CA1091156A - Cosmetic compositions containing polymers prepared with cerium ions - Google Patents

Abstract

The subject of the present invention is new cosmetic compositions characterized in that they contain, in an appropriate vehicle, at least one polymer resulting from the polymerization of an unsaturated monomer on a compound carrying at least one OH function, said polymerization being carried out in an aqueous medium in the presence of Cerium ions. The compositions based on these polymers, when applied to the hair, in the form of styling lotions or in the form of lacquers lead to excellent hold of the hair and make the hair soft and shiny.

Description

109115 ~ i ~ a present invention relates to new composition cosmetic compositions based on polymers of a particular type These new compositions are characterized by the the fact that they contain, in an appropriate cosmetic vehicle at least one polymer resulting from the polymerization of a monomer unsaturated on a compound carrying at least ~ an OH function, said polymerization being carried out in an aqueous medium in the presence of ions Cerium.
The various tests carried out by the Company require have shown that the compositions based on these polymers, when applied to the hair, under lotion form ~ styling or SOU9 lacquer form ~ condui-know that the hair has an excellent hold and soft and shiny hair.
In addition, it turned out that these polymares when were present in other formulations such as sham-fists, rinses or dye compositions allowed to give the hair better disentangling and excellent shine.
Finally these polymers can enter, as an ingredient primary or secondary, in milks, creams, lotions or foundations for application to the skin or face and make these compositions excellent properties and so these polymers can be used in replacement of those commonly used in this type of compound tion.
Likewise, these polymars can advantageously replace the resins used in the compositions in the form of varnish which provides good adhesion, good held in time and excellent shine.
According to the invention, the compound carrying at least one OH function or prepolymer can be a natural, modified compound ; ~ k "` lO ~ S6 or not modified, or a synthetic polymeric compound or not polymeric.
Among the natural compounds, we can cite:
Latin, cellulose, starch, modified starches, colla-gene, chitosans, nitro-cellulose, cellulose ethers and cellulose carrying cationic functions etc ...
Among the synthetic compounds, there may be mentioned:
(1) polymers with a hydrocarbon polymer chain goodness such as:
polyvinyl alcohols, polyacetates of partially hydrolyzed vinyl, N-vinyl copolymers partially or hydrolysed pyrrolidons and vinyl acetate all, copolymers of crotonic acid and vinyl acetate hydrolys ~? s ~? n part or to ~ llit ~, polyvinylpyrrolidone (di-OH), polyacrylamide (di-OH), N methacrylate, ~ -dimethyl-amino-2 ethyl (di-OH) quaternized with ethyl bromide, polybu-tadiene with OH endings such as those known under the brands "HYCAR HTB" trade sold by GOODRICH, "NISSO PBG 2000"
sold by NIPPON SODA, "R 15" sold by SINCLAIR KOPPERS, "BUTAREZ H ~"'sold by PHILLIPS PETROLEUM, "TEL ~ GEN HT" sold by GENERAL TIRE, polyisobutylene with OH terminations such as the one known under the trademark "HTPIB" sold by ENJAY
POLYMER and N-methacryloyl D-glycosamine copolymers such than N-vinyl pyrrolidone / N-methacryloyl copolymers D-glucosamine (di-OH or not).
(ii) polymeric hydrocarbon chain compounds bonée comprising heteroatoms such as:
polyethylene glycol, polypropylene glycol, the copolymers polyethylene oxide - polypropylene oxide, co-polymers polyethylene oxide - polysiloxane or nonyl-polyoxyethylenated phenols.

109 ~ 156 As a non-polymeric compound, it is possible in particular cite pentaerythritol.
The unsaturated monomers mistletoe are polymerized with the compound carrying ~ at least one OH function can be of the type tra ~ diver ~; we can for example quote without this enumeration either restrictive:
a) acrylic acid or methacrylic acid;
b) acrylic or methacrylic esters of formula:
CH2 = C - COOR:
R
in which :
R represents a hydrogen atom or a methyl radial and Rl represents a linear or ràmifi ~ e alkyl chain having 1 ~ 18 carbon atoms. Among these compounds ~ we can in particular link quote:
methyl or ethyl methacrylate or methacrylate propyl, tert-butyl, octyl, dodecyl and dloctadecyle;
c) acrylic or methacrylic esters of N, N-dialkylaminoethyl of formula: r ~
CH2 = C - COO - CH2 - N <(II) R
dan ~ which:
R has the same meaning as above and r ~ st r ", identical or different ~, represent ~ alkyl radicals having from 1 ~ 5 carbon atoms. Among these compounds, mention may be made of:
acrylates or methacrylates of N, N-dimethylamino-

2 ethyl or N, N-diethylamino-2 ethyl;
d) acrylic or methacrylic esters of hydroxyal-kyle of formula:
CH2 = IC - COO - (CH2) n -OH (III) R

in which :
R has the same meaning as above and n is 2 or 3. Among these compounds, there may be mentioned:
acrylates or methacrylate ~ d ~ hydroxy-2 ~ thyle or d ~ hydroxy-3 propyl e) acrylamide or methacrylamide f) hydroxyalkylacrylamides of formula:
CH2 1 ~ CONH (CH2) n - OH (IV) 0 in which:
R at the same ~ ignification as above and does not ~ t 1 3.
Among these compos ~ s we can mention in particular:
hydroxyethylacrylamide and hydroxypropylacrylamide.
g) ~ -alkylacrylamides and methacrylamides of formula:
CH2 f CONH - R2 (~) R

in which :
R has the same meaning as above and R2 represents a linear or branched alkyl radical having from 1 to 5 atoms of carbon. Among these compounds we can cite:
N-methylacrylamide and N-tertio-butylacrylamide, and h) chlorides or bromide of N, N diallyl N, N-diaIkylam monium of formula:
CH2 = CH - CH2 ~ 0 / R3 N (VI) CH2 = CH ~ CH2 R4 in which :
R ~ and R4, identical or different, represent linear or branched alkyl radicals having from 1 to 16 atoms of carbon and X is Cl or Br. Among these compounds one can in particular to quote :
chlorides or bromides of N, N-diallyl N-methyl N-lU ~ 311 ~

dodecylammonium, of N, N-diallyl N-methyl N-butylammonium, N, N-diallyl N-methyl N-octylammonium, or N, N-diallyl N-methyl ~ -d ~ cylammonium.
If the compound carrying at least one OH or prepo- function lymer is a homopolymer and has at one of its ends a single OH function, polymerization in the presence of a monomer unsaturated such as those listed above leads in this case a sequenced polymar and more particularly a polym ~ re bi-sequence.
On the other hand, if the homopolymer has two OH functions, : u ~ e ~ each of se ~ ends, we then obtain a tri- polymer sequence Thus ~ i is used as homopolymer ~ re carrying ~ oin ~ two OH functions of polyvinylpyrrolidone (di-OH), the polymerization with methyl methacrylate (MAM) leads to a tri-block polymer which can be represented schematically from the following way:

[~ AM ~ ~ VP ~ MA ~

If, on the other hand, the compound carrying at least one function OH is a copolymer and has at least one of S ~ B ends an OH function and also at least one lateral OH function, polymerization in the presence of an unsaturated monomer then leads a polymer both sequenced and grafted ~.
So, if we use as a compound carrying functions O ~ l of the type indicated above ~ sus, a copolymer of N-vinylpyrrolidone / N-methacryloyl D-glucosamine (di-O ~ l) of the following formula:

Me HO- _ CH2 - CH --- CH2 - C - ~ CH2 - CH r OH
N o CO N
H ~ ~ in H- t OH ¦ H
HO_ ~ O

C ~ 20H
and that this compound is copolymerized with, for example, methacrylate of methyl, one then obtains a compound comprising from ~ a part of polymethyl methacrylate (PMAM) ~ each end of polymeric chain and, from plu8, PMAM grafts on each or some of the OH functions of the gluco- molecules samine.
In another embodiment, the compos ~ carrier d ~ at least one OH function can be a copolymer comprising no terminal OH, but on the other hand comprising at least one function OH lateral, so that in the presence of an unsaturated monomer, the polymerization leads to a polymer only grafted.
So if we use as a copolymer carrying minus a lateral OH function a polymer of the following formula:

Me 2 ~ IH CH2 ~ ~ n NO ICO
NH
OH ~ ~ H

HO ~ H o 1 ~ 9 ~ 156 and that this compound is copolymerized with mébhy methacrylate ~ e, a copolymer is obtained comprising PMAM grafts on each or on some of the OH glucosamine ounctions.
Finally, in a final embodiment, the compound carrying at least one OH function can be a non-compound polymer such as for example pentaerythritol, carrier compound of four functions ~ OH, and da ~ s ce oas, polymerization using of an unsaturated monomer, such as for example methacrylate of thyle, then leads to a compound comprising grafts on each any or some of the OH functions, these grafts being PMAM plugins; polym ~ res of this type will be called ulterior-"polymares ~ canvas".
It will be understood that for the polym ~ res according to the invention it is difficult to give a range of molecular weight counts part of the polymeric or non-polymeric measurement of the pr ~ polym ~ re and secondly the number of sequences or the rate of grafting. Consequently the molecular weights can be very varied and mainly depend on the cosmetic use that we want to give to polymers.
~ es polymares used ~ according to the invention, whether sequenced, sequenced and grafted ~ grafted or starred, are prepared 6 according to a unique process consisting in reacting in solution aqueous the compound carrying at least one OH function in the presence of an unsaturated monomer and of a cerium salt such as for example the ammonium and cerium nitrate r (NH4) 2 Ce (N03) ~.
~ es operating conditions of this procedure ~ which are known (see LJ GUILEAULT et al J. ~ ACRO.Sci Chem. A7 (8) P.1.581 (1973) The following are:
~ e pr ~ polymer and / or the ~ monomares to polymerize are placed ~ in aqueous solution (distilled water ~ e) in a reactor equipped stirring and a nitrogen adductor tube. With this mixture, we then introduces the sufficient quantity of ammonium nitrate and Cerium likely to form the sequence number and / or the rate grafting sought.
It is obvious that the quantity of catalyst can this varies within very wide limits.
Preferably, the ammonium nitrate and Cerium is introduced in solution in nitric acid ~.
Then stirred for a time which may vary from 2 to 48 hours either at room temperature or at a temperature between 40 and 80C.
After the end of polymerization ~ then precipitates the polymer formed ~ using dtu ~ organic solvent such as by example ether, isopropyl alcohol, acetonitrile, acetone or mixtures of such solvents.
It is important to note that for certain prepolymers their preparation must be carried out under special conditions3 o that is to say in aqueous solution in the presence of ~ H202 as initia-tor and of a compound such as borax this in a way to give direction to the cha ~ no polymeric OH terminations. This is the case for example polyvinylpyrrolidone (di-OH) or polyacrylamide (di-OH) used according to the invention or of the copolymer of N-vinylpyrrolidone /
N-methacryloyl DLg ~ ycosamine (di-OH).
~ Has exact structure of polymars according to the invention has could not yet be determined with certainty because the radical formed by reduction of CeIV to CeIII in the presence of at least one function OH can be located either on the oxygen of llOH or on the carbon neighbour.
~ es composition ~ cosmetics according to the invention contains-do the above defined polymers ie ~ ingredient title main active ingredient, either as an additive.
These cosmetic compositions can be presented under form of aqueous, alcoholic or hydroalcoholic solutions, the alcohol being in particular a lower alkanol such as ethanol or lV91156 isopropanol, or in the form of creams, gels, emulsions, milks or aerosol cans also containing a propellant or in the form of nail polish ~
The adjuvants generally present in the compositions cosm ~ ticks of the invention are for example perfumes, colo-rants, preservatives, questioning agents, thickening agents, etc.
It should be noted that the cosmetic compositions according to the invention are also ready-to-use compositions only concentrates to be diluted before use. Ies cosmetic compositions of the invention are therefore not limited to a particular area of polymer concentration.
Generally, in cosmetic compositions according to the invention, the polymer concentration is between 0.1 and 15 ~ by weight, and ~ preferably, between 0.5 and 10 ~. -The cosmetic compositions based on the polymers described above have in particular cosmetic properties ~
ressante ~ when applied to hair.
This is how when applied to the hair they significantly improve the quality of the hair.
For example, they promote treatment and facilitate the mixing of wet hair.
The cosmetic compositions according to the invention are in particular cosmetic compositions for hair, characterized by the fact that it ~ contain at least one polymer such as described above.
These cosmetic hair compositions include generally at least one adjuvant usually used in cosmetic compositions for hair.
These cosmetic compositions for hair can be presented in the form of ~ aqueous, alcoholic or hydroalcoholic (alcohol being a lower alkanol such as `1 ~ 191 ~ 6 ~ thanol or isopropanol), or souæ ~ elm of creams, gels or of emulsions, or in the form of sprays. They can also 8tre conditioned in the form of aerosol cans, containing ~ scabies-ment a propellant such as for example the axote r nitrous oxide or ~ NFreonn (R) type chlorofluorinated hydrocarbons, such as the "Freon" ll and the "~ réon" l2 or m ~ swaddles of these propellants.
~ adjuvants generally present in the 6 compo ~ itions cosmetic for hair according to the invention are for example the ~
perfumes, dyes, preservatives, drying agents strants, thickening agents, emulsifying agents, ~ es pelymère ~ may be present in the composi-osmetic ¢ for hair according to the ~ nvention, or ~ title additive, either as the main active ingredient, in styling lotions, treating lotions, creams or coif ~ ants gels, or as an additive in ~
8 shampoos, styling, perms, tints, restructuring lotionæ, treating lotions ~ or lacquer for che ~ them.
~ es cosmetic compositions ~ for hair according to the invention-These are in particular:
a) treatment compo ~ itions characterized in that it ~ include, ~ title ~ active ingredient ~ at least one polymer according to the invention in aqueous or hydroalcoholic solution.
The polymer content can vary between 0.1 to 10% by weight, and preferably between 0.1 and 5%.
~ e pH of these lotions is close to neutral and can vary for example from 6 to 8. The pH can be increased if necessary at the desired value, adding either an acid such as acid citric, either a base, in particular an alkanolamine such as monoethanolamine or triethanolamine.
To treat hair ~ using such a lotion, we apply said lotion to wet hair, let it work (R) mark of ~ meroe - 10 -recorded 109 ~ 56 for 3 to 15 minutes, then rinse the hair.
We can then proceed, if desired, to a styling classic;
b) shampoos, characterized by the fact that they comprise at least one polymer according to the invention and a detergent cationic, nonionic or anionicO
~ es cationic detergents are in particular ammoniums long chain quaternaries ~ esters of fatty acids and amino-alcohols, or polyether amines.
~ non-ionic detergents are in particular the esters of polyols and sugars, the condensation products of the oxide ethylene on fatty substances, on long-lasting alkylphenols chain, on long chain mercaptans or on amides long chain and ne polyethers of polyhydroxylated fatty alcohols.
~ es anionic detergents are in particular alka- salts linens, ammonium salts or salts of amines or amino alcohols fatty acids such as oleic acid, ricinoleic acid, le9 acids from coconut oil or hydrogenated coconut oil;
alkaline salts, ammonium salts or amino alcohol salts sulfates of fatty alcohols, in particular fatty alcohols C12-C14 and in C16; alkaline salts, magnesium salts, salts ammonium or amino alcohol salts 6 fatty alcohol sulfates oxyethylenated; the condensation products of fatty acids with 1eB isethionates, with taurine, with methyltaurine, with aarcosine, etc .; the alkyl benzene sulfonates, in particular with alkyl in C12; ~ aIkylarylpolyethersulfates, monoglycerides sulfates, eto. All of these anionic detergents, as well as the many others not mentioned here, are well known and are described in the literature.
These compositions in the form of shampoos can also Lement contain various adjuvants such as for example par ~ u ~ s dyes, preservatives, thickening agents, 1091 ~ 56 ~ foam stabilizers, softening agents, or other cosmetic resins.
The deterKent concentration in these shampoos is generally between 5 and 50 ~ by weight and concentration in polymer according to the inventlon between 0.1 and 10 ~ o ~ and preferably between 0.1 and 5%.
c) styling lotions, especially for hair sensitized, characterized by the fact that they contain at least one polymer according to the invention, in aqueous, alcoholic that or hydroalcoholic.
These compositions may further contain another cosmetic resin.
~ e polymer concentration according to the invention in these styling lotions generally vary between 0.1 and 5 ~ and preferably between 0.2 and 3 ~.
~ e pH of these styling lotions generally varies between 3 and 9 and preferably between 4.5 and 7.5. We can modify the pH, if desired ~, for example by adding an alkanolamine as monoethanolamine or triethanolamine;
d) hair dye compositions, laughed at by the fact that they comprise at least one polymer according to the invention, a coloring agent and a carrier.
~ e support is preferably chosen so ~ consti-kill a cream.
The polymer concentration in these compositions dye can vary between 0.5 and 15% by weight, and preferably between 0.5 and 10%.
In the case of an oxidation coloring, the composition dye can be packaged in two parts ~, the second part being oxygenated water. The two parts are mixed at the time of employment.
e) hair sprays, characterized by the fact 10911 ~ 6 that they contain an alcoholic or hydroalcoholic solution at least one polymer according to the invention, this solution being placed in an aerosol container and m ~ langée ~ a propellant.
We can for example obtain an aerosol lacquer according to the invention by adding the polymer according to the invention to the mixture d! ~ n anhydrous aliphatic alcohol such as ~ thanol or isopropanol and a propellant or a mixture of liquefied propellants such that halogenated hydrocarbons, of the trichlorofluoromethane type or dichlorodifluoromethane or mixtures thereof.
Dan ~ these hair spray compositions, the concen-Polymer tration generally varies between 0.1 and 3% by weight.
Eien heard, it is possible to add to these lacquers for hair according to the invention adjuvants such as dyes, plasticizers or any other usual adjuvant.
The polymers according to the invention also have ~
int ~ ressantes cosmetic properties when applied on the skin.
In particular, they promote hydration of the skin, and therefore avoid its drying out. They also give the skin an appreciable fluff to the touch.
The cosmetic compositions according to the invention can be cosmetic compositions for the skin characterized by the fact that they contain at least one polymer according to the invention.
In addition, they generally contain at least one adjuvant usually used in cosmetic compositions for the skin.
LeR cosmetic compositions for the skin according to the invention tion are presented for example in the form of creams, gels, aqueous, alcoholic or hydroalcoholic emulsions or solutions ques.
~ A polymer concentration in these compositions for the skin generally varies between 0.1 and 10 ~ by weight.

~ 0911 ~ 6 ~ es adjuvants generally present in these compositions cosmeti ~ ues are for example perfumes, dyes, preservatives, thickeners, dry agents trants, emulsifiers, etc.
These skin compositions in particular constitute treatment creams or lotions for the hands or face, sunscreen creams, tinted creams, cleansing milks.
These compositions are prepared according to the methods usual.
For example, to get a cream, you can emulsify an aqueous phase containing the polymer in solution and optionally other ingredients or adjuvants, and an oily phase.
The oily phase can be constituted by various pro-mixes such as paraffin oil, petroleum jelly, oil sweet almond, avocado oil, olive oil, esters fatty acids like glyceryl monosterarate, palmitateæ
ethyl or isopropyl, alkyl myristates such as propyl, butyl or cetyl myristates. We can also add fatty alcohols such as cetyl alcohol or waxes such as for example beeswax.
The compositions according to the invention can also appear in the form of nail polish and contain preference of:

3 to 15% by weight of polymer according to the invention in as ~ o-ciation with a plasticizing agent, a film-forming agent and a sy ~ teme solvent that is to say the usual solvents and / or diluents conventional for this type of composition, the solvent system constituent of 60 to 80% by weight of the varnish.
In some cases ~ these varnishes may also contain coloring agents in a proportion of 0.05% to 6% by weight relative to the total weight of the varnish.
These varnishes according to the invention provide excellent lO911S6 shine and very good resistance over time We will now give by way of illustration and without no limitation several examples of preparation of polymers as well as examples of cosmetic compositions.
EXAMPLES OF PREPARATION
PREPARATIO ~ DES P PO ~ YMERES

- Preparation of the polyvinylpyrrolidone prepolymer containing an -OH function at each end of the chain.
100 g of N-vinyl are introduced into a 1 liter flask freshly distilled pyrrolidone, 500 g of distilled water and 1.5 g of borax (Na2B407 10 H20) ~ e reaction mixture is brought to 40C under a current of axote and stirring.
After dissolving ~ on borax, we introduce lml of ~ H202 to 110 volumes and the temperature is maintained at 40C for 7 hours. ~ The polymer is precipitated in acetone and dried ~
under reduced pressure. 99 g of pure polymer are thus obtained.
Viscosity: 4.5 cpo (at 34.6C in solution at 5 ~ in the water) - Preparation of an N-vihylpyrrolidone prepolymar -Nm ~ thacryloyl D-glucosamine.
In a 500 ml flask fitted with an agitator and a nitrogen adduct tube, 100 g of ethanol, 95 g of Distilled N-vinyl-pyrrolidone, 5 g of N-methacryloyl D-glucosamine and 1 g of azobis isobutyxonitrile.
The mixture is heated at 80C for 16 hours, then the polym ~ re is precipitated in ac ~ tone (yield 60%) Viscosity: 1.8 cpo (at 34.6C in 5% solution in the water) Preparation of a prepolymer of N-vinyl pyrrolidone and lO9 ~ S6 partially hydrolyzed vinyl acetate.
800 ml of ethanol are introduced into a 2 liter flask, 12.8 g of sodium hydroxide in pellets and 80 g of copolymer composed of 70% N-vinyl pyrrolidone and 30 ~ vinyl acetate.
The reaction mixture is stirred at 30C for 2 hours, then it is poured into 8 liters of diethyl ether. After filtration the polymer is dried under reduced pressure.
Yield: 95%

- Preparation of a prepolymer of crotonic acid and partially hydrolyzed vinyl acetate.
According to the same operating mode as above ~ we hydrolyze in the presence of sodium hydroxide a copolymer ~ composed of 90%
vinyl acetate and 10 ~ crotonic acid.
Yield: 95%
EXAMPLES 5 to 12 In Table I attached) the preparation of certain prepolymers obtained either according to the procedure or of example 1 or of example 2.
PREPARATI0 ~ DES COPO ~ YMERES
All the products of depært used ~ have purified.
PREPARATI0 ~ DU CATA ~ YSEUR:
~ a solution of ammonium nitrate and C ~ rium (~ AC) is p Prepared by dissolving 58.5 g of ammonium nitrate and Cerium, in lN nitric acid solution and making up to ~ 1 liter with the same solution of nitric acid.
EMPLE 1 ~
- Preparation of a polymethacrylate triblock copolymer methyl - poly N-vinylpyrrolidone - polymethyl methacrylate (PMAM - PVP - P ~ AM).
In a 2 liter flask fitted with an agitator and a nitrogen adduct tube, 1250 ml of distilled water, 95 g _ 16 -109'1 ~ 56 of polyvinylpyrrolidone (di-OH) prepared ~ e according to Example 1. Then 5 g of distinguished methyl methacrylate and 50 ml are introduced into it dlune ~ solution of ammonium nitrate and Cerium in acid nitric (NAC). ~ e mixture is kept stirring for

4 hours ~ room temperature, then toss in ~ m mixture ethyl ether isopropanol. ~ e mixture thus precipitated is dissolved in dimethylformamide and reprecipitate dan ~ of ~ ther sul ~ urlque.
~ 70% debt.

- Preparation of a block copolymer and graft ~ alcohol polyvinyl - polymethacrylate of N, N-dimethyl amino ~ thyl-2 (50/50) quaternized with dimethyl sulfate.
In a 2 liter flask fitted with an agitator and a nitrogen adduct tube, ~ 70 ml of water and 50 g of alcohol are introduced polyvinyl sold by the company PROIA ~ O under the brand Rhodovial A / 125p. We heat ~ e with stirring ~ 80C
until the polyvinyl alcohol is completely dissolved, -then cooled to 20C. 50 g of methacrylate are then introduced into it of N, N-dimethyl aminoethyl-2 quaternized with dimethyl sulfate and 50 ml of ammonium nitrate and Cerium solution in nitric acid (NAC).
~ e reaction mixture is kept stirring for 16 hours at room temperature and then the polymer is precipitated in an acetone / isopropanol mixture 3/2.
After filtration, the polymer is dried under pressure scaled down, Yield 98%.
EXEMPIE_15 - Preparation of an alcohol grafted block copolymer polyvinyl - N-vinylpyrrolidone 50/50.
According to the same procedure as that of Example 14, 50 g of distilled N-vinylpyrrolidone are polymerized on 50 g of alcohol 1091 ~ 56 polyvinyl in 16 hours. The polymer is precipitated in acetone / isopropanol 3/2.

.
- Preparation of a triblock copolymer by cyclopo-lymerization of N9N-diallyl N, N-dimethyl ammonium bromide on poly N-vinylpyrrolidone (di-OH).
In a 500 ml flask fitted with an agitator and a nitrogen adductor tube, 500 ml of distilled water, 25 g of polyvinylpyrrolidone (di-OH) prepared according to Example 1. Then 25 g of N, N-dimethyl N, ~ -diallyl ammonium bromide are introduced into it and 25 ml of a ~ solution of ammonium nitrate and cerium in nitric acid (NAC). ~ e mixture is maintained sou ~ stirring 40C, for 48 hours, then discarded in acetonitrile. ~ e precipitated polymer is dried sou ~ pre ~ reduced sion. We obtain 15 g of pure polymer. Yield ~ 0%.
EXAMPLE 17.
Preparation of a triblock copolymer by cyclopoly-merization of N, N-diallyl N-dodecyl N-methyl ammonium bromide on poly N-vinylPYrrolidone (di-OH).
According to Example 16, 25 g of N, N-diallyl are polymerized N-dodecyl N-methyl ammonium on 25 g of poly N-vinylpyrrolidone (di-O ~). Obtained by precipitation in acetonitrile 10 g of pure polymer. Yield 20 ~.
EXEMP ~ ES 18 to 52 (see table II attached) EXAMPLES OF PREPARATION OF COMPOSITIONS
EXEMP ~ EA
We prepare ~ according to the invention a styling lotion by mixing the following ingredients:
Polymer prepared ~ according to example 13 ....................... 2 g 30 Perfume ................................................ .... 0.1 g Ethyl alcohol ......................................... 50 g Water qs .............................................. 100 g 109 ~ 156 This styling lotion applied in a way that is suitable for tional gives the hair a shiny and excellent resistance over time.
In this example, the polymer prepared according to example 13 can advantageously be replaced by the same amount of a poly-mother prepared according to Examples 14 to 16 and 25 to 30.
EXAMPLE B
We prepare according to in ~ ention a styling lotion by mixing the following ingredients:
Polymer ~ prepared according to Example 32 ................. ~ ..... 3.5 g Perfume ................................................. .. 0.1 g Dye sufficient to color the lotion ................ 0.2 g Isopropyl alcohol ...........................; ............... 50 g Water qs ................................................ ..... lOO g In this example, it is advantageous to replace the polymer prepared ~ according to example 32 by the same amount of a po-lymer prepared according to Examples 15 and 33 to 43.
After impregnating the hair with one of the lotions according to this example, the hair is rolled up on rolls of styling having a diameter of 15 to 30 mm and then drying them hair by external heat. After removal of rolls we get an excel ~ you styling a very good resistance over time.
EXAMPLE C
A styling lotion is prepared according to the invention by mixing the following ingredients:
Polymer prepared according to Example 28 ....................... 3 g Ethyl alcohol ......................................... 50 g Perfume ............ ~ .................................... ... 0.2 g 30 Water qs ............................................... ... 100 g In this example the 3 g of polymer according to the example 28 can advantageously be replaced by the same quantity `1 ~ 9 ~ 156 of a copolymer ~ res prepared according to Examples 16, 17 and 43 ~ 52.
EXEMP ~ ED
Pre ~ are according to the invention an aerosol lacquer mixing the following ingredients:
Polymer prepared according to Example 13 ......................... 8 g Perfume ................................................. ... 0.2 g Absolute ethyl alcohol qs ............................. 100 g 25 g of this solution are then packaged in a aerosol can present of 47 g of trichlorofluoromethane and 28 g dichlorodifluoromethane.
After spraying, the hair is shiny, soft to the touch and the resin is easily removed by brushing.
In this example of polymer according to example 13 can be advantageously replaced by the same amount of a polymer prepared according to Examples 18, 22 and 23.
EXAMPLE E
An aerosol lacquer is prepared according to the invention mixing the following ingredients:
Polymer prepared according to Example 28 ....................... 7.2 g Perfume ................................................. ... 0.3 g Isopropyl alcohol qs ............................... 100 g 25 g of this ~ olution are then packaged in a aerosol can in the presence of 47 g of trichlorofluoromethane and 28 g of dichlorodifluoromethane.
By spraying, we obtain a lacquering of the hair which makes them shiny and soft to the touch.
~ In this example, the polymer according to Example 28 can be advantageously replaced by the same amount of a polymer prepared according to Examples 22, 23 and 24.
EXEMP ~ EF
A film-forming body milk is prepared according to the invention by mixing the following ingredients:

109115 ~;

Diethyl hexyl adipate ..................................... 4.8 g Stearic acid ... ..................................... 2.9 g 5 mol ethoxylated lanolin alcohol. OE ..................... 0.5 g Cetyl alcohol ................................................ 0.4g Glycerol stearate ........................................... 1.0 g Triethanolamine ................................................ 0.95 g Propylene glycol ............................................... 4.8 g Polymer prepared according to Example 14 ..... ............... 0.5 g Curator .... 0 ~ ........... O ........................... qs 10 Perfume .......................... ...................... ...... qs Demineralized water ~ terile ........ qs ................... 100 g Dan ~ this example of polymer according to example 14 can be advantageously replaced by the same amount of a polymer prepared according to Examples 15 to 20 and 33 to 43.
EXAMPLE G
A film-forming cream is prepared according to the invention in proceeding to the mixing of the following ingredients:
Paraffin oil ................ ....................... 30.0 g Stearic acid ............................................ 8.0 g 20 Triethanolamine ............................................. .1.0 g Polymer prepared according to example 32 ............................ Ø5 g Curator .... ........................................ qs Perfume ................................................. .... .... .qs Sterile demineralized water ............ qs ................ 100 g In this example, the polymer according to example 32 can be advantageously replaced by the same quan ~ ity of a polymer pr ~ prepared according to examples 44 to 52 or examples 13 ~ 200 EXAMPLE H
, According to the invention, a skin lotion is prepared by mixing the following ingredients:
Polymer prepared according to Example 32 .................... .., 1.0 g Propylene glycol ....................................... .... 2.0 g - ~ 09115 ~;

Ethanol ......................................... ........ ..... lO.O g Methyl parahydroxybenxoate (preservative) ..................... 0.2 g Perfume ..........., ........, ............................ ......... qs Colorant ........., ........ ,, ............................. ...... q. 8 Sterile demineralized water 9.5 P ............................. lOO g ~ e polymer is dissolved in the preservative solution (all water + preservative) at 60C.
After cooling, the other elements are incorporated.
porous 80US moderate agitation.
In this example, the polymer according to example 32 can be replaced by the same amount of a polymer prepared according to examples 13, 18 to 24,; 26 to 31 and 33 to 48.
EXAMPLE I
We prepare ~ elon the invention a beauty mask e ~
mixing the following ingredients:
Polymer prepared according to Example 14 ....................... 20.0 g Propylene glycol ........................................... 5.0 g Methyl parahydroxybenzoate (preservative) ............... O.2 g Ethanol ................................................. .. 15.0 g Kaolin ................................................. ... lO.O g Titanium oxide ............................................ 0.5 g Triethanolamine iauryl sulfate ........................ `6.0 g Perfume ............................ ~ ..... ~ .............. ........... qs Sterile demineralized water ......... qs ....................... - 100 g ~ e propylene is dissolved in the preservative solution tor (all water + preservative) at 60C.
~ After cooling, the other constituents are incorporated ~ or moderate agitation.
In this example, the polymer according to example 14 can be replaced by the same amount of a polymer prepared according to examples ~ 15 to 20 and 44 to 52.

~) 91 ~ S6 EXEMP ~ EJ
A foundation is prepared according to the invention in mixing the following ingredients:
Partial fatty acid glyceride ......................... .. 9.00 g 10 mol ethoxylated cetylstearyl alcohol. O. ~ ........... 4.00 g Paraffin oil ....................................... 18.00 g Polymare prepared according to Example 14 ....................... 1.00 g Magnesium and aluminum silicates ..................... 0.75 g Rhodorsil antifoam ...................................... 0.20 g Parahydroxybenzoate dlalcoyles ............................ 0.20 g Deionized water ............................................. 66.85 g Mineral dyes ........................................ 5.00 g 105.00 g In this example, the polymer according to example 14 can be replaced by the same amount of a polymer prepared according to examples 27 to 37 and 43 to 52.
EXAMPLE K
We prepare according to in ~ ention a foundation in pro-yielding to the mixture of the following ingredients:
Partial fatty acid glyceride ............................. 9.00 g 10 mol ethoxylated cetylstearyl alcohol. of OE .......... 4.00 g Paraffin oil ....................................... 18.00 g Polymer prepared according to Example 32 ....................... 1.00 g Silicate ~ of magnesium and aluminum ...... ~ .................... 0.75 g Parahydroxyben ~ propylate ........................... ....... 0.20 g Deionized water ............................................. ... ... 66.85 g Mineral coagulants ....................................... ....... 5.00 g 105.00 g In this example, the polymer according to example 32 can be replaced by the same amount of a polymer prepared according to ~ examples: 18 to 26 and 38 to 42.

1 0 9 ii 5 6 In this example, the polymer according to example 32 can 8be replaced by the same quantity of a polymer prepared according to examples: 18 to 26 and 38 to 42.
EXEMP ~ E ~
A rinsing product is prepared according to the invention, or "rinse" in the form of a fluid emulsion by mixing the following ingredients:
Vaseline oil ................................. Ø .......... 9.5 g Alcohols gra9 (C16-C18) polyglycerolated (2 to 6 mol.) ........ 6.5 g Polymer obtained according to Example 18 .......................... .... 1.5 g Water qs .... ~ ........................................... ............ 100 g This product is applied to washed hair and wrung out by distributing it carefully over the entire hair and massaging it lightly. After a time of application-about 2 minutes, then rinse thoroughly. ~ es hair has a shiny shine and is easy to untangle.
In this example, the polymer according to example 18 can be replaced by the same amount of a polymer prepared according to one of the following examples: 28 to 35 and 38 to 43.
EXAMPLE M
A rinse in the form of a gel is prepared according to the invention by mixing the following ingredients:
Hydroxyethyl cellulose .......................................... O.9 g Polymer obtained according to Example 36 ............................. 0.8 g Cetyl pyridinium chloride ..................................... 3 g Dye ................................... ~ ............. ..... 0.1 g Water qs ................................................ .... ....... 100 g This product is applied to washed hair ~ and es ~ orées by massaging slightly. After a time of application of a ~ 2 minutes, then rinse the che ~ elure thoroughly. ~ es hair is shiny and detangles easily.
In this example, the polymer according to example 36 can l ~ D9 ~ 156 be advantageously replaced by the same amount of a polymer ~ according to examples 45 to 52.
EXAMPLE N
An ionic shampoo is prepared according to the invention in mixing the following 3 ingredients:
Lauryl myristyl triethanolamine sulfate ............................ 12 g Copra diethanolamide ............. ....., .......... 0 ........... 2 g Myristyl dimethylamine oxide ...................... 0.O ....... 1.5 g Polymer obtained according to Example 20 ........, .................... 1.5 g Lactic acid qs ....................., .................. pH = 6.5 Water QSP ..., ............................................ .... 100 g This shampoo has excellent properties cosmetics. After its application the disentangling of the hair wet is very easy and the hair after drying is shiny, soft and supple.
Da ~ s this example can advantageously replace the same amount of polymer according to Example 20 per polymer obtained selo ~ Examples 21, 22, 24, 30, 41, 43 and 44.
EXEMP ~ EO
A cationic shampoo is prepared according to the invention by mixing the following ingredients:
~ cetyl trimethyl ammonium romure ............................... 2 g Lauryl alcohol polyglycerolated with 4 moles of glycerol .............. 12 g Polymer obtained according to Example 16 ............. ~ .................. 1 g Perfume ................................................. ......... 0.2 g Lactic acid qs ................................... ........ pH = 4.5 Water qs .............................................. .. ...... 100 ml This shampoo applied to the hair provides a soft and airy foam. It allows a very easy disentangling of wet hair. After ~ drying, the hair ~ is soft, very shiny and have a light appearance.
In this example we can advantageously replace the ~ L091156 Polymer according to Example 16 by the same amount of a polymer prepared according to the examples: 21 to 25 and 32 to 36.
EXEMP ~ EP
A nonionic shampoo is prepared according to the invention by mixing the following ingredients:
in Cll - C14 polyglycerolated at 3-4 moles of glycerol ...,. ,,,,,. ,,,., ...... ,,,, .. ,, ................... ................. 17 g Polymer obtained according to example 40 ......., .......................... 2 g Cetyl pyridinium chloride ............................... ........ 0.8 g Diethanolamine lauric .................., ........................ 2.5 g Perfume ...................................... ........... ........... 0.2 g Lactic acid qs ........................ ........... .......... pH = 5.5 Water qs .., ....,. ,,,, .................., ................ .............. 100 ml This shampoo is crystal clear and provides abundant foam and have sweet.
It promotes the detangling of wet hair that they are natural, colored or discolored.
After ~ drying the hair is soft, light and shiny ~.
In this example, the polymer can be replaced according to Example 40 by the same amount of a polymer obtained according to the examples 41, 43 and 44.
EXAMPLE Q.
A dye composition is prepared according to the invention in the form of li ~ gelable uide.
TEI ~ IURE SUPPORT
2 mol glycerol oleic alcohol. of glycerol, .., ......................... 20 g 4 mol glycerol oleic alcohol. glycerol ............... .............. 20 g Butyl glycol ...................................., ........... ............... 8 g Propylene glycol....... ,,....................................... .., 12 g Ammonia 22 Be ...... ~ ................., ......... ~ ............ ... 10 ml Para-aminophenol base ...................... ~ ....................... ..... 0.08 g Meta-diaminoani sulfate ~ ol .............................. ............ 0.025 g - ~ 6 -lO9 ~ S6 ~ esorcine ................................................ ............ 0.3 g Meta aminophenol base .................... .. ....... O.06 g Nitro-para phenylanediamine .................. ....... ................ 0.003 g Para-toluylene diamine ............................................ 1.05 g Hydroquinone .............................................. ... ....... 0.17 g Ethylene diamine tetracetic acid .................................... 3 g Sodium bisulphite d = 1.32 .... 0 ................. ......... ~ ....... 0.8 g Water qs ................................................ .......... .. 100 gA 50 g of this support thus obtained, it is mixed with mo ~ ent from the use 5 g of a 35% solution of the polymer obtained according to Example 29 also with 50 g of hydrogen peroxide at 20 volumes.
This composition thus obtained is then applied to hair using a brush.
We lai ~ pause 30 minutes and then rinse the che ~ them.
~ e untangling is easy, the touch silky and the hair is shiny and bulky.
On dark brown hair, we get a brown clear.
In this example, the polymer according to example 29 can advantageously be replaced by an equivalent quantity of one polymer prepared according to Examples 16, 19 to 21, 23, 24, 26 ~ t 35.
EXEMP ~ ER
We prepare according to the invention u ~ ~ nail ernis in mixing the following ingredients:
~ itro cellulose RS 1 ~ 2 seconds .............................. 16 g Polymer obtained according to Example 50 ............................. 6 g Ethyl alcohol .............................................. 4 g Butyl alcohol .............................................. 4 g Camphor................................................. ....... 2 g Butyl phthalate ............................................ 4 g Toluene ................................................. ...... 20 g ~ Ethyl acetate .............................................. 10g ~ 091 ~ 6 Butyl acetate ........................................... 34 g 100g This base varnish applied to the nails has very good adhesion and excellent shine over time.
In this example, the polymer according to example 50 can be replaced without inconvenience by one of the polymers obtained according to examples 40 ~ 44, 49 and 51.
EXEMP ~ ES
A colored nail polish is prepared according to the i.nvention LO by mixing the following ingredients:
Basic varnish as described in Example R ................. 96.88 g Bentone 27 (benzyl-dodecyl dimethylammonium-montmorillonite) .....,., .......... ,, ....................... 1 g Phosphoric acid., ....................................... 0.02 g Titanium oxide ..... ~ ............ ... ~ ..................... 1 g D and C Red N 7 ............................................ 0.4g D and C Red N 11 ...., ....................... ,, .............. .................. 0.2 g D and C Red N 5 ............................................ 0.3g Red iron oxide .. 0 ....................... .................... .., ........... 0.2 g 100g This nail polish has excellent shine and very good adhesion.

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Claims (21)

The embodiments of the invention, about which a exclusive right of property or lien is claimed, are defined as follows: 1. Cosmetic composition characterized by the fact that it contains, in a suitable vehicle, at least one polymer resulting from the polymerization of a monomer established on a com-placed carrying at least one OH function, said polymerization being carried out in an aqueous medium in the presence of Cerium ions. 2. Composition according to claim 1, characterized by the fact that the Cerium ions come from ammonium nitrate and Cerium (NH4) 2 Ce (NO3) 6. 3. Composition according to claim 1, characterized by the fact that the compound carrying at least one OH junction is a natural compound, modified or unmodified, taken from the group consisting of: gelatin, cellulose, starch, starches modified, collagen, chitosans, nitro-cellulose, cellulose ethers and cellulose carrying cationi-ques. 4. Composition according to claim 1, characterized by the fact that the compound carrying at least one OH function is a polymer with a hydrocarbon polymer chain taken from the group consisting of: polyvinyl alcohols, polyacetates of partially hydrolyzed vinyl, copolymers of N-vinyl pyr-rolidone and vinyl acetate partially or wholly hydrolyzed tee, the copolymers of crotonic acid and hydro vinyl acetate partially or fully lysed polyvinyl pyrrolidone (di-OH), polyacrylamide (di-OH), N, N-dimethyl amino-2 methacrylate ethyl (di-OH) quaternized with ethyl bromide, polybutadiè-OH-terminated ne, OH-terminated polyisobutylene and cop N-vinyl pyrrolidone copolymers and N-methacryloyl D-qlucosamine (di-OR or not). 5. Composition according to claim 1, characterized by the fact that the compound carrying at least one OH function is a polymeric compound with a hydrocarbon chain comprising heteri roatomes taken from the group constituted by: polyethylene glycol, polypropylene glycol, polyethylene oxide-polypro- copolymers pylene oxide, polyethylene oxide-polysiloxane copolymers and polyoxyethylenated nonylphenols. 6. Composition according to claim 1, characterized by the fact that the compound carrying at least one OH function is pentaerythritol. 7. Composition according to claim 1, characterized by the fact that the established monomer is taken from the group consisting of titled by:
(a) acrylic or methacrylic acid, (b) acrylic or methacrylic esters of formula:

in which :
R represents a hydrogen atom or a methyl radical and R1 represents a linear or branched alkyl chain having 1 to 18 carbon atoms.
(c) acrylic or methacrylic esters of N, N-dial-kylaminoethyl of formula:
(II) in which :
R has the same meaning as above and r 'and r "i-or different ones represent alkyl radicals having 1 to 5 carbon atoms and the corresponding quaternary esters, (d) acrylic or methacrylic esters of hydroxyal-kyle of formula:
CH2 - COO (CH2) n-OH (III) in which :
R has the same meaning as above and n is 2 or 3 (e) acrylamide or methacrylamide (f) hydroxyalkylacrylamides of formula:
CH2 = - CONH (CH2) n - OH (IV) in which :

R has the same meaning as above and n is 1 - 3, (g) the N-alkvlacrylamides and methacrylamides of formula:

CH2 = - CONH - R
2 (V) in which :
R has the same meaning as above and R2 represents te an alkyl radical, linear or branched having from 1 to 5 atoms of carbon and (h) chlorides and bromides of N, N-diallyl N, N-dialkyl ammonium of formula:

(VI) in which :
R3 and R4, identical or different, represent radicals linear or branched alkyl cals having from 1 to 16 carbon atoms bone and X is Cl or Br. 8. Composition according to claim 1, characterized by the fact that the polymer is a block polymer. 9. Composition according to claim 1, characterized by the fact that the polymer is a block and graft polymer. 10. Composition according to claim 1, characterized by the fact that the copolymer is a graft polymer. 11. Composition according to claim 1, characterized by the fact that the polymer is a star polymer. 12. Composition according to claim 1, characterized by the fact that the polymer is present in the composition in a proportion between 0.1 and 15%. 13. Composition according to claim 1, characterized by the fact that the polymer is present in the composition in a proportion between 0.5 and 10%. 14. Composition according to claim 1, characterized by the fact that the cosmetic vehicle is an aqueous solution, alcoholic or hydroalcoholic, said alcohol being ethanol or sopropanol, cream, gel, milk, or emulsion. 15. Composition according to claim 1, characterized by the fact that the cosmetic vehicle is a mixture of at least an alcohol chosen from ethanol and isopropanol and a propane gas pulsate liquefied under pressure. 16. Composition according to claim 1, characterized by the fact that it also contains a cationic detergent, not ionic or anionic in a proportion of between 5 and 50%
and constitutes a shampoo. 17. Composition according to claim 1, characterized by the fact that it contains a coloring agent in a support under form of cream, gel or emulsion and constitutes a composition of hair dye. 18. Composition according to claim 1, characterized by the fact that the cosmetic vehicle is a cream, a gel, a emulsion, a milk containing the polymer in a concentrated concentration is between 0.1 and 10% and is intended for application to the skin. 19. Composition according to claim 1, characterized by the fact that it also contains various adjuvants chosen from the group made up of: preservatives, perfumes, dyes to tint the composition, sequestering agents, thickening agents, emulsifying agents, agents sunscreens. 20. Composition according to claim 1, characterized by the fact that it is in the form of a nail polish and contains from 3 to 15% by weight of polymer, a plasticizing agent, a film-forming agent and a solvent system, the latter being present in a proportion of 60 to 80% by weight. 21. Composition according to claim 19, characterized by the fact that it also contains a coloring agent in a proportion from 0.05% to 6% by weight.