ niline and Film Corp ....... ..................... 0.3 g - Water qs ............................................... 100 g pE = 7.5 ,:.
E ~ EMPLE A 4 .-Anionic shampoo - Myristyl ether sodium sulfate condens ~ with 2.5 moles , ethylene oxide ......................................... 5 g - Lauryl ether sodium sulfate condensed with 2.2 moles ethylene oxide ........................................., 1 g - Polymer according to Example IVa ............................... 1 g `
- Water qs ............................................... .. 100 g p ~ I = 8 . . .

Anionic shampoo 30 - Lauryl sulfate of triethanolamine ........................... 10 g - Monoethanolamides of coconut fatty acids .................. 1.5 g - Protein hydrolyzate derived from collagen at 80%
. ~

~ 8 ~ 652 active ingredients, marketed under the trademark "HYDROPO 220"
by STEPAN Chemicals ......... O ............................ 5 g - Polymer according to Example IIa .............................. 2 g - Water qs ............................................... 100 g pH = 4 The action of shampoos A 2 to 4 is similar to that of Al shampoo. Shampoo A 5 also improves the condition damaged hair by giving more resistance to fibers and more hardness in the hair. ~ -Non-ionic shampoo R ~ CHOEI-CH2-0 ~ CH2-CHOH-CH2-0 ~ 3 5 H ~ 14 g R = mixture of nonyl to dodecyl radicals - Polymer according to Example Ia ............................. 2.5 g - Lactic acid q.s.p .................... pH = 5 - Water q.s.p ............................................... 100g Non-ionic shampoo .., _ _ R-CHOH-CH2-0- -CH2-CHOH-CH2-0 3 5H R = nonyl to dodecyl 12 g - Dimethyl hydroxy ethyl cetyl ammonium chloride ......... 1.5 g - Polymer prepared according to Example Ia ....................... 1.5 g - 0.2 g quaternary polyvinylpyrrolidone copolymers having a molecular weight of the order of 1,000,000 marketed under the trademark "GAFQUAT 755"
by GENERAL ANILIN alld FILM Corp.
- Lactic acid q.s.p .......... pH 3 - Water qs ............................................... . 100g ; EXAMPLE A 8 . ~
Non-ionic shampoo ' R-C ~ IO ~ I-CH2-0 ~ CH2-CHOH-C ~ 2-0 ~ 3 5H ......................... 5 g .., 366 ~; ~

R = mixture of nonyl to dodecyl radicals - Dimethyl hydroxyethyl cetyl ammonium chloride ......... 1 g - C12H25 - ~ CH2-CH-0 ~ 4 H ................................. 5 g ~ H2 0H ''. - '.
- Polymer from example Va .................................. 3 g - Lactic acid q.s.p ........... pH 5 - Water ~ .sp ........ O .................................... 100 g EX ~ MPLE A 9 Non-ionic shampoo -- Laury alcohol oxyethylenated with 12 moles of oxide ethylene .............................................. 7 g - Lauric diethanolamide ................................. 3 g - Polymer according to Example Ia ........................... 0.5 g - Polymer according to Example IIa .......................... 0.8 g ~ '- Lactic acid q.s.p ........... pH 4.5 - Water qs .............................................. 100 g Non-ionic shampoo - Laury alcohol oxyethylenated with 12 moles of oxide ethylene ...................... ... .. ~ .. ........ 6 g 12 25 ~ CH2 ~ 1C ~ I ~~ 4 H .........
. 'CH20H `., - Lauric diethanolamide .................................. 1.5 g - Poly ~ era according to Example IV a ............................ 2 g ; ' - Lactic acid q.s.p. pH 3 ... . .
- Water q.s.p ... ................. ................... c. 100g The non-inonic shampoos of examples A6-A 10 apply like the anionic shampoos of examples Al -AT 5. There is a very great ease of disentangling the hair . . ~.
~ topped and dry hair. The disentangling is excellent and the hair retain flexibility and lightness, The , hair has volume and styling is easy to assemble.
'' . ~ - 27-':' ','. ! ;,, ~, '' . .

Reinforcement, styling cateur.
The following lotion is prepared:
- Vinyl acetate / crotonic acid 90/10 copolymer MW (molecular weight) = 10,000 ....................... 2.5 g - Polymer according to Example Ia ............................. 0.3 g ~; - 2-amino 2-methyl propane 1,3-diol q.s.p. pH 7 , - Ethanol q.s.p. 50 - Dye ................................................ 0.01g - Perfume ...... ~ ......................, ....,., ........... .. 0.2 g - Water qs .............................................. 100 ml E ~ EMPLE A 12 Styling enhancer for oily hair The following lotion is prepared:
- Polymer according to Example Ia ............................. 0.3 g - Vinyl acetate / crotonic acid 90/10 copolymer M.P. = 50,000 ........................................... 2.5 g - Polyvinylpyrrolidone / vinyl acetate copolymer 60/40 0.5 g `~ having a viscosity of 3.3 cps (measured at 25C in solution 5% in ethanol) - 2-amino 2-methyl propane 1,3-diol q.s.p. p ~ 7 , - Ethanol ....... q.s.p. 50 - Colorant ............................................... 0 , 01 g - By ~ um ........ ~. ~ ...................... 0.2 g - S-carboxymethylcysteine (antiseborrheic) ............. 0.7 g - Water q.s.p ...... 100 ml The lotions of examples All and A12 apply on wet hair and wringing ~ s after shampooing and before - ~
winding of the setting.
We notice on wet hair an ease of demem-age. After winding the styling, we see that the hair is more nervous, softer and slightly shiny.
'' '' "
- 28 - ~

. . . .., ~ .., ..,:. . .

SZ

The holding of the styling is considerably prolonged.
; EXAMPLE A 13 Lotion for "brushing" (shaping) The following lotion is prepared:
- Polymer according to Example Ia ........................... O, 5 g - Ethanol q.s.p .... 50 - Dye .............................................. 0, 01 g - Perfume ........... ~ .................................... 0.2 g - Water q.s.p ........ ...................... ~ ............... 100 ml `10 We apply this lotion on wet hair and - wrung after shampooing. We shape the hair using ~
a brush ~ out in ~ sample the hair using a blow dryer hand.
There is a very good passage of the brush and a prolonged holding of the hairstyle. We also note that the hair is shinier and softer.

Rinse ~ rinsed lotion e) for fine and soft hair.
We prepare the following lotion:
- Cetyl / stearyl alcohol 30/70% oxyethylenated at 33%
marketed under the brand name "Cire de Sipol AO" by SINNOVA ................................................. 1.5g - Dimethyl dist ~ arylammonium chloride, marketed SOU5 the trademark "ARQUAD 2 ~ T 75" by A ~ MOUR 1.5 g - R-CHO ~ -CH2-0- ~ H2-CHOH-CH2- ~ 3 5H .............. 1 g R = mixture of nonyl to dodecyl - Polymer according to Example IIa .... ~ ........................ 2 g - Quaternary polyvinylpyrrolidone copolymers having a molecular weight of the order of 1,000,000 marketed under the brand "GAFQUAT 755" by GENERAL ANILIN and FILM Corp ... ........ ~ ................ 0.5 g * Trademark . ~.

6 ~ i52 - Hydroxyethylcellulose .................................... 0.9 g - Maleic acid q.s.p ..... pH 8 - Water qs ............................................... 100g We apply this lotion to wet hair and towel-dried after shampooing, leave to stand for 5 minutes, then rinse.
There is a very good disentangling of wet hair.
'' After styling and drying, the hair is nervous, easy to style and shine.

Styling lotion The following lotion is prepared:
- Polymer according to example Va .............................. O, 5 g - Silicone oil ........................................ 0.1 g - Hydroxyethylcellulose .................................... 0.2 g - Ethanol ................................................ .. 50 ml - Perfume ................................................ ... 0.2 g - Water qs ............................................... 10C ml This lotion for men is applied to hair wet. The hair is styled and then dried. We aknowledge that the hair is nervous, slightly hardened and maintained-, l nent perfectly in place.

Styling gel - Polymer according to example Ia .............................. l g - Hydroxyethylcellulose .................................... 2 g , - Silicone oil ........................................ 0.5 g - Ethanol ............; .................................. ~ rO ml - Perfume ................................................ 0.02 g - Water q.s.p ........... ~ .............. ~. .... ~ ............ 100 g i ~
A small amount of this gel, applied to hair ~ dry, ensures good hold of the hairstyle while communicating ,, ,, '.

.

~ a ~ 86652 hair shine.

Structured lotion without rinsing.
- Dimethylol ethylene thiourea formu ~ e.
~ CH20H
~ 2 - ~ / CS ~ 0.5 g CH OH

`10 - Polymer according to Example Ia ............................ 0.5 g , - Phosphoric acid q.s.p ... pH 3 - Water q.s.p .............................................. 100 ml '; We apply this lotion on washed and towel-dried hair after shampooing and before styling. We see that in the state wet hair is easily detangled and has a silky touch.
After styling and drying, the hair is shiny -~ and nervous, they have body and volume and their touch is i sweet.
..

We obtain a similar result by replacing the polymer prepared according to Example Ia by the polymer prepared according to Example IIa.

Structuring lotion, applied with rinsing.
- Thiourea ethylene dimethylol of formula ~ CH20H

, '. C ~ I2 ~ \;
CS ................................................ 1 g CII - N
2 - \
C ~ 2H
,, - Polymer according to Example Ia ......................... 1 g ~::

6 ~ i ~

- Phosphoric acid q.s.p ..... pH 3 - Water q.s.p ............................................. 100 ml We apply this lotion on wet hair and clean. Leave to stand for 10 minutes then rinse.
Hair has a soft feel and is easy to detangle is lying .
After styling and drying, the comb passes easily-; in hair that is shiny, curly and has volume.

- By replacing, in the lotion above, the polymer ; according to example Ia with the polymer according to example IIa, we `Obtained an equally good result.
EXAMPLE_A21 - A 22 Styling lotion for sensitized hair. '' "
A 21 An aqueous solution containing 1% of active material is prepared of the compound prepared in Example Id and 0.5% of adjusted NaCL
with citric acid at pH 7.
Apply to bleached hair. We do the setting folds and dried.
The hair is hardened and nervous, the touch is so ~ them and easy disentangling.
A 22 An aqueous solution containing 1% of material is prepared active compound prepared in Example Ic and 1.5% N ~ I4CL
a ~ ustée at pH 5 with lactic acid.
We apply ~ ue on bleached hair. We do the setting folds and dried. The hair is hardened. They are elastic and shiny. The touch is silky and the detangling faclle. ~ -`

EXAMPLE A 23 ^ ~ -Treatment lotion applied with rinsing.
Apply to wet and clean hair 25 ml of ... . . .

6S; ~
. : ,, the following solution:
- Polymer according to example Ib ............................. 1.5 g - Citric acid q.s.p. pH 5 - Water qs .............................................. 100 g Leave to stand for 5 minutes and rinse. The hair have a soft touch and detangle easily. We make the bet `in folds and dried. Dry hair is easily disentangled.
They are bright and nervous. ~;

The same result is obtained by replacing ~ cant 1.5 g of polymer according to example Ib per 1 g of polymer according to example IIIa.

.
Structuring lotion applied without rinsing.
- Dimethylolethylene thiourea of formula / CH2 ~ l CS

OEI2OH ............................................ 0.6 g - Polymer according to Example III b .......................... 0.5 g - Phosphoric acid q.s.p.` pH 3 ~ Water qs .............................................. 100 g Apply the mixture to washed and towel-dried hair : before proceeding to styling. Hair untangles easily, the touch is silky. We do the styling and we dry.
The hair is shiny, nervous, elastic and has volume. The touch is silky, the disentangling easy.

We get the same result if we replace the polymer according to Example III b with the polymer according to Example IV b.

.
..:

38 ~ 165 ~

Structuring lotion applied with rinse - Dimethylolethylene thiourea of formula CH -., / S

CH20H ........................................... 1.5 g - Polymer according to Example VIa ........................... 1 g - -, Hydrochloric acid q.s.p. pH 3, 10 - Water q.s.p ........................................ ~ 100 g;
, The mixture is applied to washed and towel-dried hair.
Leave for 10 minutes and rinse. Detangling is easy, the hair has a soft and silky touch. We do the setting;
folds and dried under helmet.
Dry hair is easily untangled, it is bright, nervous and full of volume.

Anionic shampoo.
- monoethanolamine lauryl sulfate .................. 10 g 20 - Monoethanolamides of coconut fatty acids ........... 1.5 g - Polymer according to e ~ example Ic. ~ ....................... 1 g - Lactic acid, q.s.p. pH 7.2 ~ Water q.s.p ........................................... 100 g ..

Anionic shampoo, Laurylether sul ~ ate of oxyethylenated sodium with 2.2 moles of ethylene oxide - Triethanolamine lauryl sulfate .................... 6 g - Diethanolamides of coconut fatty acids ............. 3 g 30 - Polymer according to Example IIIa ....................... 1.5 g - Lactic acid q.s.p. pH 7.6 '; '' "

::. :,,. .:,. . . . . ... .

; 2 - Water qs ............, ................. O ................ 100g Anionic shampoo.
~ same composition as the shampoo of Example A 29, except that the polymer according to Example IIIa is replaced by the polymer according to Example IIIb.

Anionic shampoo.
- Myristyl ether sodium sulfate, oxyethylenated with 2.5 moles ethylene oxide ....., ........, .......................... 6 g - Lauryl ether sulfate of monoethanolamine, oxyethylenated with 2 moles of ethylene oxide ............................. 9 g Diethanolamides of coconut fatty acids ................ 3.5 g - Protein hydrolyzate derived from collagen, 80%
; of active ingredients, sold under the trademark "Hydropo 220" by STEPAN chemicals ..................... 3 g - Polymer according to Example IV b .......................... 1 g - Lactic acid q.s.p. pH 7.5 ~
- Water qs ............................................. 100 g ;

Anionic shampoo.
Same composition as the example shampoo A 31, except that the polymer according to example IVb is replaced with the polymer according to Example VIa.
The action of the shampoos of examples A 28 to A 30 is similar to that of the shampoo of Example A 1. The shampoos of examples A 31 and A 32 further improve the condition of damaged hair by giving more resistance to fibers and more hardness to the hair.

Non-ionic shampoo.

8 ~ 2 , C12H250 - ~ EC2 ~ I3 (CH20H ~ n n represents an average statistical value of approximately 4 ~
- Laury alcohol oxyethylenated with 12 moles of ethyl oxide-, '; lene ................................................. .... 6 g - Carboxylic derivative of imidazole of formula -1 ~, '~' ';
I / CE ~ 2-COONa ¦¦ ¦ ~ CH2-CH2-0-CH2-COONa ......................... 4 g \ / CH2 H

- Polymer according to Example III b ................... a 1 g - Lactic acid q.s.p. pH 5 - Water q.s.p .............................................. 100 g ; Same composition as the shampoo of example ~ 33, except that polymer III b is replaced by polymer Ic.
EXAMPLE A_35 Same composition as shampoo A 33, sau ~ that the polymer III b is replaced by polymer IIIa.

, Non-ionic shampoo.
- Laury alcohol oxyethylenated with 12 moles of oxide of ~ thylene .............. ~ ................... 10 g - Monoethanolamides of coconut fatty acids ............... 1.5 g -- Lauryl dimethylamine oxide ........................... 3 g ~ - Polymer according to Example VIa ............................ 0.5 g ; - Lactic acid q.s.p .... pH 3.3 - Water q .. sp ............................................ .. 100 g Same composition as shampoo A 36, except that polymer according to example VIa is replaced by the polymer according to . 1 ,,,, ..,,. ,. ,, - ,, - ", ~,,", .. .. .. ...

. ~.
~ example IVb.
: EXAMPLE A 38 12 25 ~ C2H30 (CH20H ~ nH
n represents an average statistical value of approximately 4. ~:
R-CHOH-CH2-0- ~ CH2-CHOH-CH2-0 ~ nH ........ 10 g ~;
"R = mixture of Cg-Cl2 alkyl radicals - n represents an average statistical value of approximately 3.5.
.- Polymer according to Example III b ......... 1.5 g - Lactic acid q.s.p. pH 5 - Water q.s.p .............................. 100 g Same composition as the shampoo of example A 38, except that the polymer according to Example IIIb is replaced by:
polymer according to Example IVb.
; The action of shampoos according to examples A 33 - A 39 is similar to that of the shampoos according to examples A 6 -At 10.

;:
No-rinse structuring lotion, cage : 20 - Thiourea dimethylolethylene of formula . ~ CH2OH
CH - N

. / CS .................................... 0.5 .:. 2 - Polymer prepared according to Example VII ............. 0.6 g ;: ~ - Phosphoric acid q.s.p ......................... p ~ 3 - Water q.s.p ....................... ~ .................... 100 cm ; We apply this lotion on washed and towel-dried hair after shampooing and before styling 5. We see that in the state wet, the hair is easily detangled and has a silky touch.

,. ~, ~.
.

lB ~ ÇiÇiSiZ
. ``

After styling and drying, the hair is bright and nervous they have body and volume and their touch is soft. ; ~

Lotion increasing the volume of sensitized hair applied with rin ~ a ~ e Calcium acetate ....................................... 2 g ; - Polymer prepared according to Example IX .................... 2 g - Phosphoric acid q.s.p ......... pH 8 `

- Water q.s.p .............................................. 100 cm3 We apply this lotlon on wet hair and clean.
Hair has a soft feel and is easy to detangle is lying.
After styling and drying, the comb passes easily-lies in hair that is shiny, nervous and has volume.

.: ' Structuring lotion, applied with rinse, cage - Thiourea dimethylolethylene of formula: `

; I \ CS ............................................... ... 1 ~. ' ', CH - Nj - Polymer prepared according to Example VII ................... O, 5 g - Polymer prepared according to Example VIII .................. 0.4 g - Phosphoric acid q.s.p ......... pH 3 - Water q.s.p ..... ................................. ~. 100 cm 30We apply this lotion to wet hair and clean. Leave to stand for 10 minutes then rinse.
`" ' - 3 ~ -86 ~

Hair has a soft feel and is easy to detangle is lying.
After styling and drying, the comb passes easily-lies in hair that is shiny, nervous and has volume.

Non-ionic shampoo 'R CHOH CH -O- ~ CH2-CHOH-CH2- ~ 3,5 15 g R = Cg to C12 alkyl - ~ ~ -Polymer prepared according to Example Ia .................... 1.5 g - NaCl ...................... O ...................... 1 g - Lactic acid q.s.p ...... ~ ...... pH 3 - Water qs ............................................... 100 ml Applied to sensitized hair, this shampoo of clear aspect gives an abundant and rather soft foam.
; It very clearly improves the detangling of hair wet.
After drying, the hair is nervous, light and brilliant.
20 ~ XAMPLE ~ A 44 Non-Lonic Shampoo ~ _for sensitized hair ~ s R-CHOH-CH2-0 ~ CH2-CHOH-CH2 ~ 3.5 17 g R = Cg to C12 alkyl Pol ~ m ~ re prepared according to Example Ia ....................... 0.8 g Polymer with motif N-CH2-CH2-C-O-C-cH2-cH2 prepared by the condensation of piperazine and piperazine bis-acrylamide (preparation described in the Luxembourg patent Applicant's N 64371) .............................. 3 g .

665; ~

NH (CH2-CH2-0) X -H

C18H37 1.5 g \ NH- (CH2-CH2-0) y -H

x - ~ y = 5 NH4Cl ................................................. .... l, 2 g ~ `
Lactic acid q.s.p ........... ~ pH 3.5 Water qs ................................................ 100 ml Applied to sensitized hair, this shampoo of clear aspect provides an abundant and soft foam which eli-; ~
mine ~ easily rinsing.
Hair detangles without difficulty and after séha ~ e have swelling and nervousness, while remaining soft and docile to styling. ``

Shampoo ~ non-ionic for sensitized hair , C12H250- ~ C2EI30 tC ~ 2H) ~ 4H 17 g ; Polymer prepared ~ according to Example IVa ...................... 1.8 g Diethanolamide lauric ................................... 3 g ~ -MaCl ................................................. ..... 0.8 g Lactic acid q.s.p .............. pH 5 Water qs ................................................ 100 ml Applied to sensitized hair ~ 5, this shampoo; ~
clear appearance provides abundant and pleasant foam and helps to detangle wet hair.
`After drying, the hair is soft, shiny and very nervous staying disciplined.

Ren ~ or ~ styling agent for qras hair;
; 90/10 crotonic vinyl acetate copolymer Molecular weight 25,000 .................................. 2.5 g Polyvinylpyrrolidone / vinyl acetate 60/40 copolymer ~,.

(viscosity 3.3 centipoise, 5% in ethanol and 25C) ................................................ ..... 0.5 g - Polymer prepared according to Example VII ..................... 0.3 g - S-carboxymethylcysteine (antiseborrheic agent) ......... 0.7 g - Triethanolamine q.s.p. pH 8.6 - Ethyl alcohol ......................................... 10 ml- Water qs. .............................................. 100 ml Apply this lotion to wet and towel-dried hair after shampooing and before rolling up the setting.
- We notice on wet hair an ease of disproportion-age.
After winding the styling we see that the hair is nervous, softer and slightly shiny.
The holding of styling is considerably prolonged.

Hair styling enhancer - Vinyl acetate / crotonic acid 90/10 copolymer molecular weight 70,000 ................................. 2.5 g - Polyvinylpyrrolidone / ac copolymer vinyl 60/40 (viscosity 4 cps at 5% in ethanol and at 25C) .......... 0.5 g - Polymer prepared according to Example VII ..................... 0.3 g - Triethanolamine q.s.p ........ pH7 - Ethyl alcohol ......................................... 10 ml - Water ~ .sp ............................................. .. 100 ml Apply this lotion to wet and towel-dried hair after shampooing and before rolling up the setting.
We notice on wet hair an ease of mismatch.
After winding the styling we see that the hair is more nervous, softer and slightly shiny.

'.

: `` '' 6 ~ i2 The holding of styling is considerably prolonged.
EXAMPLE N A ~ 8 Hair styling enhancer - Vinyl acetate / crotonic acid 90/10 copolymer molecular weight 50,000 ................................ 2.5 g - Polyvinylpyrrolidone / vinyl acetate 60/40 copolymer (viscosity 3.5 cps (at 5% in et ~ anol and at 25C) 0.5 g - Polymer prepared according to Example IX. ................... 0.3 g - Triethanolamine q.s.p ......... p ~ 7 - Ethyl alcohol ........................................ 10 ml - Water qs .............................................. 100 ml , We apply this lotion on molded and towel-dried hair -after shampooing and before rolling up the setting.
We observe on soft hair ~ ease of ,.,. i `~
unraveling.
After winding the styling we see that the hair is more nervew ~, softer and slightly more shiny.
The holding of styling is considerably prolonged.

Reinforcing styling agent for colored hair - Vinyl acetate / crotoni acid copolymer ~ eu 90/10 ,.
molecular weight 50,000 ................................ 2.5 g neutralized with triethanolamine - Polyvinylpyrrolidone / vinyl acetate 60/40 copolymer (viscosity 3.7 cps at 5% in ~ thanol and at 25C). 0.5 g - Polymer prepared according to Example Ia ..................... 0.5 g;
- Dimethyl hydroxymethyl ketylammonium chloride ........ 0.1 g -- Hydrochloric acid q.s.p .... pH 8 - Ethyl alcohol ........................................ 50 ml - Water qs .............................................. 100 ml Apply this lotion to wet and towel-dried hair .; ~,.

:.
. ~. ~ ... ... . .

hair conditioner. We shape the hair using a brush while drying the hair using a hand dryer.
There is a very good passage of the brush and a prolonged holding of the hairstyle. We also note that the hair is shinier and softer.

E ~ EMPLE N A 50 No-rinse structuring lotion ~ aqe - Thiourea ethylene dimethylol of formula / C ~ I2OH
2 \
I / CS ... ..... ~ ............................... 0.5 g C 2 \
. CH20H
- Polymer prepared according to Example X ..................... 0.6 g - Phosphoric acid q.s.p .... pH 3 - Water q.s.p ..... ........................................... 100 ml We apply this lotion on hair washed and es ~ golden after shampooing and before styling.
It is found that in the wet state the hair is disentangled easily and have a silky touch.
After styling and drying, the hair is shiny and nervous ~
They have body and volume and their touch is soft.

E ~ EMPLE N A 51 Rinse (rinsed lotion) for fine and soft hair - Vaseline oil ...................................... 7.5 g ~ Dimethyl distearyl ammonium chloride ................ 1 g ; - R-0 ~ C2H30 (CH2OH) 3 6H (R = alkyl C16 to C1 ~ 3) --- 3 ~ 75 g _ _ - C12H250 - _ C2H30 (CH2OH) - 4H .......................... 3.75 g - Polymer pr ~ prepared according to e ~ ample IX .... ~ ............... 2 g - Quaternary copolymer of polyvinylpyrrolidone having a molecular weight of the order of 1,000,000, ... . . ~.

sold under the "GAFQUAT 755" trade mark by General Aniline and Film Corporation .............. 2.5 g - Citric acid q.s.p..O. pH 3 - Water q.s.p ........................................ 100 g `
, ''.::.
Apply this lotion to wet and towel-dried hair after shampooing, leave on for 5 minutes, then rinse.
There is a very good untangling of wet hair.
i After styling and drying, the hair is nervous, easy to style and shiny.
EXAMPLE NO A 52. . .
Anionic shampoo ~ `- Triethanolamine lauryl sulfate at 40% material ~ ~, active ............................................ 30 g - Diethanolamides of coconut fatty acids ......... ~ 1.5 g - Polymer prepared according to Example Ia (100% of . . .
active ingredient) ....................... ........... 1 g; `
- Polymer with the motif ~ -CH2-OEIO ~ I-CH2 ~ ....... 0.5 g where Y denotes ~
'~; -N 11- or ; CEI2-0-CH2OH
these two groupings being distributed statistically - Distilled water ~ q.s.p ................ ~ ................... 100 g pH = 7.5 ~ `
We apply approximately 10 cm3 of this clear solution on previously wet hair. We massage lightly.
`We rinse with water and make a second application. We mass energetically to obtain an abundant foam, let stand for a minute to secure the polymer on hair then rinse.
there is great ease of dismantling the CheVe11X

, ~ - 44 -wet (the comb goes easily through the hair), the hair is ~ very soft, flexible, malleable, the styling is assembled with great ease. After drying and when styling the dry hair, there is also an ease of disentangling.
; ~ The hair is nervous and disciplined.

Cationic shampoo - Tetradecyltrimethylammonium bromide ... .. ~ ........... 75 g - Polyoxyethylenated lauryl alcohol with 12 moles of oxide ethylene ............ O ................................. 50 g - Pre-prepared polymer according to Example Ia .................... 5 g - Polymer with the motif ~ Y-CH2-CHOH-CH2 ~ ......... 0.5 g where Y denotes ~
-N N- or -N-f ~ I2 CH -0 ~ CH -CH OH
these two groupings being statistically distributed.
- Lactic acid q ... pH 5 - 5.5 - Distilled water q.s.p ................................... 1000 g This clear-looking solution is applied to dyed hair. After massaye, we rinse ~ with water, then we efEectue a second application. We massage energetically to obtain abundant foam, then rinse.
There is a great ease of disentangling the hair wet (the comb slides easily through the hair), the hair is very soft, flexible, malleable, the styling is mounts with great ease. After drying and during styling dry hair there is also an ease of disentangling.
The hair is nervous and disclplined.
':

. ' .

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... .
~. . . . . .

Claims (60)

The realizations of the invention, about which a right exclusive of property or lien is claimed, are defined as follows: - 1. Cosmetic composition for hair containing in an aqueous or hydroalcoholic solution at least one agent anionic, cationic, nonionic or amphoteric surface, and at least one crosslinked water-soluble polymer, chosen from (I) the crosslinked polymers obtained by the crosslinking of a polyamino-polyamide prepared by polycondensation of a compound acid chosen from (i) organic dicarboxylic acids, (ii) double aliphatic mono- and dicarboxylic acids ethylenic bond, (iii) the esters of the abovementioned acids, (iv) mixtures of these compounds, (v) the products obtained by reaction of a primary bis or secondary bis amine on one of compounds i), ii), iii) or iv), on a polyamine chosen from polyalkylene polymines bis primary and mono- or disecondai-res, 0 to 20 mole% of this polyamine which can be replaced by hexamethylenediamine or 0 to 50% of this polyamine which can be replaced by a primary bis amine, or by a bis-secondary; the crosslinking being carried out by means of an agent crosslinker chosen from epihalohydrins, diepoxides, dianhydrides, and bis unsaturated derivatives; either from (II) crosslinked polymers (I) alkylated with an alkylating agent chosen from (a) epoxides, (b) ethylenically composed unsaturated, (c) chloracetic acid, (d) propane sultone or butane sultone; polymer characterized in that the crosslinking is carried out using 0.025 to 0.35 mole of agent crosslinking by amine group of polyaminoamide; in the composition obtained the crosslinked polymer having all of the following characteristics:
(1) it is perfectly soluble in water at 10% without formation gel;
(2) the apparent viscosity of a 10% polymer solution by weight in water at 20 ° C, and at a speed gradient of 26.3 sec.-1, is greater than 3 centipoise;
(3) it does not contain alkyl groups and it is chemically stable. 2. Composition according to claim 1, characterized by the fact that it comprises at least one antiseborrheic agent, an anti-dandruff agent, a perfume, a reinforcing agent for hair, electrolyte or other cosmetic resin. 3. Cosmetic composition for hair containing in an aqueous or hydroalcoholic solution at least one polymer water-soluble crosslinked as defined in the claim tion 1, as well as an additive capable of application human hair, which consists of an anti seborrheic, an anti-dandruff agent, a perfume, an agent hair enhancer, hair resin, perfume, an electrolyte with desensitizing action on the hair or a cationic, anionic, amphoteric surfactant or zwitterionic. 4. Composition according to any one of the claims 1 to 3, characterized in that the acid compound used for the preparation of the polyamino-polyamide is chosen from adipic acid, terephthalic acid, the esters of these acids, the adduct of 1 t ethylenediamine on the acrylic, methacrylic, itaconic acids or their esters. 5. Composition according to claims 1, 2 or 3, charac-terrified by the fact that the polyalkylene polyamine used for the preparation of the polyamino-polyamide is chosen from diethylene triamine, dipropylene triamine, triethylene tetramine and their mixtures with ethylene diamine, hexa-methylenediamine and piperazine. 6. Composition according to claims 1, 2 or 3, charac-terrified by the fact that the crosslinking agent is chosen from divinylsulfone, methylene-bis-acrylamide, diglycidylether and N, N'-bis-epoxy propyl piperazine. 7. Composition according to claims 1, 2 or 3, charac-terrified by the fact that it is used as crosslinking agent chlorohydrin. 8. Composition according to claim 1, characterized by the fact that the crosslinked polymer is obtained using 0.025 to 0.2 mole of crosslinking agent per amine group of polyamino-polyamide. 9. Composition according to claim 8, characterized by the fact that the crosslinked polymer is obtained using 0.025 to about 0.1 mole of crosslinking agent per amine group of polyamino-polyamide. 10. Composition according to claims 3 9 8 or 9 characters laughed at by the fact that the polymer is prepared by crosslinking using 11 moles of epichlorohydrin per 100 amino groups polyamino-polyamide, a polyamino-polyamide prepared by polycondensation in stoichiometric proportions of the acid adipic and diethylene triamine. 11. Composition according to claims 3,8 or 9, charac-terrified by the fact that the bis-primary amine is chosen from the group consisting of ethylene diamine and hexamethylene diamine. 12. Composition according to claims 3, 8 or 9, charac-terrified by the fact that the secondary bis amine is piperazine. 13. Composition according to any one of claims 3, 8 or 9, characterized in that the polyamino amide is made up of formula patterns - OC - R - CO - Z
where R represents:
, - (CH2) 4- Z represents:
in the proportions of 60 to 100 mol%, the radical (II) where x = 2 and n = 2 or 3, or x = 3 and n = 2 in the proportions of 0 to 20 mole%, the radical - NH - (CH2) 6 - NH -;
in the proportions of 0 to 50 mol%, the radical (II) above where x = 2 and n = 1, or the radical 14. Composition according to claims 3, 8 or 9, characterized in that the polyamino-polyamide is prepared by polycondensation of adipic acid and diethylene triamine. 15. Composition according to claims 3, 8 or 9, characterized in that the polyamino-polyamide is prepared by polycondensation of adipic acid and a mixture of diethylene triamine and piperazine. 16. Composition according to claims 3, 8 or 9, characterized in that the polyamino-polyamide is prepared re by polycondensation of adipic acid and triethylene tetramine. 17. Composition according to claims 3, 8 or 9, characterized in that the polyamino-polyamide is prepared re by polycondensation of methyl itaconate with ethylene diamine and diethylene triamine. 18. Composition according to claims 3 9 8 or 9, characterized in that the polyamino-polyamide is prepared by polycondensation of methyl acrylate with ethylene diamine and diethylene triamine. 19. Composition according to Claims 3, 8 or 9, characterized in that the polyamino-polyamide is prepared by polycondensation of methyl methacrylate with ethylene diamine and diethylene triamine. 20. Composition according to claim 1, characterized by the fact that the crosslinked polymer has been alkylated with an epoxide. 21. Composition according to claims 3, 8 or 9, characterized in that the epoxide is chosen from glycidol, ethylene oxide and propylene oxide. 22. Composition according to claim 1, characterized by the fact that the crosslinked polymer has been alkylated by a compound dried ethylenically unsaturated. 23. Composition according to claim 3 characterized by the fact that it contains a hair desensitizing agent, which is a water soluble electrolyte. 24. Composition according to claim 23, characterized by the fact that the electrolyte is a chloride or an acetate of sodium, potassium, calcium or ammonium. 25. Composition according to claim 23, characterized by the fact that the electrolyte is present at 0.01 to 5%
in weight. 26. Composition according to claims 23, 24 or 25, characterized in that the proportion of electrolyte by ratio to polymer varies between 0.1: 1 and 1.5: 1. 27. Composition according to Claims 3, 8 and 9, characterized by the fact that it is in the form of solution, dispersion, gel, cream or aerosol. 28. Composition according to claim 3, characterized by the fact that it is in the form of a liquid emulsion petroleum derivative base, and contains a surfactant cationic or nonionic. 29. Composition according to claim 28, characterized by the fact that it also contains a resin for treatment capillary. 30. Cosmetic composition for hair containing in an aqueous hydroalcoholic solution a crosslinked polymer water soluble selected from the group consisting of A) a polyamino-polyamide prepared by polycondensation (1) methyl itaconate with a mixture of ethylene diamine and diethylene triamine, or (2) methyl acrylate with a mixture of ethylene diamine and diethylene triamine, or (3) methyl methacrylate with a mixture of ethylene diamine and diethylene triamine, said polyamino-polyamide being crosslinked with 0.025 to 0.35 mole of a crosslinking agent per group polyamino-polyamide amine chosen from epichlorohydrin, methylene bis-acrylamide, N, N'-bis epoxy propyl piperazine and divinyl sulfone; and B) the crosslinked polymer (A) alkylated with an al-coylant chosen from glycidol, ethylene oxide, oxide propylene, acrylamide, acrylic acid, chloro- acid acetic acid, sodium chloroacetate, propane sultone and butane sultone; said crosslinked polymer being soluble in water at 10% by weight without gel formation, viscosity apparent from a 10% polymer solution in water being greater than 3 centipoise at 25 ° C, said crosslinked polymer soluble in water being present in an amount of 0.1 to 5% in weight of the composition. 31. Process for conditioning human hair characterized by the fact that a composition is applied to them comprising an aqueous or hydroalcoholic compatible medium and at least one crosslinked water-soluble polymer, chosen among (I) the polymers obtained by the crosslinking of a polyamide no-polyamide prepared by polycondensation of an acidic compound chosen from (i) organic dicarboxylic acids, (ii) double bond mono- and dicarboxylic aliphatic acids ethylenic, (iii) esters of the above acids, (iv) mixtures ges of these compounds, (v) the products obtained by reaction of a primary or secondary bis amine on one of the compounds (i), (ii) (iii), or (iv), on a polyamine chosen from polyalkylene-primary and mono- or dis-secondary bis polymines, 0 to 20 mole%
of this polyamine which can be replaced by hexamethylene-diamine or 0 to 50% of this polyamine can be replaced by a primary bis amine, or by a secondary bis amine; reti-culation being carried out by means of a crosslinking agent chosen from epihalohydrins, diepoxides, dianhydrides, and bis unsaturated derivatives;
either from (II) the crosslinked polymers (I) alkylated by a alkylating agent chosen from (a) epoxides, (b) compounds ethylenically unsaturated, (c) chloracetic acid, (d) pro-pane sultone or butane sultone polymer characterized by the fact that the crosslinking is carried out by means of 0.025 to 0.35 mole of crosslinking agent per amine group of the polyamino-amide in the composition the crosslinked polymer having all of the following characteristics:
(1) it is perfectly soluble in water at 10% without formation gel;
(2) the apparent viscosity of a 10% polymer solution by weight in water at 25 ° C, and at a speed gradient of 26.3 sec.-1, is greater than 3 centipoise, (3) it does not contain alkyl groups and it is chi-mically stable. 32. Method according to claim 31, characterized by the fact that the acidic compound used for the preparation of the poly-amino-polyamide is chosen from adipic acid, acid terephthalic acid, the esters of these acids, the adduct ethylenediamine on acrylic and methacrylic acids, itaconic or their esters. 33. Method according to claim 31, characterized by the fact that the polyalkylene polyamine used for the preparation tion of the polyamino-polyamide is chosen from diethylene triamine, dipropylene triamine, triethylene tetramine and mixtures thereof with ethylene diamine, hexamethylenediamine and piperazine. 34. Method according to claims 31, 32 or 33, characterized in that the crosslinking agent is chosen from divinylsulfone, methylene-bis-acrylamide, diglycidylether and N, N'-bis-epoxy propyl piperazine. 35. Method according to claims 31, 32 or 33, characterized in that the crosslinking agent is epichloro-hydrin. 36. Method according to claim 31, characterized by the fact that the crosslinked polymer is obtained using 0.025 about 0.2 mole of crosslinking agent per amine group of polyamino-polyamide. 37. Method according to claim 36, characterized by the fact that the crosslinked polymer is obtained using 0.025 to about 0.1 mole of crosslinking agent per amine group of polyamino-polyamide. 38. Method according to claim 31, characterized by the fact that the polymer is prepared by crosslinking using 11 moles of epichlorohydrin per 100 amino groups of the polyamino-polyamide, a polyamino-polyamide prepared by poly-condensation in stoichiometric proportions of adipid acid that and diethylene triamine. 39. Method according to claims 31, 36 or 37, characterized in that the primary bis amine is ethylene diamine or hexamethylene diamine. 40. Method according to claims 31, 36 or 37, charac-terrified by the fact that the secondary bis amine is piperazine. 41. Method according to claims 31, 36 or 37 charac-terrified by the fact that the polyamino amide consists of formula patterns - OC - R - CO - Z

where R represents , - (CH2) 4- Z represents:
in the proportions of 60 to 100 mol%, the radical - NH -? (CH2) x - NH? N (II) where x = 2 and n = 2 or 3, or x = 3 and n = 2 in the proportions of 0 to 20 mole%, the radical - NH - (CH2) 6 - NH -;
in the proportions of 0 to 50 mol%, the radical (II) above above in which x = 2 and n = 1, or the radical 42. Method according to claims 31, 36 or 37 charac-terrified by the fact that the polyamino-polyamide is prepared by polycondensation of adipic acid and diethylene triamine. 43. Method according to claims 31, 36 or 37, characterized in that the polyamino-polyamide is prepared by polycondensation of adipic acid and a mixture of diethylene triamine and piperazine. 44. Method according to claims 31, 36 or 37, characterized by the fact that the polyamino-polyamide is prepared by polycondensation of adipic acid and triethylene tetramine. 45. Method according to claims 31, 36 or 37, characterized in that the polyamino-polyamide is prepared by polycondensation of methyl itaconate with ethylene diamine and diethylene triamine. 46. Method according to claims 31, 36 or 37, characterized in that the polyamino-polyamide is prepared by polycondensation of methyl acrylate with ethylene diamine and diethylene triamine. 47. Method according to claims 31, 36 or 37, characterized in that the polyamino-polyamide is prepared by polycondensation of methyl methacrylate with ethylene diamine and diethylene triamine. 48. Method according to claim 31, characterized by the fact that the crosslinked polymer has been alkylated with an epoxide. 49. Method according to claim 48, characterized by the fact that the epoxide is selected from glycidol, the oxide ethylene and propylene oxide. 50. Method according to claim 31, characterized by the fact that the crosslinked polymer was alkylated by a compound ethylenically unsaturated. 51. Method according to claims 31, 36 or 37, characterized by the fact that the composition contains a nonionic, anionic, cationic, amphoteric surface, or Zwitterionic. 52. Method according to claims 31, 36 or 37, characterized in that the composition is a reinforcing agent hair cutter. 53. Method according to claims 31, 36 or 37, characterized in that the composition is in the form of solution, dispersion, gel, cream or aerosol. 54. Method according to claim 31, characterized by the fact that the composition has a pH of between 2 and 11. 55. Method according to claim 54, characterized by the fact that the composition has a pH of between 3 and 8. 56. Method according to claims 31, 36 or 37, characterized by the fact that the crosslinked polymer is present in the composition in an amount between 0.1 and 5% by weight. 57. Method according to claim 31 characterized by the fact that the composition contains an electrolyte soluble in the water. 58. Method according to claim 57, characterized by the the electrolyte is sodium chloride or acetate, potassium, calcium or ammonium. 59. Method according to claim 57, characterized by the fact that the electrolyte is present in an amount between 0.01 and 5% by weight. 60. The method of claim 57, 58 or 59, characterized in that the proportion of electrolyte by ratio to polymer varies between 0.1: 1 and 1.5: 1.