CA1088250A - Hair conditioner - Google Patents

Abstract

Polyamino-polyamide polymer prepared by the crosslinking of a polyamino-polyamide prepared by polycondensation of an acid compound chosen from (i) organic dicarboxylic acids, (ii) aliphatic mono- and dicarboxylic acids with ethylene double bonds, (iii) esters of the abovementioned acids, (iv) mixtures of these compounds; on a polyamine chosen from bis-primary and mono- or bis-secondary polyalkylene polyamines, 0 to 20 mole% of this polyamine can be replaced by hexamethylene diamine or 0 to 50% of this polyamine which can be replaced by a bisprimary amine, preferably ethylenediamine, or by a bis-secondary amine, preferably piperazine. Crosslinking being carried out using 0.025 to 0.35 mol of a crosslinking agent by amine group of polyamino-polyamide chosen from epihalohydrins, diepoxides, dianhydrides and bis unsaturated derivatives. This polymer is alkylated by an alkylating agent chosen from acrylamide and glycidol, the crosslinked polymer having all of the following characteristics: 1) it is perfectly soluble in water at 10% without gel formation; 2) the viscosity of a 10% solution in water at 25.degree. C is greater 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 centipoises: 3) it does not contain a reactive group and in particular it does not have an alkylating property and it is chemically stable. This polymer is especially useful for the preparation of cosmetic compositions which make it possible to improve the condition of the hair as well as the appearance of the hair.

Description

325 ~: ~

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 condition or degradations following the action of atmospheric agents or the action of treatments, such as discoloration, perms or stains, are often difficult to unravel and style especially with regard to abundant hair. They are generally, and have degrees ~, various, dry, dull and ragged or lacking in "vigor" and "nerv ~
vo ~ ity ".
We tried to limit or correct these faults by applying a conditioning composition to the hair "intended to improve the condition of the hair, moist 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 cited, which ensures good maintenance of the hairstyle. The agents ensuring the "conditioning of the hair" are called "condition-neurs ".,;
We have already used for the conditioning of the hair synthesized polymers ~ u ~ such as polyethylene imines, polyvinylpyridines, polyvinyl benzyl trimethyl chloride ammonium, diallyldimethylammonium polychloride. These poly-mothers have the disadvantage of not being compatible with anionic shampoos.
We have also already used in compositions for ~ hepous polyamino-amide polymers (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 25 ~

close to the stoichiometric proportions compared to the groups-amine of the poluamino-amide. The addition of these quantities important epichlorohydrin 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. ~ OA as an example such alkyl groups, mention may be made of rings azetidinium.
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 alkylating groups;
makes these products highly suspicious for application to the skin of man.
We also recommended the use as ~ condition-neur for hair "of thermosetting polymers to crosslink by the heat.
The present invention relates to a ~ 'conditioner for hair "which removes these l ~ convenience, and which is constituted ~ ~
by a crosslinked polyamino-polyamide having no group - ``
reactive and chemically stable.
The present invention also relates to a composition conditioner, which can be applied ~ 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 picnics, while ensuring satisfactory detangling of hair; ~
damp, and good elasticity of dry hair, so as to ensure good maintenance of the hairstyle.

The present invention also relates to a

2 ~
cosmetic composition for hair containing at least one cross-linked water-soluble polymer obtained by cross-linking of a polyamino-polyamide (A) prepared by polycondensation of a acidic 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 having 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 one; ~
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 in that it is r ~ alized by means of 0.025 0.35 mole of crosslinking agent per amine group of the polyamino-polyamide (A) and generally from 0.025 to less than 0.2 and in part layer of 0.025 to less than 0.1 mole of crosslinking agent by amine group of the polyamino-polyamide (A), In the composition according to the invention the p ~ l ~ mother r ~ ti-cul ~ pr ~ s ~ nte all of the following characteristics:
~ 1) it is perfectly soluble in water at 10% without formation of 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 specifically it is equal to or greater than 20 centipoises and less than 50 centipoises, ~ 3) it does not include any grouping reactive and in particular it has no alkylating property and it is chemically stable.

S ~;
The acids which can be used for the preparation of polyamino-polyamides (A) are chosen from:
- saturated organic dicarboxylic acids having from 6 to 10 carbon atoms, for example ad.ipic 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 adipic acid and ~ -addition compounds of an alkylenediamine with acids unsaturated such as acrylic acid, methacrylic acid, 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 rn ~ lange of r ~ active, then heating between 80 and 250C, and ;;
preferably between 100 and 180C for 1 to 8 hours depending on the reagents used. After heating ~ total reflux for 1/2 hour by hour, the water or alcohol formed during polycondensation, first at ordinary pressure then under pressure 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 t ~ amount of dicarboxylic acid and amines in proportions - 4 -;

equimolecular with respect to primary amine groups polyalkylene polyamines.
According to a preferred method of preparation, the polycondensation of the pre-selected polyalkylene polyamine ference among diethylene triamine, triethylene t ~ tramine, dipropylene triamine and their mixtures, i.e. (i) on a diacid preferably carboxylic adipic acid or its dimethyl ester lique, that is (ii) on the intermediate product of addition of a ethylenediamine molecule and two methyl ester molecules an ethyl ~ nically unsaturated acid such as acrylate, methacrylate or methyl itaconate.
Addition reactions of ethylenediamine on unsaturated esters are made by mixing the reagents between 5 and 80C, and polycondensation reactions by heating for 30 ~ 60 minutes at reflux and then with elimination of alcohol methyl at 120-150C, or water at 1 ~ 0-175CI 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 - CO - Z ~ (I) o ~ R represents a bivalent radical which d ~ bank of 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:

{3, - (C1 ~ 2 ~

~ 88 ~ 5 ~ ~

- TH - CH - NH - CH2 - CH2 - NH - CH ~ - CH
CH3 3 ~:.

- CH - CH2 ~ ~ CH2 CH
N - CH - CH --N ;;
2 ~ C 2 OO, -:
These radicals are respectively derived from acid: ~
terephthalic acid, adipic acid, adduct of ethylenediamine on acrylic, methacrylic and ita- acids. : ~
conical or their esters.
Z represents::
1) in the proportions of 60 to 100 mol%, the radical - NH - ~ (CM2) X - M ~ I ~ 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,.
~) in the proportions of 0 to 40 mol% the radical (II) below ~ us, dan ~ le ~ uel x = 2 and n = 1 and ~ ui d ~ ethylene bank-diamine, or the root , ~
-N ~ - derived from piperazine, `

3) in the proportions of - to 20 mole% the radical - NH - (CH2) 6 - NH - derived from hexamethylen2diamine. -The polyamino polyamides thus obtained are then crosslinked by adding a crosslinking agent. We use as:
crosslinking agent for a bifunctional compound chosen from (a) epihalohydrins, for example epichlorohydrin, (b) diepoxides.

~ 382 ~ (1 for example diglycidyl ether, N, N'-bis epoxy propyl pip ~ razine, (c) dianhydrides, for example dianhydride hutane 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 the ~, N'-bis epoxy propyl piperazine.
These crosslinking agents give birth respectively to the following radicals:
- CH2 - ~ HOH - ~ H2 ~ '.....
- CH2 - CH2 - CONH CH ~ NHCO ~ CH2 ~ C ~ I2 - CH ~ - CHOH - CH2 - N ~ 2 CHOH - CH2 Cross-linking reactions are carried out between 20C
and 90C, from aqueous solutions of 20 to 30% of polyamino-polyamide to which we add the crosslinking agent by very small fractions until a significant increase in the screw cosit ~ but without however reaching the gel which does not dissolve would be more in the water. Concentration is then quickly adjusted to 10% by ~ water supply 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 1 ~ 382 ~:
pol ~ crosslinked mothers is obtained using O ~ 025 unless 0.2 mole of crosslinking agent per amine group of the poly-amino polyamide. Another advantageous category of polymers reticul ~ s is obtained using 0.025 to less than 0.1 mole agent crosslinking 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 above crosslinker proportions 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 cycle ~ az ~ tidinium.
j N \ Cl ~

F H /
OH

Crosslinked polymers obtained from polyamino-polyamides known in the art and used in compositions for the hair contain reactive groups : '' ~ L ~ 88 ~

and therefore do not keep well.
The crosslinked polymers according to the present invention are keep well and are compatible with anio-surfactants picnics while ensuring a good mix of damp hair.
This compatibility with the 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, ~ thylene oxide, 1'o ~ yde of propylene, 2) a compound with an ethylenic double bond, for example acryl-lamide, acrylic acid;
3) chloracetic acid;

4) an alkane sultone, for example propane sultane 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 fixed ~ relative to the total number of groups amine ranges from 0 to 80%. The basicity index of the expressed polymer 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 of 0.1 to 5%, preferably 0.2 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 shampoo, cationic, nonionic, _ g _ ,. 1, ~ 35 ~ Z ~ ~

amphoteric or zwitterionic, coloring shampoo, dye, styling gel, styling lotion, brushing lotion, styling lotion, rinsed lotion, lotion leave-in styling enhancer, in compositions restructuring, in more specific cosmetic compositions such as anti-dandruff, antiseborrhic compositions.
We mean by rinsed lotion, a lotion that apply after shampooing to obtain a "condition- - - - effect 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 performed on wet hair ~ its using a brush, while drying the hair using a hand dryer.
This technique is suitable for relatively short hair.
By ren rening lotion or setting styling leave on, a lotion applied after shampooing and before styling, which is not rinsed and which facilitates the m en fold ~ and improves its shape and hardness ~ e.
By restructuring lotion is meant a lotion which contains products strengthening the keratin chain hair. To this class of products belong the derivatives meth ~ lolé ~ such as those described dan ~ patents ~ ran ~ ais 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.

. ' . '.'', , "

11D81 ~ 25 ~

They can come in various forms usual, that is to say: aqueous or hydroalcoholic solutions -ques, gels, creams, dispersions or in the form of aerosols.
They may contain in addition to the reti 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, perfumes, 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:.
easier detangling of hair, Among the preferred cosmetic ouresin polymers can be used in combination with r ~ crosslinked polymers -we can cite the crotonic acid 10 ~ / 0-acetate copolymers vinyl 90% with a molecular weight of 10,000 to 70,000, the copo-vinylpyrrolidone (VP) -vinyl acetate (AV) lymer having a molecular weight from 30,000 to 360,000, the VP: AV ratio being between 30:70 and 70:30, polyvinylpyrro- copolymers quaternary lidone having a molecular weight of the oxide of 1,000,000, such as for example the polymer sold under the brand "GAFQ ~ AT 755" by GAF Corporation, polymers cationic resulting from the condensation of pip ~ razine or seY derivatives ~ 1) on bifunctional compounds such as dihalides of alkyls or alkyl-aryls, bis-epo ~ ydes, 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, 32S ~ -(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) anionic surfactants such as alkali or alkali salts nolamines of alc ~ nes sulfonates, alkyl sulfates and alkyl ether sulfates and their condensation products with ethylene oxide. ~
for example lauryl and myristyl ~ ther 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 d ~ sign 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 RO ~ C2H10 (CH2oH) ~ n in which R denotes an alkyl, alkenyl or alkylaryl radical.
and n 10, ~ c ~ cationic surfactants such as ~ i) dimethyl hydroxym chloride ~ t ~ yl cetyl ammonium or (ii) bromu-re of t ~ tradécyl trim ~ thylammonium, (d) le ~ sur ~ ace agents amphot ~ re ~ such as ~ dexiv ~ carboxylic imidazole. '! , The cosmetic compositions for hair according to 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:
sensitized hair to permanently fix polymers.
The electrolytes used are alkaline salts or alkaline earth mineral or organic acids, soluble in water and preferably sodium chlorides and acetates, , .- .. .., ,.,. .
,,,. . .,. ; . :, ~

~ 8Z5 potassium, ammonium and calcium. The electrolyte q ~:
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.
Polyamino-amide polymers (I) 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 .amider ~ ticulated with acrylamide of formula CH2 = CH-CONH2 the latter ~ e condenses on primary and / or secondary amine groups giving formula strings glycidol under the same conditions leads to chains of formula -M-CH2 -CHOH-CEI20H ':

- 13 - ' Z5 ~
~ XEMPL ~ I

Polycondensation of adipic acid and diethylene triamine.
The constitution of the polymer obtained can be caract ~ risée by the following reason:

~ OC - (CH2) 4 - CONH - (CH2 - CH2 - NH) 2 619 g (6 moles) of diethylene triamine are added, ~ with stirring and in a nitrogen atmosphere, in 15 minutes, 876 g (6 moles) of adipic acid. Chau ~ fe then the reaction mixture at 145-150C, temperature at which water condensation is noted Maintain at reflux for 45 minutes 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.

EXAMPLE Ia;

Crosslinking of the polymer obtained according to Example I with epichloro-hydrin.
At 200 g of resin, obtained according to the process described in Example I, dissolved in 800 g of water, is added, with stirring tion, 9 g of epichlorohydrin. The mixture is heated JUSqU ~ 90C, then we add in very small fractions and at intervals from 5 to 10 minutes, 1.8 g of ~ pichlorohydrin until obtained.
of a viscosity ~ sup ~ greater than 50 centipoises ~ 6SC.
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 ~ ' 32 ~

epichlorohydrin per 100 g amine cuts.

EXAMPLE Ib Crosslinking of the pol ~ mother obtained according to Example I with the methyl- -lene bis acrylamide.
70 g of resin prepared according to the process described in Example I and dissolved in 280 g of water is added to the room temperature and with stirring, 7 g of methylene bis acry-lamide, then the mixture is heated to 80-90C. After 1 hour of heating there is a significant increase in viscosity.
The mixture is then diluted to 10% of dry extract by adding 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 of m ~ thylene bis acrylamide per l00 amine groups of the polyamino-polyamide.

EXAMPLE Ic Crosslinking of the polymer obtained according to example ~ with N, N '~
bi ~ - ~ poxy 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 ordinal and with stirring, 1.50 g of N, N'-bis-epoxy propyl piperazine, then the mixture is heated to 70-80C. After 15 minutes of heating, a gel is obtained which is immediately diluted.
tement at 10% dry extract by addition of 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.

,::

1 ~ S ~

EXAMPLE 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, added dropwise at temperature '' ambient, until obtaining a gelling goal, 1.7 g of divinyl sulfone. ' Then diluted quickly with 100 ml of water. ', The apparent viscosity of a 10% solution, measured after 24 hours, at 25C and at a speed gradient of 26.3 sec. , 1 is 27 centipoise.
~ the amount of crosslinker used is 13.9 moles' ~
of divinyl sulfone per 100 am ~ ine groups of polyamino-polyamid ~ ' EXEMP ~ E II ', Polycondensation of adipic acid and the diethylene mixture triamine-piperazine. '', ' The constitution of the prepared polymer can be shown; ~
felt by the two reasons below distributed statistically in ',''~' the ratio of 2: 1. ',,' - ~ OC - (CH2) 4 - CONH - (OEI2 CH2 2 and;, - ~ OC - (CH2) 4 - CO - ~

The mixture of 438 g (3 moles) of adipic acid and 86 g (1 mole) of piperazine is heated, under a ~ itation, and nitrogen atmosphere for 2 hours at 120-135C. We add, ~
then, at that temperature and within 90 minutes, 206 g (~ moles) of di ~ thylene 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, ca ~ healthy, transparent and yellow-green resin ~ L ~ 81 ~

EXAMPLE IIa Crosslinking of the polymer obtained according to Example II with ~ pichlorohydrin.
200 g of resin obtained according to Example II and dissolved in 800 g of water, o ~ add, with stirring, 9 g 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.
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 1 is 52 centipoise.
The amount of crosslinker used is 13.2 moles of epichlorohydrin per 100 amino groups of the polyamino-polyamide EXAMPLE III
Polycondensation of adipic acid e ~ of triethylene tetra-mine.
The constitution of polymer prepared in this example ~ `can be represented by the pattern:

~ OC - (CH2) ~ - CONH - (CH2 - CI12 - NH) 3 ~

At 292 g ~ 2 moles) of triethylene tetramine, we add, under a nitrogen atmosphere, within 20 minutes, 292 g ~ 2 mole ~) 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 water formed is removed by distillation with ordinary pressure for 3 hours and under reduced pressure ds 15 mm of mercury for 1 hour by gradually raising the temperature up to 170-175C.

Z ~

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

EXAMPLE IIIa Crosslinking of the polymer obtained according to Example III with the epi-chlorohydrin.
200 g of aqueous 20% polymer solution obtained according to the process described in Example III, the following is added, quickly and with stirring, 1.8 g of pichlorohydrin and heated LO mix it at 90 ~ 95C for 30 minutes. Then we add, to the same temperature, very slowly, 0.4 g of epichlorohydrin up to obtaining a viscosity greater than 50 centipoise, measured at 65C.
The solution is then immediately diluted to a concentration of 10% 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 methyl-lene-bis-acrylamide.
With 100 g of aqueous solution containing 20% of polymer, obtained according to the method described in Example III, 0.8 is added g of m ~ thylene-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 1 is 43 centipoise.

1 ~ 8E ~

The amount of methylene-bis-acrylamide added equivalent to 3.4 moles of crosslinker per 100 amine groups polyamino-polyamide.

EXAMPLE IV
Polyconsensation 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:

1 ~ ~
~ c - fH - CH ~ / CH2 - CH - CO ~ H - (CH2 - C ~ 2 - NH) 2J
I / {: H2-CEI2-N ¦:

CH2 - ~ ~ - CH2 o First stage A 620 g (3.9 moles) of methyl itaconate on 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, it is heated ~ 80C, to remove methanol, first at ordinary pressure, then SOUs pressure reduced by 15 mm of Hg. No ~ e then the appa-rition of a precipitate. We resume the reaction mixture 500 ml of benzene and distill.e the azeotrope m ~ thanolbenzene.
One concentrates and one takes again the E ~ sidu with acé
tone. Ain ~ i is obtained, with a yield of 82% N, N'-éthyLèn ~
-bis- [methyl 4-carboxylate 2-pyrrolidone], in the form of white powder with a melting point of 141-142C and an index 6.3S milli equivalent saponification / gram.
Second stage At 198 g (0.63 mole) of diester thus obtained, we a ~ ute, at temp ~ rature ambinate, 65.5 g (0.63 mole) of di ~ thylene:
triamine and distilled m ~ thanol formed by heating to 120-130C.
first at ordinary pressure for 90 minutes, then under pressure .:. .,. ,,,. . ,::

~ 8 ~ S ~

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 fractions, 5 or 10 minutes apart, 2 g epichlorohydrin, until a start of gelation is obtained.
Then diluted quickly with 1135 g of cold water to bring the 10% solids solution.
A clear solution is thus obtained, the viscosity, measured after 24 hours at 2SC and at the gradient of speed of 26.3 sec 1 is 49 centipoise.
The amount of epichlorohydrin used corresponds to 22 moles for 100 amine groups of the polyamino-polyamide.
EXAMPLE IVb ~,.
Crosslinking of the polymer obtained according to Example IV with the methylene-bis-acrylamide.
50 g of polymer obtained in Example IV and dissolved in 200 g of water, at room temperature is added and 90US stirring, 1.5 g of m ~ thylene-bis ~ acrylamide, then heating mixing at 85-90C. Then we gradually add the crosslinking until a viscosity greater than 50 centi-poises at ~ 5C. 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 ~ -.

3Z5 ~

of 3.9 g and it corresponds to 16 moles per 100 groupings polyamino-polyamide amine.
EXAMPLE V
Polyconclensation of a mixture of 2 moles of methyl acrylate and of 1 mole of ethylenediamine with diethylene triamine.
The constitution of the polymer prepared in this example can be represented by the pattern:

2 2 ~ H CH2 C ~ 2- ~ H- ~ H2-CH2-CONH- (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 form ~ by 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 colored resin yellow-orange, which in 10% solution of dry extract, presents a viscosity ~ inf ~ lower than 2 centipoises. ;;
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 - 2 ~ -. ..

5 ~

viscosity of 25 centipoise, measured after 24 hours at 25C and at 26.3 sec speed gradient F ~ EMP ~ E VI
Polycondensation of a mixture of 2 moles of methyl methacrylate and 1 mol of ethylene diamine with diethylene triamine.
The constitution of the polymer prepared in this example can be represented by the pattern:

oc-fH - CH2 - ~ H - CH2 - CH2 NH - CH2 - CIH-CO ~ H- (CH2 CH2 NH) 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 di ~ thylene triamine ~ 3 moles) and heated to 120-125C for 4 hours at press-ordinary and for 90 minutes under reduced pressure 15 mm Hg. The polycondensate thus obtained is present in the shape of a worm-bronze colored resin.

EXAMPLE VIa Crosslinking of the polymer obtained according to Example VI with the m ~ thylene-bis-acrylamide.
~ 84.6 g of polymer pr ~ prepared according to the process described in Example VI and di ~ under in 338, ~ g of water, we add, at room temperature and with stirring, 27.3 g of methylene-bis-crylamide. 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 26.3 ~ 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.

- ~ 2 -, . ~ ~

zs ~

EXAMPLE VII
Alkylation at 1 ~ _ ~ ro ~ sultone donkey of the ~ cross-linked olvmer 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 contains 0.45 10 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. Dilute with 1020 g of water to bring the concentration at 10% of dry extract. The solution thus obtained e ~ t yellow in color, and has a viscosity of 12.6 cps at 25C.
EXAMPLE VIII
:
Alkylation with sodium chloracetate of the crosslinked polymer according to ~ ;,.
Example Ia:
To 2000 g of solution obtained according to example Ia, SOU9 is added stirring and ~ room temperature 70 g (0.6 mole) of chlorac ~ tate of sodium hydroxide, and the reaction mass is then heated to 90C, for lG hours. Coated 270 g of water are added to bring the concentration at 10% of dry extract. We thus obtain a solution clear, straw yellow in color and with a viscosity of 25C
21 cps. ; ~
EXAMPLE IX
Alkylation with ~ lycidol of the crosslinked polymer ~ according to Example Ia:
A 1000 g of 10% solution of cationic polymer prepared according to Example Ia is added over two hours, with stirring and at room temperature.
rature, 27 g ~ 0.36 mol) 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-cosity measured at 25C, is 13.8 cps.

~ 8 ~ Z ~
.
EXAMPLE X
Alkylation with acr ~ lamide of the crosslinked polymer according to example Ia ~
At 1000 g of 10% aqueous polyamino amide solution pr ~ 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 60C. -By adding 180 g of water, a clear solution of polymer with 10% active material and viscosity equal to 11.2 cps at 25C.
10TH SAMPLE OF APPLICATI O_N

Anionic shampoo - Triethanolamine lauryl sulfate ......................... 15 g - Di ~ thanolamides of acids ~ ras de copra .................. 3 g - Polymer prepared according to Example Ia ...................... 1.5 g - Water qs .... ..... ........................, ............ 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 the fixing of the polymer on the hair for S on rlnce.
We find ~ a great ease of mixing ~
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 ease of mixing.
The hair is nervous and disciplined.

Anionic shampoo - Modified alkanolamide disodium sulfosuccinate semi-ester 5 g , ~ at8 ~ 25 ~

(marketed under the trademark "Monomate DHL 50"
- Sodium lauryl ether sulfate condens ~ with 2.2 moles ethylene oxide ........................................ 15 g - Polymer prepared according to Example I a ...................... 1 g - Water qs ....................... ..... ................ 100 g pH - 7.8 'EXAMPLE A 3 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 Aniline and Film Corp .... ...................... 0.3 g - Water qs ............................................... 100 g, ' p ~ = 7.5 '~'"'"
EXAMPLE A 4 '' ~ ' Anionic shampoo - Myristyl ether sodium sulfate condensed with 2.5 moles ethylene oxide ........................................ 5 g - Lauryl ~ ther sul ~ ate of sodium condenses with 2.2 moles, ~ ,, ethylene oxide .................. ~ .................... 1 g - Polymer according to Example IVa ................................ 1 g - Water q. ~ .P ........................... ........... ~ .... ..... 100 g,, pH = 8 Anionic shampoo -, 30 - Lauryl sulfate of triethanolamine ........................... 10 g - ~ coco fatty acid onoethanolamides ................. 1.5 g, ~ '- Protein hydrolyzate derived from collagen at 80%

~ 8825 ~

active ingredients, marketed under the trademark "HYDROPO 220"
by STEPAN Chemicals ........................................ 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 ~ CHOH-CH2-0 ~ CH2-CHOH-CH 2-o3 3 5 H ........................ 14 g R - mixture of nonyl to dodecyl xadicals - Polymer according to Example Ia ...... ~ ....................... 2.5 g - Lactic acid qs ............ pH = 5 - Water q.8.p ......................................... .. ..... 100 g Non-ionic shampoo R-CHOH-CH2-0 ~ CH2-CHoH-CH2-o3 3 5H R- nonyl to dodecyl 12 g - Dim chloride ~ thyl hydroxy ethyl ketyl ammonium ........ 1.5 g - Polymer pr ~ prepared according to Example Ia ...................... 1.5 g; ; ~
- Quaternary polyvinylpyrrolidone copolymers ~ 0.2 g having a molecular weight of the order of 1,000,000 marketed under the trademark "GAFQUAT 755"
by GE ~ ERAL ANILIN and FILM Corp.
- Lactic acid qs ......... pH 3 - Water qs ........................................, ...... l00 g EXAMPLE A 8; -Non-ionic shampoo R cHoH cH2-o ~ H2 cHo ~ I cH2 o3 3.5 :

1 ~ 8 ~ 5 ~

R = mixture of nonyl to dodecyl radicals - Dimethyl hydroxyethyl chloride c ~ tyl ammonium ......... 1 g -- C12H25 - ~ CH2-CH-0 ~ 4 H .......,., ...,.,., .............. 5 g ~ H2H
- Polymer of the example goes ........ ~. 3 g - Lactic acid qs ........... pE 5 - Water qs ............................................... l00 g Non-ionic shampoo - Oxyethylenated lauryl alcohol with L2 moles of oxide ~
ethylene ............................................... 7 g;
- Di ~ thanolamide laurique .................................. 3 g - Polymer according to Example Ia ............................ 0.5 g - Polymer according to Example IIa ........................... 0.8 g - Lactic acid qs ........... pH 4.5 - Water qs ............................................... 100g Non-ionic shampoo - Laury alcohol oxyethylenated with 12 moles of oxide ethylene ... ~ ..... ~ ............. ... .. ~ ... ........ 6 g C12 ~ l25 ~ CH2 ~ l H-o34 ~ I --------------.........., ...,. 4 g , C ~ I20 - Lauric diethanolamide .................................. 1.5 g - Poly ~ re according to Example IV a ............................ 2 g - Lactic acid ~ .sp pH 3 - Water qs .... ...................................... 100 g 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.

~ 3825 ~

Styling enhancer.
The following lotion is prepared:
- Vinyl acetate / crotonic acid 90/10 copolymer PM (molecular weight) = 10 ~ 000 ....................... 2.5 g - Polymer according to example Ia ~ ......... ~ ................. O, 3 g - 2-amino 2-methyl propane 1,3-diol qs pH 7 - Ethanol qs 50 - Colorant ............................ O .................. 0 , 01 g - 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 ............................. O, 3 g - Vinyl acetate / crotonic acid 90/10 copolymer PM = 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 qs pH 7 - Ethanol .... qs 50 - Dye ... ~ .......................................... 0, ~ 1 g - Perfume ..... ..................... ~ ..................... 0.2 g - S-carboxymethylcysteine (antiseborrheic) ............. 0.7 g - Water ~ .sp. . 100 ml The lotions of examples All and A12 apply on wet and towel-dried hair after shampooing and before wraps the setting.
We note on wet hair ~ acility of dememe-age. After winding the styling, we see that the hair is more nervous, softer and slightly shiny.

zs ~

The holding of styling is considerably prolonged.

Lotion for "brushing" in shape) The following lotion is prepared:
- Polymer according to Example Ia .................. ... O ........ 0.5 g - Ethanol qs ........ 50 - Colorantu ................................. ... ~ ........... 0.01 g - ~
- Perfume ................................................ 0.2 y - Water qs ............................................. 100 ml We apply this lotion to wet hair and boom ~ s after ~ shampoo. We shape the hair using a brush while drying the hair using a blow dryer by hand.
There is a very good passage of the brush and a prolonged holding of the hairstyle. We also note that the hair is longer ~ shiny ~ and softer.
EXAMPLE A_14 Rinse (rinsed lotion) for fine and soft hair.
We prepare the following lation:
- Alcohol c ~ tyl / stearyl 3Q / 70% oxyethylen ~ at 33%
marketed under the brand "Sipol AO Wax" by SINNOVA ... ~ ...... ~ .............., ................ 1.5 g - Dim chloride ~ hyl distearyl ammonium, commercially available ~
. . .
under the trademark "ARQUAD 2HT 75" by ARMOR 1.5 g - RC ~ IOH-CH2-0- ~ H2-CHOH-CH2- ~ 3 5H .. ~ ....
R = m ~ nonyl mixture ~ 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 ZS ~
- Hydroxyethylcellulose .... O .................. 0.9 g - Maleic acid qs .... p ~ -I 8 - Water ~ .sp ......... ~ ................................... 100g We apply this lotion to wet hair and wrung out after shampooing, leave to stand for 5 minutes, then rinse.
There is a very good detangling 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 ............................. 0.5 g - ~ Silicone oil ...................................... 0.1 g - Hydroxyethylcellulose ................................... 0.2 g - Ethanol ................................................ 50 ml - Perfume .... ~ ........................................... 0.2 g - Water qs .............................................. 100 ml This lotion for men is applied to hair wet. The chev ~ ux are styled and then dried. We aknowledge that the hair is nervous, slightly hardened and maintained nent perfectly in place.

Styling gel - Polymer according to Example Ia ............................. 1 g - ~ Hydroxyethylcellulose ............... ~ ................... 2 g - Silicone oil ....................................... 0.5 g Ethanol ....; .................................. 40 ~ ml - Parum ..... ~ ........., ................... ......., ..... ... 0.02 g - Water ~ .sp. , ......... .................. ........... 100 g A small amount of this gel, applied to hair dry, ensures good hold of the hairstyle while communicating . .

~ ~ 38Z5 ~) ~

hair shine.

Structuring lotion without rinsing.
- Dimethylol ethylene thiour ~ e of formula:
~ CH20H

S ................................ O ............ 0.5 g - Polymer according to Example Ia ............................ 0.5 g - Phosphoric acid qs ... pH 3 - Water qs ............................................. 100 ml :.
We apply this lotion on hair washed ~ s and towel-dried ~.
after shampooing and before styling. We see that ~ 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 t: oucher est. .
~ loux.

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.
- Dimethylol ~ thylene thiourea of formula ~ H2 / CS .............................................. 1 g '~
Cl ~ 2 - \.
C ~ 2OH
- Polymer according to Example Ia ............................ 1 g - .. ... ,. . ~. . ,,. :

~ L ~ i38; 2S ~

- Phosphoric acid qs .... pH 3 - Water qs .................................., ......... 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-lies in hair that is shiny, nervous and has volume.

By replacing, in the lotion above, the polymer according to example Ia by the mother according to example IIa, we also obtained a good result.

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% NaCL a ~ ustée 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 silky and easy to disassemble.
A ~ 2 An aqueous solution is prepared at 1% of material active compound prepared in Example Ic and 1.5% NH4CL
; adjusted to pH 5 with lactic acid.
Apply to colored hair. We do the setting folds and one ~ dries. The hair is hardened. They are ~ elastic and shiny. The touch is silky and the detangling easy.

Treatment lotion applied with rinsing.
Apply to wet and clean hair 25 ml of .

8ZS ~

the following solution:
- Polymer according to example Ib ............................ 1.5 g - Citri acid ~ eu qs 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 1.5 g of polymer according to example Ib per 1 g of polymer according to example IIIa.

Structuring lotion applied without rinsing.
- Dim ~ thylourethylene thiourea of formula \VS :., / S

CH20H ........................................... 0.6 g - Polymer according to Example III b ......................... 0.5 g - ~ phosphoric acid qs pH 3 - Water qs ............................................. 100 g Apply the mixture to washed and towel-dried hair before proceeding to the 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.

EXAMPLE A_26 We get the same result if we replace the polymer according to Example III b with the polymer according to Example IV b.

... . .

18 ~

Structuring lotion applied with rinse;
- Dim ~ thylol ~ thylène thiour ~ e of formula L ~ CH2 0H, / CS

CH2OH ........................................... 1.5 g - Polymer according to Example VIa ........................... 1 g;
-, Hydrochloric acid qs pH 3 - Water qs ............................................. 100 g The mixture is applied to washed and towel-dried hair.
We go 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 disentangled; they are bright, nervous and full of volume.

Anionic shampoo.
- monoethanolamine lauryl sulfate ..................... 10 g - Monoethanolamides of coconut fatty acids ..... ~ ........ 1.5 g - Polymer ~ according to example Ic ................... ~ ........ 1 g - Lactic acid, ~ .sp pH 7.2 Water ~ .sp .......... ~ ................ ~ .................. ......... 100 g Anionic shampoo ~
- Lauryl ~ ther oxyethylenated sodium sulfate with 2.2 moles of ethylene oxide ............. .......... ~
- Triethanolamine lauryl sulfate ........................ 6 g - Diethanolamides of coconut fatty acids ................. 3 g - Polymer according to Example IIIa ~ .......................... 1.5 g - Lactic acid qs pH ~, 6 .
.

1 ~ 8 ~ 3ZS ~

.
- Water qs ............................................. 100 g 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- Hydrolyzate of proteins derived from collagen, 80%
of active ingredients, sold under the trademark "Hydropo 220" by S ~ EPAN chemicals ..................... 3 g - Polymer according to Example IV b .......................... 1 g, - Lactic acid qs pH 7.5 - Water qs ............................ ~ ................ 100 g Anionic shampoo.
Same composition as the shampoo in the example 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.

Z5 ~

-C12H250 - ~ C2H30 (CH2oH ~ n 6 n represents an average statistical value of approximately 4 - Laury alcohol oxyethylenated with 12 moles of ethyl oxide-lene ......................................, .......... .... 6 g - D ~ riv ~ carboxylic imidazole of formula OH
I / CH2-COON ~ -11 23 ~ l N \

ll ¦ CH2-cH2-o-cH2-cooNa. ~. 4 g ~ ~ CH2: `

- Polymer according to Example III b ........................... 1 g - Lactic acid qs pH 5 Water qs ............ ~ ................................ 100 g Same composition as the shampoo of example A33, except that polymer III b is replaced by polymer Ic.

Same composition as shampoo A 33, sa ~ f as polymer III b is replaced by polymer IIIa.

~ non-ionic shampoo.
- A1COQ1 lauric oxy ~ thyl ~ born 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 ............................ O, 5 g - Lactic acid qs. pH 3.3 - Water q .. 5.p ....... ,, ..............., .. ~ .............. .... 100 g . .
Same composition as shampoo A 36, except that the polymer according to example VIa is replaced by the polymer according to ~ 8Z ~

Example IVb.

C12H250- ~ C2H30 (CH20 ~ I) 3 n 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 qs p ~ 5 - Water qs ............................................. 100 g Same composition as the shampoo of example A 38, except that the polymer according to Example IIIb is replaced by the 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 -10. '', No-rinse structuring lotion - Dimethylolethylene thiourea of formula Cl ~ I2 \; ``
I / CS .................. ~ .......... ~ ............ 0.5 g CH2 ~

Polymer prepared ~ according to Example VII ................. 0.6 g - Phosphoric acid qs ..... ~ ................. pH 3 - - Water qs ~ .......................................... 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.

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

~ 88,250 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 rinse ~ e Calcium acetate ...................................... 2 g - Pol ~ mother prepared ~ prepared according to Example IX .................... 2 g - Phosphoric acid qs ........ pH 8 - Water qs ............................................. 100 cm We apply this lotion to wet hair and clean.
The hair has a soft touch and detangles.
is lying.
After styling and drying, the comb passes easily-lies in hair that is shiny, nervous and has volume.

I. structuring lotion, applied with rinsing - Dimethylolethylene thiourea of formula:

C ~ 2 ~ N
I ~ S .. .... ....... ~. .... lg CH ~ OH
- Polymer prepared according to Example VII ................... 0.5 g - Polymer prepared according to Example VIII .................. 0.4 g - Phosphoric acid qs ........ pH 3 - Water ~ .sp ... ...................................., 100 cm3 30We apply this lotion to wet hair and clean. Leave to stand for 10 minutes then rinse.

r ~ 38 ~

. ......... ... . ... ~

382S ~) 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-CH2-0- ~ CH2-CHOH-CH2- ~ 3 5 H ..................... 15 ~ -R = Cg to C ~ 2 alkyl - Polymer prepared according to Example Ia .................... 1 5 g - NaCl ................................................ ... 1 g - Lactic acid qs ............ 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.

Shampoo non-io ~ only for sensitized hair CHOH-cH2-O-EcH2-cHoH CH2 ~} 3, 5H- 17 g R - Cg to C ~ 2 alkyl Polymer prepared according to Example Ia ...................... 0.8 g Polymer with motif _I ~ \ N-CH2-CH2-CN ~ IC-CH2-CH2-prepared by the condensation of piperazine and piperazinebis-acrylamide (preparation described in the Luxembourg patent Applicant's N 64371) .................., ............ 3 g ~ 825 ~

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

C18H37 1.5q NH- (CH2-CH2-O) y -H

x + y = 5 NH4Cl ...................... ~ ............, ............. ... 1.2 g Lactic acid q, sp ...... pH 3.5 Water qs ................................................ 100 ml Applied to sensitized hair, this shampoo clear appearance provides abundant and soft foam which mine ~ neatly rinse, age.
The hair is disentangled without difficulty and after drying have bulk and nervousness, while remaining soft and docile to styling.

EXEMP ~ ENA 45 Non-ionic shampoo for sensitive hair Cl2H250- ~ C2H30 ~ CH20H) 3 4H 17 g Polymer prepared according to Example IVa ...................... 1.8 g Diethanolamide lauric ................................... 3 g NaCl ....... O ............................... ~ ......... ..... 0.8 g Lactic acid qs ..... ~ ...... pH 5 Water qs. ~ ........... ~ ......... ~ .... ~ ...... ~. ~. 100 ml Applied on sensitized hair ~, this shampoo aspect .limpi ~ 1e provides an abundant foam and ~ gr ~able 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 vinyl acetate / crotonic acid copolymer; ~ -Molecular weight 25,000 ............. u ................... 2.5 g Polyvinylpyrrolidone / vinyl acetate 60/40 copolymer - 40 ~

25 ~:

(viscosity 3.3 centipoise, 5% in ethanol and 25C) ................................................ ... 0.5 g - Polymer prepared according to Example VII ................... O, 3 g - S-carboxymethylcyst ~ ine (antiseborrhoeic agent) ....... O, 7 g - Triethanolamine qs pH 8.6 - Ethyl alcohol ....................................... 10 ml - Water qs ....., .... ~ ............, ...................... 100 ml We apply this lotion on wet and towel-dried hair after shampoo ~ g and before winding the setting.
We observe on wet hair a facilit ~ deme- `;
age.
After winding the styling we see that the hair is nervous, softer and slightly brighter.
The holding of styling is considerably prolonged.
EXEMP_E NA 47 Hair styling enhancer - Vinyl acetate / crotonic acid copolymer 90/10 molecular weight 70,000 .......... ~ ....................... 2.5 g - Polyvinylpyrrolidone / vinyl acetate 60/40 copolymer (viscosity 4 cps at 5% in ethanol and at 25C)., 0.5 g - Polymer prepared according to Example VII .... ~ .............. O, 3 g - Triethanolamine qs ....... pH7 - Ethyl alcohol ............. ~ ........., ~. ,, .., 10 ml - Water qs .... ~ ........................................ 100 ml Apply this lotion to wet and towel-dried hair after s ~ lampooing and before winding the setting.
We see ~ ur wet hair ease;
of mixing.
After winding the styling we see that the 30hairs are more nervous, softer and slightly brighter.

382 ~

The holding of styling is considerably prolonged.
EXAMPLE NA 4 ~
Styling enhancer8 for qras hair - Vinyl acetate / crotonic acid 90/10 copolymer molecular weight 50,000 ................................. 2.5 g - Polyvinylpyrrolidone / vinyl acetate copolymer 60 / ~ 0 (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 qs ........ pH7 - Ethyl alcohol ......................................... 10 ml - Water qs ............................................... 100 ml Apply this lotion to molded and towel-dried hair after shampooing and before rolling up the setting.
We notice on wet hair an ease of unraveling.
After winding the styling we see that the hair is more nervous, softer and slightly shiny.
The holding of styling is considerably prolonged.

Styling enhancer for colored hair - Copol ~ mother of vinyl acetate / crotonic acid 90/10 molecular weight 50,000 ..........., ~ ................... 2.5 g neutralized ~ sorting ~ thanolamine - Polyvinylpyrrolidone / vinyl acetate 60/40 copolymer (viscosity 3.7 cps at 5% in ethanol and at 25C). 0.5 g - Prepared polymer according to Example Ia .................... 0.5 g - Dimethyl hydroxymethyl ketylammonium chloride ....... 0.1 g - NaCl. ~ ...... ~ .. ~ .................................... ... 0.5 g - Hydrochloric acid qs ... 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.

No-rinse structuring lotion ~ age -- Dimethylol ethylene thiourea of formula ~ CH20H ~, 2 \

I f S ... ..... ~ .................................. 0.5 g - Polymer prepared according to example X ..................... 0.6 g - Phosphoric acid qs ... pH 3 - Water qs ... ~ ......... ..................., ........... 100 ml We apply this lokion on washed and towel-dried hair 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.

EXAMPLE Na A 51 Rinse (rinsed lotion) for fine and soft hair : ' - Vaseline oil..n ................................... 7.5 g - Dimethyl distearyl ammonium chloride ................ 1 g - RO- ~ C2H30 (CH20H) 3 6H (R = C16 to C18 alkyl) '''3'75 g 12 25 ~ C ~ H30 (CH20H, 3 4H ............................. 3.75 g - Polymer prepared according to Example IX. ~ .................. 2 g - Quaternary copolymer of polyvinylpyrrolidone having a molecular weight of the order of 1,000,000, - \
~ 158Z ~ I ~

marketed under the trademark "GAFQUAT 755" by General Aniline and Film Corporation .................... 2.5 g - Citric acid qs ... pH 3 - Water qs ~ ............................................. 100 g We apply this lotion on wet and towel-dried hair after shampooing, leave paus ~ r 5 minut ~ s, then rinse.
There is a very good disentangling of wet hair.
After styling and drying, the hair is nervous, easy to style and shiny.

~ po i lonique - Triethanolamine lauryl sulfate at 40% material active ............................................... .. 30 g - Diethanolamides of coconut fatty acids ................. l, S g ~ Pol ~ mother prepared according to Example Ia (100% of active ingredient) ....................... ........... 1 g - Polymer comprising the motif ~ -CH2-CHOH-CH ~ .......... 0.5 g ;;

where Y denotes ~
-N N- or -N-~ ~ H2 `
CH ~ -O-CH20H
these two groups ~ as statistically distributed.
- Distilled water q-9-p ..... ---- 4 ------ ~ --.-....... - 100 g pH = 7.5 We apply about 10 cm of this clear solution on previously wet hair. We massage lightly.
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 pulsed hair is rinsed.
There is a great ease of disentangling the hair . . .
,. . :. . . . . :.

1 ~ 18Z ~

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 ~ ease of disentangling.
The hair is nervous and disciplined.

..
Cationic shampoo - Tetradecyltrimethylammonium bromide. ~ ... ~ ........... 75 g - Polyoxyethylenated lauryl alcohol with 12 moles of oxide ethylene ............................................. 50 g - Polymer prepared according to Example Ia .................... 5 g - Polymer comprising the motif ~ Y-CH2-CHOH-C ~ 3 ......... O, 5 g ! OR Y indicates ~
-N N- or -N-\ - / CH2 CH2 -o-cH2-cH2oH ', these two groupings being statistically distributed. -- Lactic acid qs ... pH 5 - 5.5 - Distilled water qs .................................. 1000 g This clear-looking solution is applied to ; 20 dyed hair. After massage, rinse with water, then efect One two application. We massage energetically to obtain abundant foam, then rinse.
There is a great ease of hair disentangling wet (the comb slides easily into the hair), the hair is very soft, flexible, malleable, the styling is mounts with great ease. After drying and during coifag ~
dry hair there is also an ease of disentangling.
The hair is nervous and disciplined.
~ this request is a division of request no 214,990 filed November 29, 1974.

,,,:. . .

Claims (2)

The embodiments of the invention, about which an exclusive right of property or privilege is claimed, are defined as follows: 1. Polyamino-polyamide polymer prepared by cross-linking tion of a polyamino-polyamide prepared by polycondensation of a acid compound chosen from (i) organic acids dicar-boxylic, (ii) aliphatic acids mono- and dicarboxyli-with an ethylenic double bond, (iii) esters of acids above, (iv) mixtures of these compounds: on a polyamine chosen from bis-primary polyalkylene polyamines and mono- or bis-secondary, 0 to 20 mole% of this polyamine can be replaced by hexamethylene diamine or 0 to 50%
of this polyamine which can be replaced by a bis-primary, preferably ethylene diamine, or with an amine secondary bis, preferably piperazine; crosslinking being carried out using 0.025 to 0.35 mole of an agent crosslinker by amine group of selected polyamino-polyamide among epihalohydrins, diepoxides, dianhydrides and bis unsaturated derivatives; characterized by the fact that it is alkylated by an alkylating agent chosen from acrylamide and glycidol, the crosslinked polymer having all of the following characteristics:
1) it is perfectly soluble in water at 10%
without gel formation;
2) the viscosity of a 10% solution in water at 25 ° C is greater than 3 centipoise and usual-between 3 and 200 and more especially it is equal to or greater than 20 centipoise and less than 50 centipoise;

3) it does not contain a reactive group and particular it has no alkylating property and it is chemically stable. 2. Process for the alkylation of polyamino-amide polymers crosslinked, described in claim 1, characterized by the polymer is treated in an aqueous solution, at the temperature stripping between 10 and 95 ° C with a selected alkylating agent among acrylamide and glycidol.