DK168059B1 - Process for treating hair, skin and nails, and an agent for use in the process - Google Patents

Description

DK 168059 B1 i

The present invention relates to a method for treating hair, skin and nails with an agent based on a mixture of a component A containing a cationic polymer and a component B containing an anionic polymer having a molecular weight of 500 to 5,000,000, the cationic and anionic polymer being present in a solvent and in a proportion of 0.01 to 10% by weight, based on the total weight of the agent.

Eg. after a treatment of keratinous fibers, especially hair, it is generally desirable to obtain a lightness, a pleasing touch, a suppleness of the moist hair which is otherwise easy to put and is not sticky.

In the case of dry hair, the treatments are aimed at obtaining shiny hair that is easy to cut, is electric, is strong, is soft to the touch and is not sticky, and has a good behavior, does not become too fast. greasy and makes the hairstyle full.

Numerous agents containing either anionic polymers or cationic polymers are known. If these agents are of interest for use to an extent where they provide certain properties, especially cosmetic ones, they do not always allow all the desired properties to be obtained simultaneously.

The same is true in the treatment of the skin with polymer-containing agents, whereby the coating is avoided to be smooth or sticky, or in the treatment of the nails, where the film should be glossy and durable while ensuring a good suppleness to avoid fractures under the mechanical stresses of the nails.

Among the various polymers, the anionic polymers are known to impart certain properties, such as the hardness of the keratin fiber and the behavior of the hairstyle. These polymers also have interesting properties in terms of glossiness which one wishes to use in the treatment of keratin-containing materials.

DK 168059 ΒΊ 2

However, the anionic polymers have the disadvantage of being poorly adhered to the keratin-containing materials. Thus, when applied to the hair in agents that are not destined to be rinsed off, such as hair lotions, varnishes or reconstructive lotions, a powder is often found which results in the hair becoming very crumbly. have poor drug effect.

One of the objects which is desired to be achieved by means of the present invention is the fixation of anionic polymers on keratin-containing materials, which may in particular consist of hair, skin or nails.

It has now been found, contrary to the teachings of the prior art, to fix the anionic polymers on keratin-containing materials in amounts which may be of importance.

The cationic polymers are well known and are particularly characterized by their substance (substantivity), which is of the utmost importance, since the cationic property is very pronounced and allows them to be fixed and retained, especially on hair. When applied to hair, these polymers facilitate hair straightening and provide softness and suppleness.

However, their isolated application does not allow the application of keratin-containing materials, especially hair, nails and skin, to all the desired cosmetic properties.

Thus, when used in skin care agents, they present the disadvantage of making the skin smooth and sticky. When used for hair treatment, this often lacks fullness and when used for nail treatment, the coating for 25 is supple.

It has now surprisingly been found that the coupling of anionic polymers to the keratin-containing material becomes possible by their use in combination with cationic polymers.

This coupling of anionic polymers to the keratin-containing material 30 with the involvement of cationic polymer is largely due to an interaction between the two polymer types. Although the exact nature of this interaction is not completely known, it is believed that in some cases it is a complex which in the event of precipitation can eventually be redissolved.

This interaction also enables good results to be obtained in the resulting product.

The process according to the invention is characterized in that the agent is applied to the hair, skin or nails, the anionic polymer present in component B being selected from polymers having structural units derived from the following acids, their salts or acid derivatives (a) sulfonic acid, (b) phosphoric acid, (c) crotonic acid derivatives selected from: - the grafted polymers of vinyl esters and esters of acrylic acid or methacrylic acid, alone or in admixture, copolymerized with the crotonic acid, grafted onto polyalkylene glycols if terminal OH groups are optionally etherated or esterified, or seeded on azotated polyalkylene glycol oxides; the grafted and cross-linked polymers obtained by copolymerization of a nonionic monomer, of crotonic acid, of polyethylene glycol and a crosslinking agent; - the terpolymers derived from: crotonic acid, vinyl acetate, an allyl or methallyl ether of the formula i 'r2 - c - c - o - ch2 - c = CH2 (11) I. in CH3 O R * 25 wherein 4 is a hydrogen atom or a -CH3 group,

R 1 represents a saturated, straight or branched hydrocarbon chain having 1 to 6 carbon atoms and R 2 represents either the -CH 3> group or the group -CH (CH 3) 2, 5 - the tetra and pentapolymers obtained by copolymerization of: • crotonic acid , • vinyl acetate or vinyl propionate, • an allyl or methalyl ester of formula (11), a monomer selected from: - a vinyl ether of formula CH2 = CH - O - R3 wherein R3 represents an alkyl group, - a vinyl ester of fatty acid chain of formula R4 - C - O - CH * CH2

II

Wherein R 4 represents a straight chain alkyl group having 7 to 11 carbon atoms, - an allyl or methallyl ester of the formula:

R5 - C - O - CH2 - C = CH2 II I

O is R 'wherein R' is a hydrogen atom or a methyl group and R 5 is an alkyl group; - the terpolymers of vinyl acetate, crotonic acid and of vinyl esters 20 of an aliphatic saturated monocarboxylic acid branched in α-position and containing at least 5 carbon atoms in the carboxy group; - copolymers obtained by copolymerization of: DK 168059 B1 5 - esters of unsaturated alcohols and saturated short chain acids, esters of saturated alcohols with short chain and unsaturated acids, esters of crotonic acid, esters of long chain acids and unsaturated alcohols, esters of unsaturated acids and esters saturated or unsaturated alcohol having 8 to 18 carbon atoms or a lanolin alcohol, alkyl vinyl ethers, alkyl allyl ethers, alkylmethallyl ethers, alkylcrotyl ethers and the α-olefins; - copolymers of crotonic acid with ethylene, vinylbenzene, vinylmethyl ether and acrylamide and water-soluble salts thereof; 10 - the copolymers of vinyl acetate / crotonic acid with acrylic or methacrylic acid esters or an alkyl vinyl ether; the copolymers of vinyl acetate / crotonic acid and a monomer selected from vinyl, allyl and methyl carbon esters of long carbon, (d) acrylic or methacrylic acid, the polymer being selected from: - graft copolymers obtained by grafting vinyl esters, acrylic or methacrylic acid esters, individually or in admixture and copolymerized with acrylic or methacrylic acid, onto an etherified or esterified polyalkylene glycol, or to an oxide of a nitrogen-containing polyalkylene glycol; the grafted and crosslinked polymers obtained by copolymerization of a nonionic monomer, acrylic or methacrylic acid, polyethylene glycol and a crosslinking agent; 25 - ter-, tetra-, penta- and higher polymers of a monomer of the formula II-CH2 = c - c - NH - c - (CH2) n - CH3 (15)

. 11 I

Wherein R 1, R 2 and R 3 are hydrogen or methyl and n is 0 or is an integer from 1 to 10; - a water-soluble monomer of formula R '

5 I

R 4 - CH = C - (CH 2) m - CON - Z - OH (16) r 5 wherein R 'is hydrogen or methyl, Z represents a straight or branched alkylene group optionally substituted by one or two hydroxymethyl groups, m has the value is 0 or 1, R 4 is hydrogen or -CORg (R 6 = OH or -NH-R 7, where R 7 is hydrogen or -Z-OH), R 5 is hydrogen or methyl when m = 0, or R 4 and R 5 are - COR g when m = 1; acrylic or methacrylic acid, optionally together with one or more copolymerizable monomers; - N-tert-butyl acrylamide, N-isopropylacrylamide / acrylamide, methacrylamide / acrylic and methacrylic acid / N-vinylpyrrolidone ter polymers; - water-soluble polymers of acrylic and methacrylic acid and copolymers of acrylic or methacrylic acid with a monoethylenically unsaturated monomer; - polyacrylamides containing carboxylate groups; and - copolymers of 40 to 90 mole% vinylpyrrolidone, 40 to 50 mole% vinyl ester and 20 to 30 mole percent of acrylic or methacrylic acid; (e) ethylene-α-β-carboxylic acid; ) allyloxyacetic acid, methallyloxyacetic acid, 3-allyloxypropionic acid, allylthioacetic acid, allylaminoacetic acid, vinylacetic acid, vinyloxyacetic acid, crotyloxyacetic acid, 3-butene-7-acidic acid, 4-pentenoic acid, allyoic acid, 10-undecenoic acid - or N-dihydroxyalkyl-maleamic acid or itaconamic acid, with the exception of anionic homopolymers of acrylic acid cross-linked with an allyl ether of sucrose or pentaerythritol, and then the treated keratin material is not rinsed.

In the process of the invention, fixation of anionic polymers to a keratin-containing material is achieved.

The invention also relates to a means for use in the method according to the invention, which is characterized by the characterizing part of claim 4.

The compositions of the invention are generally intended for use in cosmetics. They can be used especially for the treatment of hair, nails and skin.

Thus, the use of the combination of cationic polymer and an anionic polymer in hair lotions and reconstructive lotions for the hair makes it possible to detect a decreased propensity for powdering.

Surprisingly, when the combination is applied to nails, it cures them.

The skin, treated with "after shaving" and "toilet water" lotions, remains smooth and supple.

Certain combinations which are within the scope of the present invention may be preferred depending on the desired result.

Thus, after obtaining a good shelf life after a hair treatment, particularly interesting results are found using a combination of anionic polymers, cationic polymers which are strongly or moderately substantial, such as those containing a large number of tertiary or quaternary amine groups, and when one wishes to obtain a hairstyle that is soft, supple and full and has diminished static electricity, interesting results are found in connection with cationic polymers and anionic polymers derived from carboxylic acids, especially those derived from acrylic acid or metha = cilic acid, crotonic acid containing at least one group different from the vinyl acetate group, or derived from maleic anhydride.

The combination results in beneficial results when used in conjunction with a surfactant. This surfactant may play a role as transfer agent for the combination 10 to the keratin-containing material, and in some cases a role as solubilizer for the precipitate which can be formed by certain combinations of cationic and anionic polymers.

Particularly interesting results are obtained when the most substantive cationic polymer is combined with a weakly surfactant which is anionic but which in case of precipitation is sufficient to solubilize the combination to obtain the maximum amount of anionic polymer on the hair and to obtain of good durability.

Preferably, surfactants which are nonionic to weakly anionic are used in combination with medium-sized cationic polymers of the type polyaminoamides or polyalkylenamines, as well as anionic polymers, or also highly anionic surfactants, together with cationic polymers which are very substantial and of the type cyclopolymers or quaternary ammonium compounds, as well as anionic polymers.

In the case of precipitate formation after the mixture of anionic polymer and cationic polymer, it is possible to use, or instead of the surfactant, cosmetically acceptable solvents or to redissolve the complex by adding an excess of either the anionic polymer or the cationic polymer.

Finally, it is possible to influence the pH of the agent to dissolve it. It is also possible to prepare and apply the agent of the invention to the keratin-containing material at a pH at which the combination is soluble in aqueous medium, and then to apply another agent to reach a pK value at the level of the keratin-containing material, which takes place with a maximum application and especially with a precipitation of the combination on the keratin-containing material.

DK 168059 B1 9

Another possibility may be to prepare the agent under the pH conditions at which the combination is soluble, lyophilize it, and prepare the agent just before application to the keratin-containing material by dissolving in a suitable medium.

5

Finally, the combination of the invention may be prepared at the site of the keratin-containing material, such as the hair, which may be of interest when the polymers tend to precipitate under the normal application conditions of the agent. Thus, it is possible to sequentially apply a lotion or shampoo containing the cationic polymer and then a shampoo containing an anionic polymer, which treatment may optionally comprise a step of intermediate rinsing, to produce a permanent, in the first agent. a reducing agent, a cationic polymer, and in the second agent, the anionic polymer is used together with the fixing agent. This two-step process also allows working under conditions of different pH values which are adjusted in a way to obtain them under the solubility conditions of each polymer and to obtain, after mixing, a pH which results in a good application of 20 the combination of the invention on the keratin-containing material.

The agent based on polymers intended for the treatment of keratin-containing material and preferably for the treatment of hair, skin or nails, according to the invention is characterized in that it contains at least one anionic polymer and at least one cationic polymer in a solvent. .

The anionic polymers used in the combination of the invention have a molecular weight in the range of about 500 to approx. 5,000,000, advantageously in the range of approx. 10,000 to approx. 3,000,000.

The cationic polymers used in the combination of the invention have a molecular weight in the range of about 500 to 2,000,000.

35

The cationic polymers useful in the present invention contain a significant number of primary, secondary, tertiary or quaternary amines.

The anionic polymers which can be used according to the invention contain a considerable number of sulfonic acid groups, carboxylic acid groups or phosphoric acid groups.

10 DK 168059 B1

The agents have a pH ranging from 2 to 11, preferably from 4 to 10, and may be in the form of aqueous solutions, aqueous alcoholic solutions, gels, emulsions, creams, emulsions and dispersions.

5

The solvent may consist of water or any cosmetically acceptable organic or inorganic solvent or a mixture thereof.

The cationic polymers useful in the composition of the invention contain a considerable number of primary, secondary, tertiary and / or quaternary amines. They have a molecular weight of approx. 500 to approx. 5,000,000.

Among the cationic polymers which can be used in the composition of the invention are mentioned: 15 (1) - The quaternary derivatives of cellulose ethers disclosed in French Patent No. 1,492,597 and incorporated herein by reference and having the formula: RRR * CL 0 'o (1) uell J y wherein RCeu is the residue of an anhydroglucose group, y is a number from ca.

25 to approx. 20,000, and each group R individually represents a substituent which is a group of the general formula - (c2H2a ° -> m- <CH2-CH-O-) n- (C1-Oy <CcH2c) qE · CK2 3® 11 -

R -N-R ± [X] V

k1 2 3 wherein a is the number 2 or 3, b is the number 2 or 3, c is an integer 35 from 1 to 3, m is an integer from 0 to 10, m is an integer from 0 to 3, p is an integer from 0 to 10, q is the number 0 or 1, R 'is a group of the formula: 0 0 0 0 -H, -C-OH, -CON, -COK or -CO-NH.

CL 4 * 2 2

with the proviso that when q equals zero, R 'represents -H, R, R

3 and R each represent an alkyl group, an aryl group, an aralkyl group, an alkaryl group, a cycloalkyl group, an alkoxyalkyl group 123 or an alkoxyaryl group, each of groups R, R and R may contain up to 10 carbon atoms, and with the proviso that in the case of an alkoxyalkyl group, it contains at least two carbon atoms which separate the oxygen atom from the nitrogen atom, and the further proviso that the total number of carbon atoms present 12 3 12 3

in the groups R, R and R are between 3 and 12, wherein R, R and R are

together with the nitrogen atom to which they are attached may represent one of the following groups: Pyridine, α-methylpyridine, 3,5-dimethyl = 10 pyridine, 2,4,6-trimethylpyridine, N-methylpiperidine, N-ethylpiperidine , N-methyl-morpholine or N-ethyl-morpholine, X is an anion, V is an integer equal to the valence of X, the mean of n per anhydroglucose group in the cellulose ether is between 0.01 and ca. 1, and the mean of (m + n + p + q) per anhydroglucose group in the cellulose ether is between about 0.01 and approx. 4th

The most preferred polymers are the polymers of the above formula (1), wherein a and b are equal to 2, q is equal to 0, m, n and p are the sizes indicated above, R 'is hydrogen, and R is R and R 20 represent a methyl group. The mean values of n are 0.35-0.45 per.

anhydroglucose group and 1-2 for the sum m + p, with X being chlorine.

The preferred ethers have viscosities at 25 ° C from 50 to 35,000 centipoise in 2 wt% aqueous solutions measured by the method of ASTM D-2364-65 (Brookfield Viscometer, model LVF, 30 rpm, spindle # 2 ) and particularly preferred ethers are Union Carbide Corporation products marketed under the designations "JR-125", "JR-400" and "JR-30M", each of which is a polymer of the type described above with viscosities 30 and 30, respectively. 125 centipoise, 400 centipoise and 30,000 centipoise.

(2) - Water-soluble copolymers having a molecular weight of 20,000 to 3,000,000 selected from the following homopolymers and copolymers, the homopolymers as the main constituent containing the chain whose units have the formula (2) or (2 '): --CHO-R "C CR" --pti - r "c CR" -

(2) 2 I I (2 ·) H2 I I

H2 <X + / R4 + + R 'r 12 wherein R "represents hydrogen or a methyl group, R and R' independently represent an alkyl group having 1 to 22 carbon atoms, a hydroxyalkyl group wherein the alkyl group is preferably have 1-5 carbon atoms, or a lower amidoalkyl group, or wherein R and R1 together with the nitrogen atom to which they are attached may represent heterocyclic groups, such as piperidinyl or morpholinyl, in association with a cosmetically acceptable anion.

The copolymers may be copolymers of acrylamide or of diacetone = 10 acrylamide and of monomers which in the copolymer obtained result in groups of formula (2). These polymers are in the form of acetates, borates, bromides, chlorides, citrates, tartrates, bisulfates, bisulphites, sulfates, phosphates and succinates.

Among the quaternary ammonium polymers of the type defined above are the most preferred homopolymers of dimethyldiallyl ammonium chloride sold under the designation "Merquat 100" and having a molecular weight below 100,000, and the copolymers of dimethylallyl ammonium chloride and acrylamide having a molecular weight of over 500,000 and 20 is sold by the company Merck under the designation "Merquat 550".

These cyclopolymers are described in French Patent Specification No. 2,080,759 and the specification of the supplementary patent No. 2,190,406 thereto. The homopolymers and copolymers of formulas (2) and (2 ') can be prepared as described in United States Patent Nos. 2,926,161, No. 3,288,777, and 3,412,013.

(3) - Homopolymers or copolymers derived from acrylic acid or methacrylic acid and comprising as a group:

1 in X

R Rx Rx - CH- - C -, - CH- - C - or - CH- - C - Δ \ Δ, Δ x c = o c = o c = o «« · α O 0 NH Xw

35 A A A

'2 * 4 o' 4 NR - N - R4 RZ - N - R4 ς / \ 6 λ i® RR R3 X R3 13 wherein R · * "is H or CH 2, A is a linear or branched alkyl group with 1-6 carbon atoms or a hydroxyalkyl group having 1-4 carbon atoms, 2 3 4 R, R and R which are the same or different are an alkyl group having 1-18 carbon atoms or the benzyl group, R alkyl group having 1-6 carbon atoms, and X represents a halogen atom such as chlorine or bromine or the methosulfate group.

The useful comonomer (s) belongs to the group comprising: Acrylamide, 10 methylacrylamide, diacetone acrylamide, acrylamide and methacrylamide which are substituted at the nitrogen atom by lower alkyl groups, alkyl esters of acrylic acids and methacrylic acids, vinylpyrrolidone and vinyl esters.

Examples include: The copolymer of acrylamide and 8-methacryloyloxyethyltrimethylammonium = methosulfate sold under the terms "Reten" 205, 210, 220 and 240 by Société Herculés, the copolymers of ethyl methacrylate, oleyl methacrylate and & Quaternium 25 38 "is mentioned in the" Cosmetic Ingredient Dictionary ", the copolymer of ethyl methacrylate, abiethyl methacrylate and | 3-methacryloyl = oxydiethylmethylammonium methosulfate, which under the term" Quaternium 37 "is mentioned in" Cosmetic Ingredient Dictionary ", the polymer of β-methyl The term "Quaternium 49" is mentioned in the "Cosmetic Ingredient Dictionary" and the copolymer of | 3-methacryloyloxyethyltrimethylammonium methosulfate and 8-methacryloyloxystearyl dimethyl ammonium methosulfate, which under the term "Quaternium 42" is mentioned in "Cosmetic Ingredient Dictionary".

35

Also mentioned are the phosphate / acrylate copolymer of aminoethyl acrylate sold under the designation "Catrex" by "Société Nation Starch" which copolymer "Catrex" has a viscosity of 700 centipoise at 25 ° C in an 18% aqueous solution, and the compounds described in U.S. Patent No. 3,372,149, the grafted and cross-linked cationic copolymers having a molecular weight of 10,000 to 1,000,000 and preferably from 15,000 to 500,000, obtained by copolymerization of: a) at least one cosmetic monomer; b) dimethylaminoethyl methacrylate; c) polyethylene glycol; and d) a polyunsaturated crosslinking agent disclosed in French Patent No. 2,189,434.

The crosslinking agent belongs to the group comprising: The dimethacrylate of ethylene glycol, the diallyl phthalates, the divinylbenzenes, tetraallyl = oxyethane and the polyallylsucroses with 2-5 allyl groups per ml. mole of sucrose.

The cosmetic monomer can be of a very varied type, e.g. a vinyl ester of an acid having 2-18 carbon atoms, an allyl ester or methallyl ester of an acid having 2-18 carbon atoms, an acrylate or methacrylate of a saturated alcohol of 1-8 carbon atoms, an alkyl vinyl ether wherein the alkyl group has 2-18 carbon atoms , an olefin having 4-18 carbon atoms, a heterocyclic vinyl derivative, a dialkyl maleate or a Ν, dial-dialkylaminoalkyl maleate wherein the alkyl group has 1-3 carbon atoms, or an unsaturated acid anhydride.

The polyethylene glycol has a molecular weight between 200 and several million, preferably between 300 and 30,000.

These grafted and crosslinked copolymers preferably consist of: a) 3-95% by weight of at least one cosmetic monomer selected from vinyl acetate, vinyl propionate, methyl methacrylate, stearyl methacrylate, lauryl methacrylate, ethyl vinyl ether, cetylvinyl ether, stearyl vinyl ether, hexene-1-, hexene-1-, vinylpyrrolidone and N, N-diethylaminoethyl monomaleate, maleic anhydride and diethyl maleate, b) 3-95 wt% dimethylaminomethyl methacrylate, c) 2-50 wt% and preferably 5-30 wt% polyethylene glycol, and d) 0.01-8 wt% of a crosslinking agent such as the one mentioned above, the percentage of the crosslinking agent being calculated relative to the total weight of a) + b) + c).

(4) The cationic polymers selected from: a) The polymers of the formula -AZAZ- (3), wherein A represents a group / v having 2 amino functions and preferably the formula -N N-, Z represents the V_ / 5 symbol B or B ', wherein B and B1 are the same or different, and denotes a divalent group which is a straight or branched chain alkylene group containing inflil 7 carbon atoms in the main chain and either unsubstituted or substituted by hydroxyl groups and may further comprise oxygen atoms, nitrogen atoms, sulfur atoms. , 1-3 aromatic and / or heterocyclic rings, the oxygen atoms, nitrogen atoms and sulfur atoms being in the form of the ether or thioether group, sulfoxide group, sulfone group, sulfonium group, amino group, alkyl = amino group, alkenylamino group, benzylamino group, amine oxide group, amine oxide group , the imido group, alcohol ester = group and / or urethane group, which polymers and the process for their preparation are described know in French patent no.

2162025.

b) The polymers of formula -Α-ΖΊ-Α-ΖΊ- (4), wherein A represents a group XX ^ \ 20 containing 2 amino functions and preferably has the formula -N ^ _ ^ N-, and represents the symbol B ^ or B ' and B represents at least once the symbol B 1, where B 1 represents a divalent group which is an alkylene group or straight or branched chain hydroxyalkylene group containing up to 7 carbon atoms in the main chain, and B1 is a divalent group which is an alkylene group with straight or branched chain and containing up to 7 carbon atoms in the main chain unsubstituted or substituted by one or more hydroxyl groups and interrupted by one or more nitrogen atoms, wherein the nitrogen atom is substituted by an alkyl group optionally having 1-4 and preferably 4 carbon atoms. 30, optionally interrupted by an oxygen atom, and mandatory comprising one or more hydroxyl and / or carboxyl functions.

c) The polymer of formula -A'-Z'-A'-Z'- (5) wherein R 'represents a blend - / s. + / v of the groups -N N- and - N-, 35' CH 2 'coo wherein Z' is B ', B, B' or B '' with the meaning given above.

d) the quaternary ammonium salts and the oxidation products of the polymers of formulas (3) and (4) listed above under a) and b).

DK 168059 B1 16

The polymers of formula (4) and of formula (5) and the process for their preparation are described in the disclosure to French Publication No. 2,280,361.

The polymer of formula A-Z-A-Z- (3) and A-Z ^ -A-Z ^ (4) can be prepared as disclosed in French Patent No. 2,152,025.

Particularly preferred polymers are the polycondensation product of N, N'-bis (2,3-epoxy-propyl) piperazine or of pierazine bis-acrylamide and 10 of piperazine as described in Examples 1, 2 and 14 of French Patent No. 2,162,025. / and the polycondensation products of piperazine, of diglycolamine and epichlorohydrin or of piperazine, 2-amino-2-methylpropanediol-1,3, and of epichlorohydrin as described in Examples 2, 3, 4, 5 and 6 of the disclosure to French publication no.

15,280,361.

(5) The quaternized polymers of the formula:? X f 1 M 9 20 -1¾-AN-- B-- _ *; «_ n wherein R 1, R 3, R 3 and R 2, which may be the same or different, represents 25 aliphatic, alicyclic or arylaliphatic groups containing a maximum of 20 carbon atoms, or lower hydroxyaliphatic groups, 12 3 4 or wherein R and R and R and R together or separately together with the nitrogen atoms to which they are attached denote heterocyclic groups containing optionally another heteroatom besides the nitrogen, or wherein R, R, R and R represent the group R · 3 / - ch 2 - cir 2 3 4 wherein R 1 represents hydrogen or a lower alkyl group and R 1 35 0 0 0 / R'6 0

Il c II c il / Il η ner - CN, - C - OR ', - C - R', - C - N <. , - C - O - R '- D, 0 II * 7 cg or -C-NH-R 1 -D, R' represents a lower alkyl group, R 'represents hydrogen or a lower alkyl group, R' 'represents an alkyl = long group, D represents a quaternary ammonium group, A and B may represent polymethylene groups containing 2-20 carbon atoms, which groups may be linear or branched and saturated or unsaturated and inserted into the main chain containing one or more aromatic rings or one or more groups - CE ^ - Y - C ^ - me <^ Y in the sense 0 / S, SO, SO2, - S - S -, 5 R'9 0 0 0 -N-, - N -. , - CH -, -NH-C-NH, - C - N - or -C-O-

I I y “1 I

r, 8 r, 9 OH r, 8

ISLAND

with R 'in the sense hydrogen or a lower alkyl group, and 10 9 12

R * is, in the sense, a lower alkyl group, or wherein A and R and R are

together with the two nitrogen atoms to which they are attached denotes a piperazine group.

IC Θ 15 X is an anion derived from an inorganic or organic acid.

n is of such a size that the molecular weight will be between 1,000 and 100,000.

Polymers of this type are particularly described in French Patent No. 2,320,330 and U.S. Patent Nos. 2,273,780, No. 2,375,853, No. 2,388,614, No. 2,454,547, No. 3,206,462, No. No. 2,261,002 and No. 2,271,378.

Other polymers of this type are disclosed in United States Patent Nos. 3,873,870, 4,001,432, 3,929,990, 3,966,940, and 4,005,193.

Among these polymers are mentioned the quaternized polymers on the basis of repeated units of the general formulas: Χθ X6

R R

-N®-A-N®-B- (6) 35 1 1 R 'R' X® X® R'2 CH3 - N® - Αχ- N® - B1 - (7).

R'1 CH3

A

wherein X represents an anion derived from an inorganic or organic acid, ice is a lower alkyl group or the group -CH2 ~ CH2OH, R 'is an aliphatic group, an alicyclic group or an aryl aliphatic group, R' 2 contains a maximum 20 is an aliphatic group containing a maximum of 20 carbon atoms, R 1 is an aliphatic group, an alicyclic group or an aryl aliphatic group containing a maximum of 20 and at least 2 carbon atoms, or wherein the groups R and R 'are 2 and R 2, respectively. and R *, which is attached to the same nitrogen atom, together with this forms a ring which may contain another heteroatom in addition to the nitrogen atom, A represents a divalent group having one of the following formulas: - '' Ok CH 2 - (o, m or p) 15 - (CH0) - S - (CH0) - 2 n 2 n - (CH-) - 0 - (CH.J - 2 n 2 n - (CH_) - S - S - (CH,) - 2 n 2 n - (CH, -) SO - (CH,) - 20 2 n 2 n - (CH,) - SO, - (CH,) - 2 n 2 2 n „-O- n is all 2 or 3, A1 and also A represents a divalent group of formula n: - (CH,) - CH - (CH,) - CH - (CH,). - Y, ^ Λ i Δ L ·

E K

Wherein x, y and t are integers which can range from 0 to 11 such that the sum (x + y + t) is greater than or equal to 0 and lower than 18, and E and K represent a hydrogen atom or a aliphatic group containing less than 18 carbon atoms, B and represents a divalent group of formula: CH 2 - (o, m or p) or - (CH 2) - CH - (CH, K - CH - (CH 2) -

2 V, 2 2, 2 U

D G

wherein D and G represent a hydrogen atom or an aliphatic group 19 containing less than 18 carbon atoms, and v, z and u are integers which may vary from 0 to 11, two of which may simultaneously be 0, so that the sum (v + z + u) is greater than or equal to 1 and less than 18, and so that the sum (v + z + u) is greater than 1 when the 5 sum (x + y + t) is equal to 0, a divalent group of the formula:

OH

- CH 2 - CH - CH 2 - or - (CH 2) n - 0 - (CH 2) n, where n is as defined above. The terminated groups in the polymers of formula 7 may be of the type 10 R'2 CH- \ 3 \ NA - NA or X - B-.

1 '/ R · CH3 Θ In general phonics 6 and 7, X denotes in particular a halide anion (bromide, * -5 iodide or chloride) or an anion derived from other inorganic acids such as phosphoric acid or sulfuric acid etc., or also an anion derived of an organic sulfonic acid or carboxylic acid, especially an alkane carboxylic acid containing from 2 to 12 carbon atoms, (e.g. phenylacetic acid), benzoic acid, lactic acid, citric acid or paratoluene sulfonic acid.

20

The substituent R preferably represents an alkyl group containing 1-6 carbon atoms, and when R 'or R' and R 'represent an aliphatic group, it is in particular an alkyl group or a cycloalkyl alkyl group containing less than 20 carbon atoms and preferably not γ more than 16 carbon atoms, preferably from 1-8 carbon atoms.

When R 1 or R 1 represents an alicyclic group, it is especially a 5 or 6 membered cycloalkyl group.

1 When R 'or R' represents an aryl aliphatic group, it is especially an aralkyl group, such as a phenylalkyl group, wherein the alkyl group preferably contains 1-3 carbon atoms. When two groups R and R * or R'1 and R'2, attached to one and the same nitrogen atom, form a ring therewith, R and R1 or R1 and R * together may in particular denote a polymethylene group containing 2-6 carbon atoms and the ring may contain another heteroatom, e.g. an oxygen atom or a sulfur atom, and in particular they may represent the group - (CH2) -O- (CH2) 2 ~.

Preferably, R'1 is an alkyl group containing 2-18 carbon atoms, especially 2-16 carbon atoms, a benzyl group or a cyclohexyl group.

Among the polymers of formula (7), in particular, are the polymers wherein R R is an ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, hexadecyl group, cyclohexyl group or benzyl group, A, is a polymethyl group containing 3, 5, 6, 8, 9 or 10 carbon atoms, optionally branched by one or two alkyl substituents containing 1-12 carbon atoms, 5 and is an o- or p-xylylidene group, or is a polymethylene group containing 3, 4.5 or 6 carbon atoms, optionally branched by one or two alkyl substituents containing 1-12 carbon atoms, preferably the substituent -CE 2 -CHOH-Cl 2 -.

The invention encompasses the cosmetic use of the polymers of formula 6 or 7, wherein the groups A, B, R or R ', A,, B,, R', 2 11 R 'have several different meanings in one and the same polymer 6 or 7. .

Such polymers are described in particular in French Publication Nos. 2,270,846 and 2,316,271.

The preferred polymers are polymers containing the following group: 20 Γ ~ CH, CH, ~ 1-5 in -5 -N®- (ch2) 6 - (CH2) 4-- (GI) CH, CH,

_J J

25 H3 ^ H3 - N © - (CH2) 6- N®-CH2-CHOH-CH2 - (G2) CH3 CH3 _ Br® Br® _ - N + -CH, -CHOH-CH, -N + - (CH,), - (G3) Π 2 0 6 35 V 0 _ Br® Bre _ CH, CH, IJ t * 5 - R®- (CH2) 3-N®- (ch2) 6- (G4) CH, CH,

J

21 DK 168059 B1 CH2 O CH-, ~ '2 n + --N- (CH2) 3- NH-C-NH- (CH2) 3- N - (Cfi2) 2-0- (CH2) 2 2nC1- (G5) _CH3 CH3 5 wherein n is equal to approx. 6th

The polydimethylbutylammonium chloride - a, w-bis (triethanolammonium chloride) - is sold under the designation "ONAMER M" by ONYX Chemical Co.

10

Other polymers of this type that may be used in the practice of the invention are those disclosed in French Publication No. 2,336,434, in particular the polymers of the above formula wherein B represents the group: o-o · “= 20 The polymers of this type are also disclosed in United States Patent Nos. 4,025,617, 4,025,627, 4,025,653, 4,026,945 and 4,026,645.

4,027,020 *

It is also possible to use in the compositions of the invention polymers of the above-mentioned ionogenic type of formula: R1 R1

I V

- N®-A-Nft- (CH2) CO - B - OC - (CH2) - ioi® ainine _2 X _2 X® 30 LRR __ wherein A represents an alkylene group or a linear or branched, saturated or unsaturated hydroxyalkylene group, B represents: (a) a glycol group of the formula - O - Z - O - wherein Z represents a linear or branched hydrocarbon group or a group of the formula: - [CH 2 -CH 2 -OxCH 2 -CH 2 - or -O-CH 2 "CH-0 - CH2-CH-L έΗ3 _y iH3 wherein x and y represent an integer from 1 to 4 representing a designated and particular degree of polymerization or any number from 1 to 4 representing an average degree of polymerization, (b ) a bis-secondary diamine group, such as a derivative of piperazine of the formula: - i / -, (c) a bis-primary diamine group of the formula: - NH - Y - NH - wherein Y represents a linear or branched hydrocarbon group or the divalent group - CH 2 - CH 2 - S - S - CH 2 - CH 2 -, (d) an ureylene group of the formula - NH - CO - NH -, 1 2 15 R represents an alkyl group containing 1 to 4 carbon atoms, R represents a linear or branched hydrocarbon group containing from 2 to 12 carbon atoms, the groups R also being able to represent methyl groups which are interconnected and when A represents an ethylene group together with A and the two nitrogen atoms form a bivalent group 20 derived from piperazine of the formula: / \ - NN - \ _ / X * 'represents a halide group, especially a bromide or chloride group, and n represents the number 1 or an integer from 3 to 10.

These polymers are prepared in a manner known per se by polycondensation of a bis-tertiary diamine of the formula: K 1 -R 1 N - A - N r 2 x / 2 R 2 with a bis-halo-aryl compound of the formula: 35

X - (CH ~) - CO - B - OC - (CH0) - X

z n z n wherein the various substituents have the meanings set forth above.

Among these polymers, the most preferred are the polymers containing the following groups which have been prepared by polycondensation.

23 DK 168059 B1 CH, CH, CH, ~

I J I «3, J

- © Ne "CH" {CR2} 2 ~~ © N-eCH2 "COO (CH2) 3 - O CO CH2 - (G6) in Cl Cl CH3 CH3 _ with absolute viscosity 0.99 centipoise CH, CH, II - j, _ / \ - N —— CH - (CH,) ^ -N - CH, - CO NK CO - CH, - (G7) ® · Cl® 2 2 © 'Cl® 2 N'-' 2 CH, CH, - 3 3 - with absolute viscosity 1.62 centipoise CH 3 ch 3 - N - (CH,), - N-_CH, - CONH- (CH,), - NHCO - CH, - (GS ) Absolut 'Cl® 22®' Cl® 2 22 2 CH3 CH3 with absolute viscosity 1.39 centipoise CH, CH, - I 3 i -5 - N -— (CH,), - N -s CH, - CONH - (CH,), - NHCO - CH, - (G9) © 'Cl® 2 J ©' Cl® 2 2 2 2 ch3 ch3 with absolute viscosity 1.94 centipoise CH, CH2 CH3, 3, 3 - -N - - CH- (CH,), - N-CH, -CONH - (CH,), - NHCO - CH, - (GIO) ® in cle 2 z © 'cl® 2 2 2 2 ch3 ch3 with absolute viscosity 1.73 centipoise (6) The copolymers of vinyl pyrrolidone of the formula: NN ^ 0 j * 1 r -j __c! h_CH, --CH? -C - M -

Jn L1 _m LJP n (C = o) v 0 -R2-N (R3) 2 R4, x® 24 n in which n is between 20 and 99, preferably between 40 and 90 mol%, and m is between 1 and 80, preferably between 5 and 40 mol%, p represents 0 to 50 mol%, and n + m + p = 100, represents H or CH 3, y represents 0 or 1, R 1 is -CH 2 - CHOH - - or c x H 2 x * wherein 5 x = 2 to 18, R 2 represents CH 2, C 2 H 2 or ^ CH 2, R 2 represents CH 3 or C 2, x 3 is selected from Cl, Br, J, 1/2 SO 4, HSO 4, CH 3 SO 3, and M is a monomeric group obtained by heteropolymerization using a suitable copolymerizable vinyl monomer. The polymers can be prepared in accordance with the procedure described in French Patent Specification No. 2,077,143.

The preferred copolymers have a molecular weight between 100,000 and ca.

1,000,000, such as the commercially available products "Gafquat 734" and 15 "Gafquat 755" from GAF Corporation of New York.

(7) The polyaminoamides (A) described below: (8) The cross-linked, alkylated or non-alkylated polyaminoamides 20 selected from the group comprising at least one water-soluble cross-linked polymer obtained by cross-linking a polyaminopolyamide (A) prepared by polycondensation of an acid compound with a polyamine. The acid compound is selected from (i) organic dicarboxylic acids, (ii) aliphatic mono- and dicarboxylic acids with ethylenic double bond, (iii) the esters of the above acids, preferably with lower alkanols containing 1 to 6 carbon atoms, and (iv) mixtures of these compounds. . The polyamine is selected from bis primary and mono- or di-secondary polyalkylene polyamines. 0 to 40 mol% of this polyamine can be replaced with a bis-primary amine, preferably ethylenediamine, or 30 with a bis-secondary amine, preferably piperazine, and 0 to 20% can be replaced with hexamethylenediamine. The cross-linking is carried out by means of a cross-linking agent (B) selected from epihalohydrin, deep oxides, dianhydrides, unsaturated anhydrides or bis-unsaturated derivatives, the cross-linking being characterized in that it is carried out by using 0.025 to 0.35 moles of a cross-linking agent. per. amino group in the poly = aminopolyamide (A), generally from 0.02 to ca. 0.2 and in particular from 0.025 to approx. 0.1 mole crosslinking agent per amino group in the polyaminopolyamide (A).

This crosslinked polymer is completely soluble in water in an amount of 10% without gelling, the viscosity of a 10% solution in water at 25 ° C being more than 3 centipoise and usually being between 3 and 25 centipoise.

The acids which can be used to prepare the polyaminopolyamide (A) are selected from saturated organic dicarboxylic acids containing 5 to 10 carbon atoms, e.g. adipic acid, 2,2,4-trimethyladipic acid and 2,4,4-trimethyladipic acid, terephthalic acid, aliphatic mono- and dicarboxylic acids with ethylenic double bond, e.g. acrylic acid, methacrylic acid and itaconic acid.

Further, the esters of the above acids or mixtures of two or more carboxylic acids or the esters thereof can be used.

The polyamines which can be used to prepare the polyaminopolyamides (A) are selected from the bis-primary or mono- or di-secondary polyalkylene polyamines, e.g. diethyltriamine, dipropylenetriamine, triethylenetetramine and mixtures thereof.

Preferably, a dicarboxylic acid amount and an amine amount are used in equimolar amounts relative to the primary amino groups of the polyalkylene polyamines.

The composition of preferred polyaminoamides (A) may be represented by the general formula (I) 25 -fOC-R-CO-Z * (I) wherein R represents a divalent group derived from the acid or addition compound used. of the acid with the bis-primary or bis-secondary amine. Z represents: 1) In amounts from 60 to 100 mole%, the group - NH - f (CH,) - - ΝηΊ - (II) L 2 x Jn 35 wherein x = 2 and n = 2 or 3, or where x = 3 and n = 2, which group is derived from triethylenetriamine, triethylenetetramine or dipropylene = triamine, 2) in amounts from 0 to 40 mol%, the above group (II), wherein x = 2 and n = 1, which are derived of ethylene diamine, or the group / \ -N N- derived from piperazm, in amounts from 0 to 20 mol%, the group - NH - (C , which is derived from hexamethylenediamine.

The preparation of polyaminoamides (A) is described in more detail in French Publication No. 2,252,840.

The polyaminopolyamides thus obtained are then crosslinked by the addition of a crosslinking agent. As a crosslinking agent, a difunctional compound selected from the (a) epihalohydrin, e.g. epi = 10 chlorohydrin, (b) the deep oxides, e.g. diglycidyl ether, Ν, Ν'-bis-epoxypropylpiperazine, (c) the dianhydrides, e.g. the dianhydride of butane = tetracarboxylic acid or the dianhydride of pyromellitic acid; and (d) the bis-unsaturated derivatives, e.g. divinyl sulfone and methylene bis-acrylamide.

The cross-linking reactions are carried out at 20 ° C by starting from 20 to 30% aqueous solutions of polyamino-polyamide, to which the cross-linking agent is added in very small amounts to obtain a significantly increased viscosity, but without forming a gel which does not again will dissolve in the water. The concentration is then rapidly adjusted to 10% by the addition of water, and the reaction medium is optionally cooled.

The secondary amino groups of the crosslinked polyaminoamides may be alkylated.

An epoxide, e.g. glycidol, ethylene oxide, propylene oxide or a compound with ethylenic double bond, e.g. acrylamide.

The alkylation of the cross-linked polyaminoamides is carried out in aqueous solution at the concentration of 10-30% at a temperature between 10 ° C and 95 ° C. The degree of alkylation relative to overall basicity ranges from 0 to 80%.

The crosslinked and optionally alkylated polyaminoamides do not contain 3 ~ * reactive groups, do not have alkylating properties and are chemically stable.

Among the polymeric polyaminoamides (A) and the polymeric polyaminoamides (A) that are cross-linked and optionally alkylated, the polymers listed below are preferred:

The polymers designated K1 which are obtained by powder condensation of equimolar amounts of adipic acid and diethylenetriamine.

DK 168059 B1 27

The polymers designated K 1a are obtained by cross-linking polymer K I with epichlorohydrin (11 moles of epichlorohydrin per 100 amine groups).

5 The crosslinked polymers designated K1b / obtained by crosslinking the polymer K1 with methylene bis-acrylamide (12.1 moles of methylene-bis-acrylamide per 100 amino groups in the polyaminopolyamide).

The polymer, designated K Ic, is obtained by cross-linking the polymer 10 k I with N 2 '- bis-epoxy-propyl-piperazine (7.3 moles of cross-linking agent per 100 amino groups in the polyaminoamide).

The polymer, designated K ld, is obtained by cross-linking the polymer K I with divinyl sulfone (13.9 moles crosslinking agent per 100 amino groups 15 in the polyaminoamide).

The polymer, designated K le, is obtained by cross-linking the polymer K 1 with the bis-acrylamide of piperazine.

The polymer, designated K II, is obtained by polycondensation of 3 moles of adipic acid with 1 mole of piperazine and 2 moles of diethylenetriarain.

The polymer, designated KIla, is obtained by cross-linking the polymer K II with epichlorohydrin (13.2 moles of cross-linking agent per 100 amino groups in the polyaminoamide).

The polymer, designated K III, is obtained by polycondensation of equimolar amounts of adipic acid and triethylenetetramine.

The polymer, designated K IIla, is obtained by crosslinking the polymer K III with epichlorohydrin (7.8 moles of crosslinking agent per 100 amino groups in the polyaminoamide).

The polymer, designated K mb, is obtained by cross-linking the polymer K III with methylene bis-acrylamide (3.4 moles cross-linking agent per

100 amino groups in the polyaminoamide).

The polymer, designated K IV, is obtained by polycondensation of the reaction product of 2 moles of methylitaconate and 1 mole of ethylenediamine with diethylenetriamine.

The polymer, designated K IVa, is obtained by crosslinking the polymeric K IV with epichlorohydrin (22 moles of epichlorohydrin per 100 amino groups in the polyaminoamide).

The polymer, designated K IVb, is obtained by cross-linking the polymer K IV with methylene bis-acrylamide (16 moles cross-linking agent per

100 amino groups in the polyaminoamide).

The polymer, designated K V, is obtained by polycondensing a mixture of 2 moles of methyl acrylate and 1 mole of ethylenediamine with diethylene = 10 triamine.

The polymer, designated K Va, is obtained by cross-linking the polymer K V with epichlorohydrin.

The polymer, designated K VI, is obtained by polycondensing a mixture of 2 moles of methyl methacrylate and 1 mole of ethylenediamine with diethyl lentriamine.

The polymer, designated K Via, is obtained by cross-linking the polymer 2® K VI with methylene bis-acrylamide (21.4 moles crosslinking agent per 100 amino groups in the polyaminoamide).

The polymer VII is obtained by alkylating the glycidol of the polymer K1a.

2 * 5

The polymer K VIII is obtained by alkylating the acrylamide of the polymer K 1a.

The preparation of all these polymers is described in French Publication No. 2,252,840.

(9) The crosslinked polyaminoamides which are soluble in water are obtained by crosslinking a polyaminoamide (A described above) by at least crosslinking agent selected from: 35 (I) The compounds selected from (1) the bis-halohydrin, (2) the bis-azetidinium compounds, (3) the bis-haloacylated diamines, (4) the alkyl-bis-halides; (II) the oligomers obtained by reacting a compound (a) selected from (1) the bis-halohydrins, (2) the bis-azetidinium compounds, (3) the bis-haloacylated diamines, (4) the alkyl-bis-haloids, ( 5) the epihalohydrinins, (6) the deep oxides, (7) the bis-unsaturated derivatives of a compound (b) which is a bi-functional compound reactive to the compound (a); (III) the quaternization product of a compound selected from compounds (a) and oligomers (II) and comprising one or more tertiary and fully or partially alkylatable amino groups together with an alkylating agent (c) preferably selected from methyl or ethyl chlorides, bromides, iodides, sulfates, mesylates and tosylates, benzyl chloride or bromide, ethylene oxide, propylene oxide and glycidol, the cross-linking being made by 0.025 to 0.35 mole, in particular 0.025 to 0.2 mole and most preferably 0.025 to 0.1 mole of crosslinking agent per amino group 1 of the polyaminoamide.

The bis-halohydrin is obtained by reaction of an epihalohydrin such as epichlorohydrin or epibromohydrin with the bis-functional compounds such as secondary bis-amines, primary amines, diols, bis-phenols or bis-mercaptans.

They may be intermediates directly to produce bis epoxides, but conversely they can be obtained by opening the oxirane ring with a hydrogen acid such as hydrochloric or hydrobromic acid.

In either case, the halogen atom may be attached to the latter or to the former carbon atom, without its position being predetermined for the reactivity of the crosslinking agent or the properties of the final product.

Examples include the following dihalohydrins: 30 X CH, - CH - CH, - N - CH, - CH - CH,, X = Cl or Br 2. y 2 v / 2 v 2

OH N- 'OH

/ \ / - \

X - CH, - CHOH - CH, - N N - CH, - CHOH - CH, - N N-CH, -CHOH-CH, X

2 2 \ _f 2 2 \ _ (2 2 35 X-CH, - CHOH - CH, - N - (CH,) - N - CH, - CHOH - CH, X, n = 2 to 6 2 2, 2 n , 2 2 CH3 CH3 1

- CH2 - CHOH - CH2 - N - CH2 - CHOH - CH2X

R

30 DK 168059 B1

R = Cn H2 n + χ or also - (CH2 ~ CH2-0) m H

n = 1 to 18 m = 1 or 2.5 X - CH 2 - CHOH - CH 2 - 0 - ICH 2 - CH 2 O] p CH 2 - CHOH - Ci 2 X, p = 0 to 25 _jT \ _ x ch 2 -cho - ch 2 - o - py - c - cr ~ ° ~ CH2 "CHOH" CH21 X - CH2 - CHOH - CH2 - S - (CH2) - S - CH2 - CHOH - CH2X, q = 2 to 6.

The bis-azetidinium compounds are derived from the N, N-dialkylhalohydroxy = 15 propylamines by cyclization.

However, cyclization can be made more difficult in the case of certain amines due to steric hindrance.

20

Since the reactivity of the azetidinium groups is only slightly different from the reactivity of the epihalohydrogen groups, compounds of the bis-halohydrin compounds whose halogenohydrogen groups are linked to the rest of the molecule via two tertiary amino groups or an azetidinium group and the azetidinium group can be used.

The bis-halogenacyl diamines useful as crosslinking agents can be illustrated by the following formula:

X - (CH-) - CON - A - NCO - (CH0) X

2 n n, 9 2 n

Rx R

where X represents chlorine or bromine / A represents -CH 2 CH 2 / -CH 2 CH 2 -CH 2 - or -C-, n represents an integer from 1 to 10, and R 1 and R 2 are 35 0 1 2 hydrogen or / where R and R may be interconnected and added 1 2

together denote the ethylene group. When A represents -C-, R and R represent

II

hydrogen. 0

Of particular interest for the purposes of the invention are the bis-chloroacetyl derivative or the bis-bromoundecanoyl derivative of ethylenediamine and of piperazine.

3i DK 168059 B1

The alkyl bis-halides which can be used according to the invention can be illustrated by the following general formula:

, -5 f J

5 X "(OL) (Z) --- N® - A - N® - (CIL) - X

x m i i j \ CH, CH, _ x® x® _ n 10 CH - CH.

S '% where X represents chlorine or bromine, Z represents C C, x = 1

CH = CbS

to 3, m is 0 or 1, and n is 0 or 1, since m and n cannot simultaneously denote the number 1. When m = 1, x = 1. A represents a saturated, dihydrogen hydrocarbon group of 2, 3, 4 or 6 carbon atoms or the 2-hydroxypropylene group.

The oligomers which can be used in the agents of the invention are statistical mixtures of compounds obtained by reacting a compound (a) described under groups I and II with a bifunctional compound (b) which is reactive to these compounds (a) , ie in the usual manner, the bis-secondary amines such as piperazine, the bis-tertiary amines such as Ν, Ν, Ν ', N'-tetramethylethylene, propylene, butylene or hexamethylenediamine, bismercaptans, such as the ethanedithiol-1,2 or the bis-phenols, such as "bis-phenol A" or propane-2,2- (4,4'-dihydroxy-diphenyl).

The molar amounts of b in ratio a are between 0.1 and 0.9.

The oligomerization reactions are generally carried out at temperatures between 0 ° C and 95 ° C, preferably from 0 ° C to 50 ° C in water or in a solvent such as isopropanol, t-butanol, acetone, benzene, toluene, dimethyl = formamide or chloroform.

The quaternization reactions leading to a quaternization product described above under III are carried out between 0 ° C and 90 ° C in water or in a solvent such as methanol, ethanol, isopropanol, t-butanol, alkoxyethanols, acetone, benzene, toluene, dimethylformamide or chloro = form.

The secondary amino groups of the above-mentioned crosslinked polymeric polyaminoamides may be alkylated, which increases their solubility in water.

An alkylating agent can be used: 5 (1) An epoxide, e.g. glycidol, ethylene oxide or propylene oxide, or (2) a compound having ethylenic double bond, e.g. acrylamide.

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

Among the crosslinking agents and preferred crosslinked polymers selected from the ones described above, the following may be mentioned:

Crosslinking agent R 1a.

This crosslinking agent of the formula + // \ CH2 \ - ^ CH * CH2 * \ _ / N - CH2 - CI1 -> CH2 cr - o 'υ ch3 ch3so4 u is prepared as follows:

To 236 g of chloric formic acid solution containing 57.2 g (0.289 mole) of bis- (epoxypropyl) piperazine is added over an hour 36.4 g (0.289 mole) of diraethyl sulfate, keeping the reaction mixture stirred at 30 ° C.

30

The quaternized derivative is then precipitated from the solution in a large ether excess. After drying, a very viscous oil is obtained. Its epoxide content is 5.19 milliequivalents / gram.

Polymer KA Ib.

This polymer is obtained by cross-linking the polymer K I with the cross-linking agent R 1a as set out below:

To 500 g of aqueous solution containing 100 g (0.585 amino equivalents) of the polyaminoamide K1 (prepared by condensation of equimolar amounts of adipic acid and diethylenetriamine), at ambient temperature 22 g (0.057 mol) of the crosslinking agent R 1a are added and the reaction mixture is increased. temperature to 90 ° C.

After 20 minutes, a gel formation is observed in the solution. It is then rapidly added 698 g of water. A clear solution of yellow-green color containing 10% active material is obtained. The viscosity measured at 25 ° C is 0.68 µ at 87.93 sec.

Crosslinking agent R Ila.

10

This crosslinking agent of the formula CH, CH, CH, - CH - CH, - - CH, - CH - CH, 15 ^ / 2 + "- - + 2 \ / 2 x o CH3SO4" CH3SO4 "as stated below:

To 187.3 g of formic acid solution containing 54.9 g (0.277 mole) of bis- (epoxypropyl) piperazine, 70 g (0.555 mole) of dimethyl sulfate is added over 1 hour, keeping the reaction mixture stirred at 30 ° C.

25

The reaction mixture thickens during the addition and solidifies after several hours at ambient temperature. The mass dissolves hot in di = methylformamide. In the cold, the solution separates white crystals of melting point 205 ° C, whose epoxide index is 4.25 milliequivalents / gram.

30

Polymer KA Ilb.

This polymer is obtained by cross-linking the polymer K I with a cross-linking agent R 11a as indicated below: 35

To 476 g of aqueous solution containing 95.2 g (0.557 equivalents of amine) polyaminoamide K I is added at ambient temperature 20 g (0.0425 mol) of the crosslinking agent prepared as above. The reaction mixture is kept under stirring at 90 ° C for one hour, after which the solution is adjusted to 10% active material by the addition of 656 g of water.

34 DK 168059 B1

The solution is clear in yellow-green color. The viscosity measured at 25 ° C is 0.27 µ at 87.93 sec.

Crosslinking agent R Illa.

5

This is an oligomeric, bis-unsaturated crosslinking agent obtained by starting from the bis-acrylamide of piperazine and piperazine in the molar ratio 3/2 as follows: 10 To 380 g of aqueous solution containing 194 g of the bis-acrylamide (1 mol) is added over an hour between 10 and 15 ° C 223 g of aqueous solution containing 56.8 g (0.66 mole) of piperazine. The reaction mixture is then left for 24 hours at ambient temperature. The solution becomes cloudy and thickened. It is heated by heating, after which it is poured dropwise into 5 liters of acetone. The crosslinking agent precipitates. After filtration and drying, a white solid is obtained, the solids content of which is 80%.

Polymer KA Hib.

20

This polymer is obtained by cross-linking the polymer K I with the cross-linking agent R IIa as follows:

To 370 g of aqueous solution containing 111 g (0.649 amino equivalents) of polyaminoamide K I is added at ambient temperature 50 g of the crosslinking agent prepared as above, and the temperature of the reaction mixture is brought to 90 ° C. After 30 minutes, the reaction mixture gels. The solution is quickly adjusted to a solids content of 10% by adding 1050 g of water.

30

A clear yellow-green solution is obtained whose viscosity measured at 25 ° C is 5.8 centipoise.

Crosslinking agent R IVa.

35

The oligomeric bis-halohydrin crosslinking agent is prepared by starting from epichlorohydrin and piperazine in the molar ratio of 5/4 and has the formula: r / - \ Ί

Cl CH, CH OH - CH, --- N N - CH, - CH OH - CH, - - Cl 2 2 ~ \ _ / 2 2J n wherein n = 4. The cross-linking agent is prepared as follows: DK 168059 B1

To 541 g of aqueous solution containing 69.4 g (0.806 mole) of piperazine is added, over an hour, without exceeding the temperature of 20 ° C, 92.5 g (1 mole) of epichlorohydrin. The reaction mixture is kept stirring for another hour at 20 ° C, then at 60 ° C, 60 g (0.6 mol) of 40% sodium hydroxide is added over one hour.

Polymers KA IVb.

This polymer is obtained by cross-linking the polymer K I with the cross-linking agent R IVa as follows:

To 787.5 g of aqueous solution containing 157.5 g (0.92 amino equivalents; polyaminoamide KI is added at ambient temperature 268 g of aqueous solution containing 54.9 g of the crosslinking agent prepared as above. The temperature of the reaction mixture is maintained for 4 hours. 50 minutes at 90 DEG C. A gel formation is observed, by the rapid addition of 1100 ml of water a clear solution containing 9.85% of active material is obtained whose viscosity measured at 25 DEG C. is 73 centipoise.

Crosslinking agent R Va.

The quaternized crosslinking agent of the formula: cn3 / 25 Cl CH2-CHOH.CH2 - Nn_- CH2 - CHOH - CH2 - Cl, n = 4 + CH3SO4 n is prepared as follows:

To 330 g of aqueous solution containing 67.7 g (0.752 amino equivalents) of the cross-linking agent R IVa is added over an hour and without exceeding the temperature 30 ° C, 47.4 g (0.376 mol) of dimethyl sulfate. The reaction mixture is kept under stirring for an additional 2 hours at this temperature. * f i

Polymer KA Vb.

t.

This polymer is obtained by cross-linking the polymer K 1 with the cross-linking agent R Va as follows:

To 327.7 g of aqueous solution containing 65.5 g (0.383 amino-equivalents) of polyamino K is added at ambient temperature 155 g of aqueous solution containing 47.25 g of crosslinking agent prepared as above. After 4 hours of heating to 85 ° C, the reaction mixture gels.

5

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

10 Crosslinking agent · R Via.

This bis-azetidinium crosslinking agent of the formula:, 6 Λ '- \ i— \ Λ

15 ho- (N N - CH_ - CHOH - CEL - N N. / -OH

\ / h - \ _ / 2 2 \ _ / + V

Cl electric manufacture · as stated below: 20

To 50 g (0.212 mol) of 1,3-bis-piperazine-propanol-2, prepared by the addition of epichlorohydrin to piperazine according to Example 15 of French Publication No. 2,162,025, dissolved in 100 g of absolute alcohol is added between 0 and 5 C 43.5 g (0.47 mol) of epichlorohydrin.

The reaction mixture is left to stand for 24 hours at 0 ° C, after which the cross-linking agent is precipitated from the solution in a large ether excess. A white solid is isolated with a softening point near 120 ° C.

Polymer KA VIb.

This polymer is obtained by cross-linking the polymer K I with the cross-linking agent R Via as follows: 35 To 386 g of aqueous solution containing 77.2 g (0.452 amino equivalents) of polyaminoamide K I is added at ambient temperature 15.4 g (0.036 mol) of the cross-linking agent R Via. After 2 hours and 30 minutes heating to 90 ° C, the reaction mixture gels. With the rapid addition of 525 g of water, a clear solution with 10% active material is obtained. The viscosity measured at 25 ° C is 0.7 poise at 67.18 sec.

37 DK 168059 B1!

Crosslinking agent R Vila,

This crosslinking agent bis- (chloroacetyl) piperazine of the formula: / - \ 5 Cl CH 2 - CO - N N CO CH ~ Cl 2 \ _ / 2 is prepared by condensing 2 moles of chloroacetyl chloride with 1 mole of piperazine in the presence of sodium hydroxide or sodium amylate.

Polymer K Vllb.

This polymer is obtained by cross-linking the polymer KI with the cross-linking agent R Vila as follows: To 1000 g of aqueous solution containing 200 g (1,170 amino equivalents) of polyaminoamide KI is added at ambient temperature 24 g (0.1 mole) of bis- (chloroacetyl) piperazine, after which the temperature of the reaction mixture is brought to 90 ° C. After 30 minutes of heating, a gelation of the reaction mixture, 20, is observed

1216 g of water is rapidly added and heating is continued to 80 ° C over one hour. A clear solution of 10% active material is obtained, whose viscosity measured at 25 ° C is 0.29 poise at 88.41 sec. First

25 Crosslinking agent R Villa.

This cross-linking agent bis- (1,1-bromundecanoyl) piperazine of the formula: / -s

Br (CH2) 10CO N N CO (CH2) 10 Br 30 N- / is prepared by condensing 2 moles of bromundecanoyl bromide with 1 mole of piperazine in the presence of sodium hydroxide or sodium methylate.

Polymer KA VHIb.

35

This polymer is obtained by condensing the polymer K I with the crosslinking agent R Villa as follows:

To 113.3 g aqueous solution containing 56.7 g (0.33 amino equivalents) of polyaminoamide K I is added at ambient temperature 60 g of an isopropanol solution containing 10 g (0.017 mole) of bis- (1,1-bromunde = canoyl) piperazine. The reaction mixture is heated for 2 hours and 30 minutes under reflux of the solvent. The isopropanol is completely distilled off with the addition of water until an aqueous resin solution containing 10% active material is obtained. The solution is slightly opalescent and its viscosity measured at 25 ° C is Q, 052 poise at 87.93 sec.

Crosslinking agent R IXa.

This statistically oligomeric crosslinking agent of the formula: 10 r / - \ n

C1 CH2-CHOH-CH2-N-CH2-CHOH-CH2 - C1_3 is prepared by starting from epichlorohydrin, piperazine and sodium = 15 hydroxide in the molar ratio of 4/3/2.

To 1149 g of aqueous solution containing 172 g (2 moles) of piperazine is added over an hour to 246.7 g (2.66 moles) of epichlorohydrin, keeping the reaction mixture with stirring at 20 ° C.

20

After an additional hour of stirring at 20 ° C, 133 g (1.33 mol) of 40% sodium hydroxide solution is added at the same temperature and over an hour. A precipitate is observed during the neutralization.

638 g of water is added and heated for a few minutes to 50 ° C to give a clear solution.

Polymer KA IXb.

This polymer is prepared by cross-linking the polymer K I with the cross-linking agent R IXa as follows:

To 2000 g of aqueous solution containing 400 g (2.34 amino equivalents) of polyaminoamide K I, 584 g of aqueous solution containing 99.8 g of cross-linking agent R IXa is added, after which the reaction mixture is kept under stirring at 90 ° C for 5 hours. 2414 g of water is then added to obtain a clear solution containing 10% active material, the viscosity of which is measured at 25 ° C is 0.22 poise.

Crosslinking agent R Xa.

This statistically oligomeric crosslinking agent of the formula: 39 DK 168059 B1 / - \

Cl CH2-CHOH-CH2 - N N - CH2-COHO-CH2 - Cl N- / 25 is prepared by starting from epichlorohydrin, piperazine and sodium hydroxide in the molar ratio 3/2/1.

To 1221 g of aqueous solution containing 172 g (2 moles) of piperazine is added over an hour at 20 ° C 277.5 g (3 moles) of epichlorohydrin, keeping the reaction mixture stirred at 20 ° C. After an additional hour of stirring, at 20 ° C, 100 g (1 mole) of 40% aqueous sodium hydroxide solution is added.

By adding 727.5 g of water and after a few minutes heating 15 a clear solution is obtained.

Polymer KA Xb.

This polymer is obtained by cross-linking the polymer K I with the cross-linking-2® agent R Xa as follows:

To 2000 g of aqueous solution containing 400 g (2.34 amino equivalents) of polyaminoamide K I put 472 g of aqueous solution containing 83.8 g of the crosslinking agent prepared according to Example Xa.

25

The reaction mixture is stirred at 90 ° C and, after 4 hours of heating, a gelation of the solution is observed.

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

A clear solution is obtained whose viscosity measured at 25 ° C is 0.64 poise at 88.4 sec.

35

The crosslinking agents and polymers listed above are described in French Publication No. 2,368,508.

(10) The polyaminoamide derivatives, which are soluble in water, are obtained by condensing polvalkylene polyamines with polycarboxylic acids followed by an alkylation with bifunctional agents.

40 DK 168059 B1

The polyaminoamides which are particularly useful in the practice of the invention are compounds obtained by reaction of polyalkylene polyamines containing 2 primary amino groups, at least one secondary amino group and alkylene groups containing 2-4 carbon atoms with dicarboxylic acids 5 corresponding to the following formula: H00C - CHm - C00H m represents an integer from 4 to 8, or with a derivative of such acids. The molar ratio of these reagents is preferably between 4: 5 and 6: 5.

The polyamide obtained by this reaction is alkylated by bifunctional alkylating agents of the formula: 15 R1, R2 R1 R2 (9)

A - CH-j - N - B - N - CH- - A

Δ + + z _ _ (x + 1) Q_ 20 wherein x represents an integer between 0 and 7, A represents the group - CH - CH- or XCH - CH-

\ / 'Y

0 OH R

R 12 represents halogen, preferably chlorine or bromine, R and R represent an alkyl group or a lower hydroxyalkyl group containing 1-4 carbon atoms, B represents an alkylene group containing 2-6 carbon atoms, the group - CH-- CH - CH- - or - (CH-) + - NH - CO - NH - (CH-) t - zi μ ώ yy

OH

Wherein y is an integer from 1 to 4 and Q is halide, sulfate or methosulfate.

The most preferred polymers are those polymers in which A represents - CH - CH -,

V

R and R represent a lower alkyl group, preferably the methyl group, and x = 0.

The amount of bifunctional alkylating agent is such that polyaminoamide derivatives of increased molecular weight are formed but are soluble in water. Such polymers are described, inter alia, in French Patent Specification No. 1,583,363.

41 DK 168059 B1

The preferred polymers of this type are the copolymeric adipic acid'-dialkylaminohydroxyalkyl-dialkylenetriamines wherein the alkyl group contains 1-4 carbon atoms and is preferably the methyl group, ethyl group or propyl group.

5

The compounds / which enable to obtain particularly remarkable results / are the copolymers adipic acid-dimethylaminohydroxypropyl-diethylenetriamine / which under the name "Cartarétine", F, F4 or Fg are sold by the company SANDOZ.

10

These copolymers have a nitrogen content of 17.0 to 18.0 wt% and a viscosity measured in 30 wt% aqueous solution from 350 to 800 centipoises at 20 ° C (determined with a Brookfield viscometer using a spindle no. 3 at 30 p.m.).

(11) The polymers obtained by reacting a polyalkylene polyamine containing two primary amino groups and at least one secondary amino group with a dicarboxylic acid selected from diglycolic acid and saturated aliphatic carboxylic acids containing 3-8 carbon atoms. The molar ratio of the polyalkylene polyamine to the dicarboxylic acid is between 0.8: 1 and 1.4: 1, and the resulting polyamide is reacted with the epichlorohydrin in a molar ratio of the epichlorohydrin to the polyamide secondary amino group between 0.5: 1 and 1. 8: 1, cf.

3,227,615 and No. 2,961,347, 25

The most preferred polymers are those polymers which, under the designation "HERCOSETT" 57, are sold by the company Hercules Incorporated and have a viscosity at 25 ° C of 30 centipoise and are sold in 10% aqueous solution under the designation "PD 170" or "DELSETTE 101 "by Hercules in the case of the copolymer adipic acid: epoxypropylene diethylene = triamine.

(12) The polyalkylenamines selected from: 35

The polymerization products of ethyleneimine and of its homologues, which optionally carry substituents, which are generally obtained in the presence of acidic catalysts, as disclosed in U.S. Pat.

2182306. The polymerization catalyst may also be an oxidizing agent or a surfactant such as the ethylene oxide compounds. Among these polymers are the polymers of ethyleneimine, of propyl = ethylenimine, of butylenimine, of phenylethylenimine or of cyclohexyl = ethyleneimine, and the copolymers of alkyleneimines with acrylic acid and derivatives thereof in the presence of amines of increased molecular weight or in the presence of ethylene oxide . The polyalkyleneimines formed by the polymerization of alkyleneimines of the formula:

5 (10) R = N - (R - NH) H

n wherein R is an alkylene-1,2 group and n is an integer below 4 is obtained by simple heating or in aqueous medium in the presence of an acid as disclosed in United States Patent No. 2,553,696. Among these 10 polyalkyleneimines are those obtained by polymerization of the following alkyleneimines: C2H4 = NC2H4 - NH2 or N, N-ethylene-ethylenediamine, C2H4 = NC2H4 - NHC2H4-NH2 or N, N-ethylene diethylenetriamine, C2H4 = N ( C2H4NH) 2 "C2H4-NH2 or N, N-ethylene-triethylenetetramine, (CH3) C2H3 = NC2H3 (CH3) NH2 or (N, N1, 2-propylene) -1,2-propylenediamine, (CH3) C2H3 = NC2H3 ( CH3) NHC2H3 (CH3) NH2 or N, N- (1,2-propylene) di-1,2-propylenetriamine, (CH3) C2H3 = N [C2H3 (CH3) NH] 2 C2H3 (CH3) NH2, N, N - (1,2-propylene) tri-1,2-propylenetetramine, (CH 3) 2 C 2 H 2 = NCH (CH 3) CH (CH 3) NH 2, N, N- (2,3-butylene) -2,3-butylene = diamine.

25

The polyethylenimines prepared by the method of U.S. Pat. No. 2,806,839 by heating heterocyclic compounds, the ring of which comprises a ketone group and furthermore an oxygen atom and a nitrogen atom, each located in α position relative to the ketone group, such as, for example, the cyclic urethanes and the 2-oxazolidones optionally substituted by the nitrogen atom, the heating being conducted under reduced pressure with complete removal of CO 2 by ring opening followed by a polymerization.

The polymers obtained by condensing alkyleneimines, such as ethyleneimine, methylethylimine or N-phenylethylenimine, with sulfur compounds such as carbon disulfide, carbonyl sulfide, thiophosgene or sulfur chloride, as disclosed in U.S. Patent No. 2,208,095 *

It is also possible within the scope of the invention to use the partially alkylated derivatives of the above-mentioned polyethyleneimines whose degree of alkylation is between 10% and 50%. Polymers of this particular preferred type are polymers obtained by alkylation with octadecyl = bromide, octadecyl chloride, heptadecyl chloride, tetradecyl bromide, hexa = 5 decyl sulfate, dodecyl chloride or decyl bromide. Such polymers are described in French Patent Specification No. 2,039,151.

Other polymers of this type are alkoxylated derivatives of the above-defined polyethyleneimines prepared by reacting one part by weight of ethylene oxide or propylene oxide with one part by weight of polyethyleneimine, as described in French Patent No. 1,506,349.

Among the most preferred polyethyleneimines and their derivatives are the compounds sold under the terms: "PEI 6", "PEI 12", "PEI 18", "PEI 300", "PEI 600", "PEI 1200" , "PEI 1800", "PEI 600 E" which is a polyethyleneimine alkylated with ethylene = oxide in a ratio of 1: 0.75, and "TYDEX 14" and "TYDEX 16" having a density of approx. 1.06 and having a viscosity at 25 ° C of more than 1000 centipoise. 20 These polyethylenimines are sold by DOW CHEMICAL.

Other polyethyleneimines which may be used in accordance with the invention are those sold under the designation "POLYMIN P" having a density d20 of approx. 1.07, a Brookfield viscosity of 10,000-20,000 centipoise in 50% aqueous solution (at 10 ° C and 20 rpm), "POLYMIN SN" having a D 20 density of approx. 1.06 and a viscosity of 800-1800 centipoise at 20 ° C in aqueous solution, and "POLYMIN® HS" having a density d20 of approx. 1.07 and a viscosity of 500-1,000 centipoise in 20% aqueous solution sold by BASF.

It is also possible to use within the scope of the invention the reaction products of polyethyleneimine with ethyl formate described in French Patent Specification No. 2,167,801. , such as acrylamide or acrylamide, which is, for example, substituted with an alkyl group or an alkyl acrylate group, the pyridinium nitrogen being substituted by an alkyl chain having 1 to 12 carbon atoms and the pyridine or pyridinium nucleus being substituted by 0 to 3 alkyl groups.

For example: 5

Polyvinylpyridine, poly (1-butyl-4-vinylpyridinium bromide), the copolymer of 1-lauryl-4-vinylpyridinium urromide and 1-butyl-4-vinyl = pyridinium bromide, the copolymer of 1-lauryl-4-vinylpyridinium bromide and of 1-ethyl-4 -vinylpyridinium bromide, the copolymer of 2-vinylpyridine and 1-benzyl-2-methyl-5-vinylpyridinium = chloride, the copolymer of acrylamide and 1,2-dimethyl-5-vinylpyridinium methylsulfate, the copolymer of methacrylamide and 1-benzyl-2-vinylpyridine the copolymer of ethyl methacrylate and 1,2-dimethyl-5-vinylpyridinium = methyl sulfate, and the copolymer of ethyl acrylate and 2-methyl-5-vinylpyridine and 1,2-dimethyl-5-vinylpyridinium chloride.

(14) The cationic urea formaldehyde resins.

(15) Water-soluble polymers / condensates of polyamines and epichlorohydrin such as e.g. the condensate of tetraethylene pentamine and epichloro = hydrin.

(16) The vinylbenzylammonium homopolymers or copolymers, such as, for example, the vinylbenzylalkylammonium polychlorides / wherein the alkyl group is preferably the methyl group.

(17) The quaternary polyureylenes of the type disclosed in Belgian Patent Specification No. 77 3892,

According to a variant, in the compositions of the present invention, polymeric dyes may be used in conjunction with the aforementioned anionic polymers and optionally other cationic polymers. Such polymers include:

Polymeric dyes consisting of a mixture of water-soluble cationic polymers having a molecular weight of between 800 and ca. 100,000 and comprising secondary or tertiary amino groups or quaternary ammonium groups which, or in part, serve to directly or indirectly connect compounds bearing chromophores or chromogenic groups hereinafter referred to as "CPGCC", aryl or aliphatic aryl since they necessarily further comprise at least 10% aliphatic amino groups relative to the total number of chain amino groups, the main chain of which comprises amino groups which form part of the CPGCC.

The cationic polycondensates useful as hair conditioning agents, and in particular the cationic polymers used to prepare the above polymeric dyes, are described in particular in French Patent Nos. 72 42279, No. 74 27030, No. 74 39242, no. 75 15162, no. 76 20261 and the Luxembourg patents no.

73,794 and No. 73,795, and they are defined in the above groups 15 in relation to cationic polymers.

In the case of cationic polymers, which have been previously described as hair conditioning agents, certain of the polymer's amino groups are seeded by starting from a colored compound, a colorant 20, or a precursor to the colorant. However, in order to preserve the adsorption properties of the keratin-containing fibers, one must not substitute all the amino positions with the remaining CPGCC to prevent the affinity of the keratin fibers from disappearing. The CPGCCs grafted onto the polymer may be soluble in water since the solubility of the cationic polymeric dye of the invention is a function of the solubility of the corresponding polymer prior to grafting with the remainder of the CPGCC. In one embodiment, the polymers are linear or branched, but not cross-linked, while in another variant the polymer may be more easily cross-linked, but in this case the cross-linking is kept within narrow limits so as not to reduce the water solubility of the polymer too much. These above polymeric dyes are water soluble.

They can be used not only in aqueous solution but also in a water-solvent medium, with the solubility remaining when adding solvents such as ethanol, alkylene glycols, ether glycols or analogous compounds.

These polymeric dyes can be obtained according to three methods listed below.

In a first process, the polymeric dyes are obtained by reacting reactive colored compounds with cationic resins containing primary, secondary or tertiary alkylatable amino groups.

46 DK 168059 B1

In another method of preparation, the polymeric dyes are obtained by reacting colored compounds containing alkylable amino or phenol groups with cationic resins containing reactive groups.

5

In a third mode of preparation, the polymeric dyes are obtained by reacting a compound or mixture of the alkylatable amino compounds with other bifunctional derivatives whose functions can react with an amine, one of the two reacting compounds 10 being a CPGCC. These functions may be, for example, epoxide groups, halide groups or activated double bonds.

In the first of the above-mentioned methods of manufacture, cationic resins such as polyamines or polyaminoamides can be used, e.g. those described in the above paragraphs as well as in French Patent Nos. 72 42279, Nos. 74 27030 and 74 39242. Commercial resins such as the polyethylene imines may also be used. All of these resins contain primary, secondary or tertiary alkylatable amino groups which can react with the reactive CPGCC, especially CPGCC with loose chlorine or bromine atoms, epoxide groups or activated double bonds.

In a first variant to carry out the first process, the reactive starting molecules which act on the cationic resin contain one or more groups -NHCOCH 2 Cl. These molecules are preferably compounds obtained by chloroacetylation of dyes containing one or more aromatic amino functions substituted by an aminoalkyl group or bearing one or more amino = alkoxy substituents, only the amino functions outside the nucleus being chloroacetylated. These reactive chloroacetylated compounds may belong to various large categories of dyes and e.g. be nitrobenzene dyes, anthraquinone dyes, azo dyes, indamines, indoanalines, indophenols, 1,4-benzoquionone dyes, such as those disclosed in French Patent No. 73,22562 or French Patent No. 1,540,423. Among the nitrogen benzene dyes are reactive dyes obtained by chloroacetylation by starting from derivatives of ortho-, metha- and paranitroanilines such as 3-nitro-N-0-aminoethylamino-4-anisole, (3-nitro-6-amino) -phen = oxyethylamine, (3-nitro-4-amino) -phenoxyethylamine, or by chloroethylation by starting from derivatives of nitroparaphenylenediamine, such as N-O-1-aminoethylemino-3-nitro-N'-4-methylamino -benzene or N, NN, N-di-β-1-hydroxyethylamino-3-nitro-N'-3-4-aminoethylamine-4-benzene. Among the chloroacetylated anthraquinone dyes which may be used are mention of 3-1-chloroacetylaminoethylamino-anthraquinone obtained by chloroacetylation of 3-aminoethyl-1-amino-anthraquinone or 3-1-chloroacetylaminopropylamino-N-4-methylamino obtained by chloroacetylation of the corresponding compound described in British Patent No. 1,159,557 or 1-hydroxy-4-chloroacetyl = aminopropylamino-anthraquinone obtained by chloroacetylation of the compound disclosed in British Patent No. 1,227,825, or γ-chloro = acetylamino -propylamino-anthraquionone obtained by chloroacetylation of the compound described in Example 7 of British Patent Specification no.

1159557. In these examples, the chloroacetylation of the starting anthraquinone compounds is preferably carried out in dioxane in the presence of sodium carbonate, and in the case of the first three of the above anthraquinone compounds, all amino functions are chloroacetylated and a selective deacylation is carried out by sulfuric acid.

In the case of the fourth anthraquinone compound mentioned above, the amino group selectively is acetylated outside the ring. The useful chloroacetylated azo compounds are obtained by coupling the diazonium salts with N-ethyl-N-3-chloroacetylaminoethylaniline. For example, the 2t * azo compound of 2-amino-benzothiazole and N-ethyl-N-β-chloroacetyl = aminoethylaniline can be mentioned. Among the chloroacetylated derivatives of the indamines, indoanilines and indophenols are N - [[(ethyl-3-chloroacetyl = aminoethyl) -4-amino] -phenyl] -2,6-dimethyl-3-amino-benzoquiononeirane obtained by reaction of 4-nitroso-N-ethyl-N-3-chloroacetylaminoethyl = 25 aniline with 2,6-dimethyl-3-amino-phenol. One may also mention N- (4-amino-2,5-dimethyl) -2-phenylmethyl-5-amino-benzoquiononimine, which is obtained by reaction of 2,5-dimethyl-paraphenylenediamine with 2-methyl-5-chloroacetylaminophenol in ammonia medium in the presence of ammonium persulphate. Among the chloroacetylated 1,4-benzoquinone dyes one may mention N-3-2-hydroxyethylamino-5- (N-ethyl-N-3 "4-chloroacetyl = amino-anilino) -1,4-benzoquinone, which is obtained by reaction of 4-nitroso-N-ethyl-N-3-chloroacetylaminoethylaniline with 3 "3-hydroxyethylamino-4-methoxyphenol in ammonia medium in the presence of hydrogen peroxide. Among the chloroacetylated derivatives of the dyes disclosed in 35 French Patent No. 1,540,423 N- [3-Nitro-3-4-chloroacetyl = aminoethylamino) -phenyl] -N '- [(4'-nitro) -phenyl] -ethylenediamine, which is obtained by chloroacetylation of the compound described in Example 17 in French Patent Specification no. 1,540,423, or 1-methylaraino-Y - [(2'-nitro-N-ethyl-N-3-5-chloroacetylaminoethylamino) phenyl] -4-aminopropylamino-anthraquinone, which is obtained by chloroacetylation of the compound described in Example 19 of French Patent No. 1,540,423.

48 DK 168059 B1

The most preferred dyes according to the invention in the dyes obtained by reacting a polymer with the group fNH- (CH3) 2NH- (CH3) 2_NHCO (CH3) 4-COt, which is described in French patent 74 74242 , with the azo derivative of 2-amino-benzothiazole and of N-ethyl-N-O-chloroacetyl = 5 aminoethylaniline, hereinafter referred to as KCl, or with Y-chloro = acetylamino-2-propylamino-anthraquinone, hereinafter referred to as KC2.

In another variant of the method of carrying out the first process, 10man colored reactive starting molecules comprising either one or more aromatic amines substituted with α-haloalkyl groups, 3-chloro-2-hydroxy-propyl groups or 2.3 may be used. -epoxy-propyl groups, or haloalkoxy groups on an aromatic core. Among these compounds may be mentioned in particular, 1-3-chloroethylamino-3-nitro-N-4-methylamino-benzene, N-ethyl-Nf} -1-chloroethylamino-3-nitro-N '-4-methylamino-benzene, Ν -β-1-Bromethylamino-N '-3-dimethylamino-4-nitrobenzene, (3-nitro-4-amino) phenylbromethyl ether obtained by deacetylation of (3-nitro-4-acetylamino) phenylbromethyl ether as described in Example 13 in French Patent No. 74 36651, (3-chloro-3-hydroxy-propyl) -1-amino-anthra = quinone or (2,3-epoxy-propyl) -1-amino-anthraquionone.

In a third variant of the method of carrying out the first process, colored reactive compounds containing chlorotriazine groups may be used, such as the compounds known under the trade name 25 "Procion" sold by the company ICI, e.g. the compounds of the formulas listed in the Color Index under designations 13 245, 13 190, 18 105 and 18 159.

In a fourth variant of the method of carrying out the former method, colored reactive compounds with activated double bond can be used, such as the compounds known under the trade name "Remazol" sold by the company Hoechst, e.g. the vinyl sulfones of the dyes of the formulas listed in the Color Index under the designations 18 852 or 61 200.

35 In the second method, colored compounds having alkylable amino or phenol groups can advantageously be used without appreciable deterioration of the color, and in particular compounds which have been mentioned for the first and second variants of the way of carrying out the first process (in the case of about compounds before chloroacetylation or haloalkylation). As cationic resins containing reactive groups, reaction products of an epihalogen hydrine (epichlorohydric or epibromohydrin) with polyaminoamides obtained by polycondensation of a diacid and a polyamide of the type: HN- [CH0 CH0 NH] - H 2 2 2 n can advantageously be used. 5 in which formula n is 2 or 3.

Among the polyaminoamides of interest are especially those mentioned in French Patent No. 74 39242. When the epihalohydrin is used 10 in amounts ranging from approx. 0.8 / 1 to approx. 1.3 / 1 relative to basic groups, a resin is obtained which may contain azetinium aluminum, halohydric or epoxide groups, all of which alkylate amines or phenols and thus by covalent bonding allows fixation of colored compounds with amino or phenol function. The alkylating reactive groups in the resin which do not react with the colored compounds may be omitted by reaction with a nucleophilic compound such as an amine or mercaptan, or may be retained for further enhancement of the polymeric dye fixation to the substrate to be stained.

In the third process for the preparation of the compounds, colored compounds of type Z-NI 2 can be used as dialkylable derivatives in the polycondensation reactions with bis-halogenated derivatives, bis-epoxides or bis-unsaturated compounds with activated double bonds. In this case, in addition to the colored compounds Z-NH 2, an additional bis-secondary amino derivative, e.g. piperazine to increase the solubility of the obtained compound in water as well as its affinity for the keratin-containing fibers. It is also possible to use bis-haloalkane derivatives or bis-halohydrin derivatives of 30-colored compounds together with secondary or tertiary bis-amines (this type of reaction is described in French Patent No. 75 15161).

Among the bifunctional derivatives which can be used for reaction with the amino compounds, in particular, the piperazine derivatives such as N, N'-35bis (3-chloro-2-hydroxy-propyl) -piperazine, Ν, Ν'-bis (2,3- epoxy-propyl) -piperazine, bis-acryloylpiperazine, diglycidyl ether or the bis-acrylamide of ethylenediamine, and, colored bis-amino derivatives may also be used together with bifunctional derivatives such as those mentioned below, or also colored bis-halogen derivatives together with bis secondary amines.

In the case of the first and second of the above processes, the preparation reactions for the reactive halogen derivatives or epoxy derivatives are generally carried out in a solvent medium, optionally in the presence of water, and at temperatures between 0 ° C and 100 ° C, preferably between 30 ° C. ° C and 70 ° C. In particular, useful solvents include the lower alcohols such as methanol, ethanol, isopropanol and t-butanol, alkoxyethanols, aromatic solvents such as benzene or toluene, or other solvents such as dimethylformamide or azetonitrile. The reaction of the reactive colored compounds with cationic resins is most often carried out in the presence of solvents such as those mentioned above and at temperatures between 30 ° C and 130 ° C, preferably between 50 ° C and 90 ° C. The reaction time is generally between ca. 1 hour and approx. 10 hours. The reactions can be carried out with cationic resins which are linear or cross-linked, but it is also possible to cross-link the cationic resin with bifunctional derivatives after grafting the colored compound. The colored resins are then precipitated in a non-solvent such as acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl ether or hydrocarbons such as hexane or heptane. In view of the reactivity of the colored compounds which are further present in the presence of a significant excess of reactive sites on the resins, and considering the possibility of precipitation of the dyeing compounds, it is generally relatively convenient to purify the dye compounds obtained and in particular to remove the dyes or dye precursors that may not be condensed on the resin. When the dye compounds cannot be precipitated, the product obtained can be purified by dialysis after dissolving in water. In the case of reacting colored compounds containing amino or phenol groups with reactive resins, the reactions are carried out in solvent or in water. When one wishes to preserve the reactive resins, these resins are acidified, e.g. with hydrochloric acid, 30 before being isolated. On the other hand, if one does not wish to preserve the reactive resins, a nucleophilic resin such as an amine or mercaptan is added to utilize the usable reactive sites.

The reactions of the third process are carried out in water, in solvents or in mixtures of water and solvents. These reactions are carried out at temperatures between 50 ° C and 150 ° C, preferably between 80 ° C and 130 ° C. The reaction times are between approx. 1 hour and approx. 10 hours. These polymeric dyes are described in more detail in French Publication No. 2,361,447.

Among the anionic polymers which can be used in the composition of the invention are the polymeric sulfonic acid derivatives and carboxylic acid derivatives.

Among the polymeric sulfonic acid derivatives are mentioned: 5

The salts of polystyrene sulfonic acid such as the sodium salts sold under the designation "Flexan" 500 and having a molecular weight of approx. 500,000, or sold under the designation "Flexan" 130 and having a molecular weight of approx.

100,000 (National Starch company). Such compounds are particularly described in French Patent Specification No. 2,198,729,

Alkali metal or alkaline earth metal salts of sulfonic acids derived from lignin, especially calcium or sodium lignosulfates, such as the product sold under the name "Marasperse" C 21 by American Can Co., and the compounds of 10-14 carbon atoms sold by Avébéne.

Among the polymeric carboxylic acid derivatives are mentioned: 20 1. The bipolar acids, such as the copolymers of vinyl acetate and crotonic acid, such as the resin sold under the designation 26.13.14 or 28/13/10 by National Starch.

2. The grafted polymers prepared as described in French Patent No. 1,222,944 by starting from polymerizable compounds (such as vinyl esters, acrylic acid esters or methacrylic acid esters, either alone or in admixture, and copolymerized with other compounds (such as protonic acid, acrylic acid or methacrylic acid) to prepare polyalkylene oxides, polyalkylene glycols or appropriate derivatives of these compounds.

The polymers grafted with vinyl esters, acrylic acid esters or methacrylic acid esters, either alone or in admixture with compounds which can be copolymerized to polyalkylene glycols, are obtained by polymerization in the heat and homogeneous phase with introduction of polyalkylene glycols into the monomeric vinyl esters or acrylic acid esters presence of radical activators.

Suitable vinyl esters may be mentioned: Vinyl acetate, vinyl propionate, vinyl * butyrate and vinyl benzoate, and as esters of acrylic acid or methacrylic acid can be mentioned the esters obtained with low molecular weight aliphatic alcohols containing 1-8 carbon atoms.

52 DK 168059 B1

Particularly mentioned as polyalkylene glycols are the polyethylene glycols having a molecular weight of 100 to several million, preferably between 1Q00 and 30,000.

In particular, mention may be made of vinyl acetate polymers grafted onto polyethylene glycols and vinyl acetate protonic acid polymers grafted onto polyethylene glycols.

The polymers grafted with vinyl esters, acrylic acid esters or methacrylic acid esters to prepare derivatives of polyalkylene gly = 10 cols whose terminated hydroxyl groups are etherified or esterified at two ends by mono- or polyfunctional compounds such as methanol, butanol, acetic acid, propionic acid or propionic acid butyric acid.

Grafted polymers of vinyl esters, acrylic acid esters or methacrylic acid esters on nitrogen oxides of polyalkylene glycol.

3. Grafted and crosslinked copolymers formed by copolymerization: a) Of at least one nonionic monomer, 20 b) at least one ionic monomer, c) polyethylene glycol, and d) a crosslinking agent, preferably from the group comprising ethylene = glycol dimethacrylate, diallyl phthalate, the divinylbenzenes , tetraallyloxy = ethane and polyallylsucroses with 2-5 ally 1 groups per sucrose molecule.

The polyethylene glycol used has a molecular weight between 200 and more 30 million, preferably between 300 and 30,000.

The nonionic monomers can be of a very varied type, and among these may be mentioned especially vinyl acetate, vinyl stearate, vinyl laurate, vinyl prop ionate, allyl stearate, allyl laurate, diethyl maleate, allyl acetate, methyl methacrylate, cetyl vinyl ether, stearyl vinyl ether.

The nonionic monomers can also be of a very varied type, and among these may be mentioned particularly protonic acid, allyloxyacetic acid, vinylacetic acid, maleic acid, acrylic acid and methacrylic acid.

The grafted and crosslinked copolymers which can be used in the compositions of the invention preferably consist of: a) 5-85% by weight of at least one non-ionic monomer, b) 3-80% by weight of at least one ionic monomer, c) 2-50 wt., preferably 5-30 wt. polyethylene glycol, and d) 0.1-8 wt. of a crosslinking agent, the percentage of the crosslinking agent being calculated in relation to the total weight of a) + b) + c).

The grafted and cross-linked copolymers thus defined generally have a molecular weight between 10,000 and 1,000,000, preferably between 15,000 and 500,000.

When the grafted and crosslinked copolymers contain free carboxylic acid functions, these can be neutralized by a base in an amount between 50 and 1001 of the amount corresponding to a stoichiometric neutralization such as an organic or inorganic base, e.g. ammonia, mono = ethanolamine, diethanolamine, triethanolamine, the isopropylamines, isopropanolaniline, morpholine, 2-amino-2-methyl-1-propanol, 2-amino-2-methyl-20, 1,3-propanediol, etc.

Such copolymers are described in the specification for German Patent Application No. 2,330,956.

The copolymers obtained by copolymerizing at least one monomer from each of the following three groups:

The first group comprises the esters of unsaturated alcohols and saturated short chain carboxylic acids, the esters of saturated alcohols of short chain and unsaturated acids, the carbon chains of these compounds being optionally interrupted by heteroatoms or divalent hetero groups such as -O-, -S- and -NH- and may further contain hydroxy groups which are substituted in the O position relative to the heteroatom, the other group comprises unsaturated acids, the carbon chains of which may be optionally interrupted by heteroatoms or divalent heterogroups such as -O-, -S- and -NH-, and may contain hydroxy groups substituted in the O position relative to the heteroatom, such as 3-butenoic acid, 4-pentenoic acid, 10-undecenoic acid, allylmalonic acid, crotonic acid, allyloxyacetic acid, crotyloxyacetic acid, with thal lyloxyacetic acid, -allyloxypropionic acid, allylthioacetic acid, allylaminoacetic acid and vinyloxyacetic acid, and the third group comprises long chain esters and unsaturated alcohols clays, esters of unsaturated acids of the second group and an alcohol which is saturated or unsaturated, linear or branched and containing 8-18 carbon atoms, or a lanolin alcohol, alkyl vinyl ethers, alkylallyl = 5 ethers, alkylmethallyl ethers or alkylcrotyl ethers, and the α-olefins, especially described in French Patent Specification No. 1,580,545.

5. The terpolymers obtained by copolymerization of: 10 a) crontonic acid, b) vinyl acetate, and c) an allylic ester or methallyl ester of the following formula: R1 R2-CC-O-CH9-C = CH- (11) IO II “I * CH OR 'wherein R' represents a hydrogen atom or the methyl group, 20 represents a saturated, linear or branched hydrocarbon chain containing 1-6 carbon atoms and R represents either the group -CH., Or the group -HC (CH,) -, 12 J Δ wherein R + R must contain a number of carbon atoms less than or equal to 7.

25

In particular, the above terpolymers are obtained by copolymerization of 6-15% and preferably 7-12% crotonic acid, 65-86% and preferably 71-83% vinyl = acetate and 8-20% and preferably 10-17% allyl ester or methallyl = ester with formula (11).

Preferably, the terpolymers of the invention have a molecular weight between 15,000 and 30,000.

In a particular embodiment, the copolymers of the invention are cross-linked by a cross-linking agent such as diethylene glycoldiallyl = 35 ether, tetraallyloxyethane, the triallylet ether of trimethylolpropane, and the diacrylates or dimethacrylates of diols such as ethylene glycol, the amount of weight being between 0.1 and 1.2%. .

According to the invention, it is also possible to use the terpolymers described above, which have undergone salt formation by their acidic function by means of an organic base of the kind mentioned in the above paragraph 55 DK 168059 B1 3.

Such terpolymers are particularly described in French Publication No. 2,265,781.

6. The tetra- and pentapolymers containing the copolymers formed by the copolymerization of: 10 a) an unsaturated acid selected from crotonic acid and allyloxyacetic acid; b) vinyl acetate or vinyl propionate; c) at least one branched allyl ester or methalyl ester of the formula defined above ( 11), d) a monomer of the group comprising: 3 (i) a vinyl ether of the formula: CH 2 = CH - O - R (12) wherein R 3 is a linear or branched alkyl group containing 1-12 carbon atoms and preferably is the methyl group, the ethyl group , isopropyl group, t.-butyl group, octyl group or dodecyl group, and (ii) a fat chain vinyl ester of the formula: R 1 - C - O - CH = CH ~ (13)

Wherein R is a linear alkyl group of 7-11 carbon atoms, preferably the octyl group, decyl group or dodecyl group, and (iii) a linear allyl ester or methalyllyl ester of the formula: R5 - C - O - CH- - C = CH_ (14 ) Wherein R 'is a hydrogen atom or the methyl group and R is a linear alkyl group containing 1 to 11 carbon atoms, preferably the methyl group, heptyl group, nonyl group or undecyl group.

In particular, the above copolymers are obtained by copolymerization of 2-15% and preferably 4-12% of the unsaturated acid, 55-89.5% and preferably 65-85% of the vinyl ester, 8-20% and preferably 10-17% of at least one allyl ester or methallyl ester of formula (11) and 0.5-10% and preferably 1-6% of a monomer of the group comprising a vinyl ether of formula (12), a vinyl ester of formula (13) and an allyl ester or metal thal ly with the formula (14).

In a particular embodiment, these copolymers are crosslinked by means of a crosslinking agent mentioned above in an amount between 0.1 and 1.2% by weight.

It is also possible to use the copolymers described above, which have been subjected to salt formation by their acidic function by means of an organic base, such as one of the ones defined under point 3.

Such polymers are described in particular in French Publication No. 2,265,781.

7. The terpolymers, tetrapolymers, pentapolymers and higher polymers selected from the copolymers obtained by copolymerization of: 20 Type A. (a) At least one water-insoluble monomer of the formula: R1 R2 CH = C - C - NH - C - (CH-) - CH, (15) 2 "2 n 3

0 R

Wherein R, R and R are either a hydrogen atom or a methyl group and n is 0 or an integer from 1-10, preferably N-tert-butylacrylamide, N-octylacrylamide, N-decylacrylamide, N -dodecylacrylamide, N - [(1,1-dimethyl) -1-propyl] acrylamide, N- [(1,1-dimethyl) -1-butyl] acrylamide and N- [(1,1-dimethyl) -1- pentyl] acrylamide and the corresponding methacrylamides, (b) at least one water-soluble monomer of the formula: R 1 R 4 - CH = C - (CH 2) - CON - Z - OH (16) »c 2 m

35 R

wherein R * represents a hydrogen atom or a methyl group, z represents a linear or branched alkyl group of 1-6 carbon atoms optionally substituted by one or two hydroxymethyl groups, m = 0 or 1, R4 represents H or or CO-R®, R is OH or -NH-R 4, R 5 is 4

represents H or -Z-OH, R represents H or -CH ,, when m = 0, and R

represents H and R CO-R when m = 1, especially mono-, bis- or trihydroxy-alkyl acrylamide or methacrylamide, the alkyl group being a linear or branched group containing 1-6 carbon atoms such as the methyl group , the ethyl group, propyl group, butyl group, 1,1-dimethylbutyl group or propyl group, N-mono- or di-hydroxy-alkylmaleic acid, N-mono- or di-hydroxy-alkylitaconic acid and the corresponding amides, with alkyl preferably meaning methyl, and (c) at least one additional monomer selected from acrylic acid, methacrylic acid, maleic anhydride, N-vinylpyrrolidone and the acrylates and methacrylates of the formula: CH2 = C - COO - (CH2 - CH2 - O) R '15 wherein R' represents a hydrogen atom or a methyl group, £ is 3 or 4 and R "is a methyl group or ethyl group, among which may be mentioned the acrylates and methacrylates of ω-methyl or ethyl polyethylene = glycol.

20

According to another embodiment, the copolymers of the invention are tetra, penta or higher polymers obtained by copolymerizing more than one polymer of formula (15) and / or more than one monomer of formula (16) and / or more than one monomer of the invention. the above third group (c).

According to a further embodiment of the invention, the copolymers are obtained by copolymerizing a monomer of formula (15), a monomer of formula (16), a monomer of the group (c) and at least one additional mo-3Q moiety of the group comprising: styrene, a monomer with one of the following formulas (18) - (22): 1) CH- = C - CN (18) R8 g wherein R represents a hydrogen atom or a methyl group, preferably acrylonitrile and methacrylonitrile, 2) CH, = C - C - OR10 (19) Å 'o »R3 0 58 DK 168059 B1 9 10

wherein R represents a hydrogen atom or a methyl group and R represents a linear or branched alkyl group of 1-18 carbon atoms, the group - (CH 2) 2 N (CH 2) 2 or the group -CH 2 -CH 2 OH, or -CH 2 -CH-CH 2 OH

OH

Preferably methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, hexyl, decyl, dodecyl, octadecyl, 2-hydroxyethyl and N, N-dimethyl-2-amino ethyl acrylate and methacrylate.

3) R 11 - C - O - CH = CH, (20) wherein R 1 represents a linear or branched alkyl group of 1-16 carbon atoms or a phenyl group, preferably the acetate, propionate, butyrate, laurate, stearate, pivalate, the neoheptanoate, neooctanoate, neodecanoate, 2,2,4,4-tetramethyl valerate, 2-isopropyl-2,3 = dimethylbutyrate and vinyl benzoate.

4) R 12 - CH = C - (CH 2) - COOR '(21) '13 ZSR · 1 "5 wherein R' is an alkyl group of 1-3 carbon atoms and s is 0 or 1, preferably the dimethyl or diethyl maleate. , or the dimethyl or diethylitaconate.

5) CH 2 = CH - O - R 14 (22) 14 wherein R is a saturated, linear or branched alkyl group having 1 to 17 carbon atoms, preferably the methyl, butyl, isopropyl, octyl, dead = cyl and octadecylvinyl ether.

According to a third preferred process, these copolymers may also be tetrapolymers or pentapolymers or higher copolymers obtained by copolymerization of more than one monomer of formula (15) and (16) as well as more than one monomer of the group (c) in the presence of styrene or another monomer such as the monomers of the above formulas (18) - (22).

Type B: The polymers of this type are obtained by copolymerizing a) at least one monomer of formula (15) b) at least one monomer of formula (23) B1 R15 - CH = C - (CH.) - CONH- (23 ) µβ 2 P 2

wherein P is O or 1, R1 is H or COOH and R1 is H

15 IS

5 or CH 2 when p = 0, or R represents H and R COOH when p = 1, and among monomers of formula (23), in particular, acrylamide, methacrylamide, maleic and itaconic acid may be mentioned, and c) at least one monomer selected from maleic anhydride and the monomers 10 of formulas (16) and (17).

According to another variant, the copolymers of type B are obtained by copolymerization of a monomer 15, a monomer 23, a monomer group c) and a monomer selected from styrene, N-vinylpyrrolidone and the monomers of formulas 18, 19, 20 and 22 and Formula 24: CH - COOR17 (24)

II

CH - COOR17 20 17 wherein R represents an alkyl group of 1-3 carbon atoms.

These copolymers preferably have a molecular weight between 1,000 and 500,000, preferably a molecular weight between 2,000 and 200,000.

In a particular embodiment, these copolymers are crosslinked with a crosslinking agent of the type defined in point 3 in an amount between 0.01 and 2% by weight relative to the total weight of monomers reacted.

30

As stated above, the free carboxylic acid groups can be neutralized with at least one organic base such as that described in point 3.

The neutralization is generally carried out in a molar ratio of between 10 and 150%. 35

These copolymers can be prepared by copolymerization dissolved in an organic solvent such as alcohols, esters, ketones or hydrocarbons.

Among these solvents are especially methanol, isopropanol, ethanol, ethyl acetate, methyl ethyl ketone, benzene, etc.

60 DK 168059 B1

The copolymerization may also take place in suspension or in emulsion in an inert solvent / such as water.

The copolymerization may also take place as bulk polymerization.

5

The polymerizations may be carried out in the presence of a free radical-forming polymerization catalyst such as benzoyl peroxide, lauryl peroxide, azo-isobutyronitrile, hydrogen peroxide, oxidoreduction coupling agents such as (NH

10

The catalyst concentration varies between 0.2% and 10% by weight relative to monomers marketed and in function of the molecular weight of the copolymers desired to be obtained.

Such polymers are described in the specification of the Luxembourg patent applications 7575 and 75371.

The water-soluble non-crosslinked polymers of acrylic acid or methacrylic acid, of crotonic acid and the copolymers thereof with a monoethylenically unsaturated monomer such as ethylene, vinylbenzene, vinyl acetate, vinyl methyl ether and acrylamide and water-soluble salts thereof.

9. The terpolymers of vinyl acetate, crontonic acid and the vinyl ester of a saturated aliphatic monocarboxylic acid branched at the α-position and having at least 5 carbon atoms in the carboxyl group.

These branched esters are especially derived from an acid of the formula: R1

30 R3 - C - C - OH

122 12 3 wherein R and R are an alkyl group and R represents hydrogen, an alkyl group, an alkylaryl group, an aralkyl group or an aryl group.

Such polymers are described in French Patent Specification No. 1,564,110.

Among these are the polymer, which under the designation "28-29-30" is sold by the company National Starch.

The tetrapolymers of the type disclosed in French Patent Specification 61 DK 168059 B1 No. 2062,801 and comprising 70-80% N-t-butylacrylamide or N-isopropylacrylamide, ca. 5-15% acrylamide or methacrylamide, approx.

5-15% N-vinylpyrrolidone and approx. 1-10% acrylic or methacrylic acid, the weight percentages being calculated relative to the total weight of the material. A particularly preferred polymer is that sold under the designation "Quadramer 5" by the company American Cyanamid, which is composed of N-t.-butylacrylamide-acrylamide-acrylic acid and N-vinylpyrrolidone.

11. An acrylic acid homopolymer crosslinked by a polyfunctional agent such as the products sold under the designation "Carboppl®" 934, 934p, 940, 941, 960 and 961 by Goodrich Chemicals.

12. The copolymers of acrylic acid or methacrylic acid, optionally in admixture with the homopolymers of the above type, such as the products sold under the designation "Versicol" E or K by the company Allied Colloid, "Ultrahold®" 8 sold by the company Ciba Geigy, and the copolymers of (S) the sodium salt of acrylic acid and acrylamide sold under the designation "Reten ^" 421, 423 and 425 by Hercules.

13. The polymers with optionally monoesterified ethylene-α, β-dicarboxyl group. The copolymers are obtained by copolymerizing a compound which can be copolymerized and containing the group ^ C = C ^, having a compound of the formula: 25 r1 C - c '

'/ Y

C - C '12

30 R

Wherein R and R are independently hydrogen, halogen, a sulfonic acid group, an alkyl group, an aryl group or an aralkyl group, and X and Y represent OH, O-alkyl, O-aryl or halogen, or wherein X and Y collectively, O.

As compounds of this type, e.g. use ethylene-α, β-dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid, phenylmaleic acid of the formula:? 6H5

C - COOH HC - COOH

62 DK 168059 B1 benzylmaleic acid, dibenzylmaleic acid and ethylmaleic acid or an anhydride of these acids, such as maleic anhydride, and other derivatives such as the esters or acid chlorides.

5 As compounds which can be polymerized and contain the group ^; C = CH 2, for example, can be mentioned the vinyl esters, vinyl ethers, vinyl halides, phenyl vinyl derivatives such as styrene, acrylic acid and the esters thereof, and the esters of amino acid etc ..

These polymers are described in U.S. Patent No. 2,047,398.

These copolymers may optionally be esterified. Particularly preferred compounds are mentioned in United States Patent Specifications No. 2,723,248 and U.S. Patent Specification No. 2,102,113, wherein the following groups occur:

R

H 0 -CH-CH-C-C- 70 i. »I

at C = 0 C = 0 Η H

where R represents an alkyl group of 1-4 carbon atoms, e.g. methylgrup-

OC

pen, the ethyl group, the propyl group, the isopropyl group, the butyl group and the isobutyl group, R * represents an alkyl group having 1-8 carbon atoms, e.g. methyl, ethyl, propyl, butyl, isobutyl, pentyl, hexyl, heptyl, octyl, isooctyl etc ..

Other polymers of this type which can be used in the compositions of the invention are copolymers of maleic anhydride and an olefin containing 2-4 carbon atoms partially esterified (50-70%) with an alcohol containing 1-4 carbon atoms, as described in English Patent No. 839,905.

35

The copolymers are obtained by copolymerization of: a) An unsaturated anhydride, such as maleic anhydride, citric acid anhydride or itaconic anhydride.

b) An allyl ester or methyl ester such as the acetate, propionate, butyrate, hexanoate, octanoate, dodecanoate, octodecanoate, pivalate, neo-heptanoate, neooctanoate, neodecanoate, 2-ethylhexanoate, 2,2,4,4-tetramethyl valerate. the isopropyl-2,3-dimethyl-allyl or methallyl butyrate. The anhydride functions are either monoesterified by an aliphatic alcohol such as methanol, ethanol, propanol, isopropanol and n-butanol, or amidified by an aliphatic, cyclic or heterocyclic amine such as propylamine, isopropylamine, butylamine, dibutylamine, hexylamine. , dodecylamine, morpholine, piperidine, pyrrolidine and N-methylpiperazine, as well as the terpolymers are obtained by copolymerizing the monomers listed under points a) 10 and b) with an acrylamide or methacrylamide such as N-tert-butylacrylamide, N -octylacrylamide, N-decylacrylamide, N-dead = cylacrylamide, N- [(1,1-dimethyl) -1-propyl] acrylamide, N- [(1,1-dimethyl) -1-butyl] acrylamide, N - [(1,1-dimethyl) -1-pentyl] acrylamide, as well as the corresponding methacrylamides, the anhydride groups being esterified or amidified as indicated above. Optionally, the copolymer may be further copolymerized with α-olefins such as propylene-1, butene-1, hexene-1, dodecene-1, hexadecene-1, and octadecene-1, vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, isopropyl vinyl ether. , butyl vinyl ether, hexyl vinyl ether, dodecyl vinyl ether, hexadecyl = 2 ° vinyl ethyl and octadecyl vinyl ether, acrylic or methacrylates such as methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, hexyl, octyl, decyl, dodecyl, octadecyl, N, N-dimethylamino-2-ethyl, 2,3-dihydroxypropyl and ω-methyl or ethyl polyethylene glycol acrylate and methacrylate, and optionally acrylic acid or methacrylic acid or N-vinyl pyrrolidone to the terpolymers. Such polymers are disclosed in French Publication Nos. 2,350,834 and 2,357,241.

Also mentioned are polymers derived from maleic acid, maleic anhydride, itaconic acid or itaconic anhydride as mentioned above, and their copolymers with a monoethylenically unsaturated monomer such as ethylene, vinylbenzene, vinyl acetate, vinyl methyl ether and optionally hydrolyzed acrylamide.

Among these polymers are the particularly preferred products sold under the designations "Gantez" AN 119, 139, 149 and 169 which are copolymers of maleic anhydride and methyl vinyl ether (1: 1), as well as "Gantez" ES 225, 335, 425 and 435, which are the monoethyl ester, monoisopropyl ester and monobutyl ester of poly (methyl vinyl ether maleic acid) sold by General Anilin, and "EMA 1325" sold by Monsato and n-butyl (poly ) ethylenmaleat.

64 DK 168059 B1

Other anionic polymers which may be used in the compositions of the invention are: 14. The polyacrylamides containing carboxylate groups such as the product sold under the designation "Cyanamer® 'A 370 by the company American 5 Cyanamide.

15. The copolymers of acrylic acid or methacrylic acid in the form of their alkali salts, such as sodium and vinyl alcohol, such as the product sold under the name "Hydagen®F" by Henkel.

16. The copolymers of vinyl acetate / crotonic acid with acrylic esters or methacrylic esters or an alkyl vinyl ether, as described in French Patent No. 1,472,926.

17. The copolymers of vinyl acetate / crotonic acid and at least one additional monomer selected from long carbon chain vinyl, allyl and methallyl esters as described in French Patent No. 1,517,743.

18. The copolymers consisting of 40-90% vinylpyrrolidone, 40-50% of a 20 vinyl ester monomer and 20-30% of an unsaturated carboxylic acid, as disclosed in French Patent No. 2,042,522.

19. The colored polymers based on maleic anhydride, as described in particular in French Patent Nos. 1,498,464 and Nos.

25 1,517,862.

Among the anionic polymers derived from a carboxylic acid, firstly, the derivatives of crotonic acid, in particular the polymers containing at least one monomer other than vinyl acetate, and the grafted and optionally crosslinked polymers, and secondly, the derivatives of acrylic acid, are preferred. methacrylic acid.

Another class of anionic polymers which gives particularly advantageous results include the polymers listed under point 13.

35

According to a variant of the invention, it is possible in certain cases to fix the anionic polymer on the hair during immediate formation of a complex with the cationic polymer. In this way, it is possible to use either complexes that are formed at the time of mixing, or complexes that are already made and possibly sold in this form.

65 DK 168059 B1

By way of example, the complexes are also called polysalts, which are obtained by complexing one of the cationic polymers with any of the aforementioned anionic polymers. Preferred complexes are those obtained by complexing in stoichiometric amounts of a highly cationic polymer, such as the cyclopolymers or quaternary polymers mentioned in paragraph 2, and of an anionic polymer of the type mentioned above.

Particularly preferred complexes are those obtained by complexing 10 cationic monomers with the groups G 2, G 2 t G g, G 2, G 2, G g, G g, G g,

Gg or G ^q or the group:

C0Hc CEL

12 b, o i5 --- <CH2> 3 -? «- <CV6 - G11 c2h5 _ ch3 _ Br- Br - - c4h9 CH3 20 - N + - (CH2> 3-N + - <CH2) 4-- ^ G12 c4h9 cb3

Br "Br - with anionic polymers such as the salts of polystyrene sulfonic acids, such as the products sold under the above designation" Flexan ", the polymers derived from crotonic acid such as the terpolymer of crotonic acid / vinyl acetate and polyethylene glycol listed under 2, the terpolymers of vinyl acetate and crotonic acid vinyl ester listed under item 8, such as the polymer designated "28-29-30", and the sodium salt of carboxymethyl cellulose.

30

Other complex polysalts which may be used in accordance with the invention are described in French Patent Nos. 2,251,843 and 2,198,976.

The prefabricated complexes are used for the purpose of the invention 35 to be dissolved by a surfactant such as that set forth below.

The present invention also aims to provide the combination of cationic polymers and anionic polymers with a nonionic or amphoteric polymer.

66 DK 168059 B1

In particular, among the amphoteric polymers are the polymers formed by the alkylation of cross-linked polyaminoamides mentioned under points 3 and 9 of the description of the cationic polymers, the alkylating agent being acrylic acid, chloroacetic acid, an alkane sulton such as propane = 5 sultone or butane sultone. As an example, the polymer K IX formed by alkylation of sodium chloroacetate of the polymer K 1a and K X is obtained by alkylation of the propane sultone of the polymer K 1a.

The compositions of the invention are prepared by following the usual methods used in this field to obtain a mixture comprising at least one cationic polymer and at least one anionic polymer in aqueous medium.

In particular, before mixing, neutralization of the polymers which are poorly soluble in aqueous medium can be neutralized to obtain the combination of the present invention.

As mentioned above, in certain cases, when the combination of the invention leads to a precipitate, it will be necessary to add a solubilizing agent, preferably selected from the surfactants and the cosmetically acceptable solvents.

An embodiment of the present invention further aims to provide a cosmetic agent which is characterized in that it contains at least one cationic polymer, at least one anionic polymer as defined above, and at least one solubilizing agent.

The solubilizers used according to the invention may be anionic, 5 ° cationic, nonionic or amphoteric surfactants used either alone or in admixture.

In particular, among the anionic surfactants are the following compounds and mixtures thereof: the alkali salts, the magnesium salts, the ammonium salts, the amine salts or the amino alcohol salts of the following compounds:

Alkyl sulphates and alkyl ether sulphates whose alkyl group is a linear chain containing 12-18 carbon atoms, alkyl amide sulphates and ether sulphates with linear chains containing 12-18 carbon atoms, alkylaryl = polyether sulphates, monoglyceride sulphates, alkyl sulphonates whose alkyl = group is a linear chain containing 12-18 carbon atoms, alkylaryl = «7 DK 168059 B1 sulphonates, α-olefin sulphonates with linear chains containing 12-18 carbon atoms, secondary n-alkanesulphonates, mono- or di-alkyl sulphosfosuccinates, alkyl ether sulphosuccinates, alkylamide sulphosuccinates whose alkyl group consists of a linear chain consisting of a linear chain 12-18 carbon atoms, alkylsulfo succinamates whose alkyl group has a linear chain containing 12-18 carbon atoms, alkylsulfoacetates whose alkyl group contains a linear chain of 12-18 carbon atoms, alkyl polyglycerol carboxylates, alkylphosphates, alkyl ether phosphates whose alkyl group has a chain of 12-18 carbon atoms, alkyl sarcosinates, alkyl polypeptidates, alkylamide polypeptidates, alkylisethionates, alkyltaurates whose alkyl group has a chain of 12-18 carbon atoms, fatty acids such as oleic, castoric, palmitic, stearic, capric, lauric, myristic, arachic, behenic, isostearic, isostea coconut oleic acid, carboxylic acids of polyglycol ethers of the formula:

Alk - (OCEL - CHn). OCEL - CO_H 2 2 n 2 2 wherein the substituent Alk has a linear chain containing 12-18 carbon atoms and where n is a whole from 5 to 15, which compounds are in the form of the free acid or in the form of their salts as stated above.

Particularly preferred surfactants are sodium lauryl sulfate, ammonium lauryl sulfate, sodium cetyl stearyl sulfate, triethanolamine acetyl = stearyl sulfate, monoethanolamine lauryl sulfate, triethanolamine laurylsulfate, ethylene oxide ethanol sulfate, 7-tideceth-carboxylic acid or its sodium salt and the compound of the formula:

Alk - (OCEL - CHn) - OCH- - COnH zz π zz where Alk represents a mixture of the laurine and ant ice group and n is equal to 10, the triethanolamide salt of lauryl keratinic acid, the sodium sulfo = succinate of laurine monoethanolamine, the oxyethyl amide of sulfate , sodium lauryl sarcosinate, sodium hemisulfosuccinate of ethylene oxide-containing laurine alcohol, sodium salt of olefin sulfonate, triethanolamine salt of condensation products of coconut acids and hydrolyzate of animal proteins, ethylene oxide-containing C

68 DK 168059 B1

Among the cationic surfactants which can be used alone or in admixture are in particular the fatty amine salts such as alkyl amine acetates, quaternary ammonium salts such as alkyldimethylbenzyl = ammonium chloride or bromide, alkyltrimethylammonium chloride or 5-bromide bromide, or dimethyldilauryl = ammonium chloride or bromide, acetyldiraethyldodecylammonium chloride, alkylamidoethyltrimethylammonium methosulfates, lactates of N, N-dimethyl 1 = amino (or N, N-diethylamino) polyoxyethyl carboxylates with 4 moles of ethylene = 10 oxide, alkylpyride, = pyridinium chloride, N [lauryl, colaminoformylmethyl] pyridinium chloride, imidazoline derivatives such as the alkylimidazolines, cationic compounds of the formula

Ills R'O [C-H, O (CH-OH)] CH. Wherein CH is a linear or branched, saturated or unsaturated alkyl group or an alkylaryl group having linear or branched 2Q alkyl chain containing 8-22 carbon atoms, and R "and R" ' separated lower hydroxyalkyl groups or alkylene groups which are interconnected to form a heterocyclic ring, and n is a number between 0.5 and 10.

Among the preferred compounds of the above formula are those compounds in which: a) R '= ci 2 H 25; n = 1; R "= R" "= β-hydroxyethyl, and b) R '= c 2 H 25; n = 1? R 2 = R 2 = 2-hydroxypropyl.

The alkyl groups of these compounds preferably have between 1 and 22 carbon atoms. One may also mention the cationic compounds such as the amine oxides, e.g. alkyl dimethyl oxides and alkylamino = 35 ethyl dimethyl amine oxides.

Among the nonionic surfactants which may be used in admixture with the aforementioned anionic surfactants are the condensation products of a monoalcohol, an α-diol, an alkylphenol, an amide or a diglycolamide with glycidol, such as the compounds of the formula: 69 DK 168059 B1

R 4 - CHOH - CH 2 - O - (CH 2 - CHOH - CH 2 - O) - H

4 wherein R represents an aliphatic, cycloaliphatic or arylaliphatic group containing preferably between 7 and 21 carbon atoms, and mixtures thereof, the aliphatic chains may comprise ether groups, thio-ether groups or hydroxymethylene groups and where p is from 1-10, thus as disclosed in French Patent No. 2,091,516, and compounds of the formula:

io r5o [c2h3o (CH2OH)] - H

wherein an alkyl group, an alkenyl group or an alkylaryl group represents and g has a statistical value from 1-10, and compounds of the formula:

R6 CONH - CH2 - CH2 - 0 - CH2 - CH2 - 0 [CH2C00H-CH2-0 -] -— H

g wherein R represents a linear or branched, saturated or unsaturated aliphatic group or a mixture of those which may optionally contain one or more hydroxyl groups and contain from 8-30 carbon atoms which are compounds of natural or synthetic origin, and r denotes an integer or a decimal fraction from 1-5 and means the mean degree of condensation.

Other compounds included in this class are alcohols, alkylphenols, polyethoxylated fatty acids or polyglycerols with linear or branched fatty chain containing 8-18 carbon atoms and usually containing 2-30 moles of ethylene oxide. Also mentioned are copolymers of ethylene oxide and propylene oxide, ethylene oxide condensates and propylene oxide condensates 30 with fatty alcohols, polyethoxylated fatty amides, polyethoxylated fatty amines, ethanolamides, esters of fatty acids with glycol esters of fatty acids with sorbitol.

Among the nonionic surfactants, the most preferred formula has:

R4 - CHOH - CH ~ - O - (CH- - CHOH - CH- - 0) - H

2 2 2 p 4

R5 - 0 [C2 H30 (CH2 OH1] q- H

where R represents a mixture of alkyl groups having between 9 and 12 carbon atoms and p has the statistical value 3.5, 70 where R represents C 2 H 25 25 ar a state; j-st; i's ^ value from 4 -5,

R6 - CONH - CH2 - CH2 - O - CH2 - CH2 O [CH2CHOH-CH2O] H

g 5 where R represents a mixture of groups derived from lauric acid, formic acid, oleic acid and coconut oleic acid, and r has a statistical value of 3-4.

Preferred ethylene oxide-containing fatty alcohols or polyglycerols are 10 polyoxyethylene oleyl alcohol with 10 moles of ethylene oxide, ethylene oxide-containing lauric acid with 12 moles of ethylene oxide, ethylene oxide-containing ethyl alcohol of 6-10 moles of ethylene oxide, ethylene oxide-containing cetylstearyl alcohol, or 20 moles of ethylene oxide, ethylene oxide-containing nonylphenol containing 9 moles of ethylene oxide, ethylene oxide-containing octylphenol containing 5.5 moles of ethylene oxide, polyglycerol-containing oleyl alcohol containing 4 moles of glycerol, and polyoxyethylene-ethylene oxide of ethylene oxide sorbitan monolaurate with 20 moles of ethylene oxide and the poly = 20 condensate of ethylene oxide and propylene glycol.

Among the amphoteric surfactants that can be used are notably alkylamino mono and dipropionates, betaines such as N-alkyl betaines, N-alkylsulfobetatines, N-alkylamidobetaines, cycloimidinium compounds such as the alkylimidazolines, asparagine derivatives such as N, N dialkylaminoalkyl-N-2-alkyl (fat) asparagine. The alkyl group of these surfactants is preferably a group containing between 1 and 22 carbon atoms.

Other solubilizers which can be used for the purposes of the present invention are cosmetically acceptable solvents such as monoalcohols, polyalcohols, glycol ethers, glycol esters, fatty acid esters and methylene chloride which can be used alone or in admixture.

Among the monoalcohols are mentioned the lower alkanols containing between 1 and 4 carbon atoms such as ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, tert-butanol, n-amyl alcohol, isoamyl alcohol, hexadecyl alcohol, 1-octyldecanol-1 , 1-octyldodecanol-1,2-dodecyl = cetyl alcohol, oleyl alcohol, benzyl alcohol, cyclohexanol, methylcyclohexanol, furfuryl alcohol and phenylethyl alcohol.

Among the polyalcohols are the alkylene glycols, such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, polypropylene® glycol, butylene glycol, hexylene glycol, ricinol alcohol and glycerol.

Glycolethrene Among the most preferred are mono-, di- and triethylene = 5 glycolmonoalkylethrene, such as for example ethylenglycolmonomethyl® ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylenglycolmonoethyletner, mono-, di- and tripropylenglycolmonoalkylethrene, propylenglycolmono® such as methyl ether, and polyethylene glycol mono butylenglycolmonoalkylethrene = 10 alkylethrene .

Among the esters, they are particularly useful for the purposes of the invention: the monomethyl ether acetate of ethylene glycol, monomethyl ether acetate of ethylene® glycol, the fatty acid esters and lower alcohols such as isopropyl myristate and isopropyl palmitate.

It will be appreciated that the above-mentioned surfactants can not only be used as long as solubilizers prevent formation of a precipitate formed by interaction between the cationic polymer 20 and Jan anionic polymer in the aqueous medium, but also can be used either simultaneously or independently of the above effect to take advantage of their foaming, wetting, cleansing, dispersing or emulsifying properties.

The cationic polymers, either alone or in combination with other polymers of this type, are present in an amount of 0.01 to 10% and preferably in an amount of 0.5 to 5% by weight relative to the total weight of agent.

The anionic polymers, either alone or in combination with other polymers of this type, are present in an amount of 0.01 to 10%, and preferably in an amount of 0.02 to 5%, relative to the total weight of the agent. .

The weight ratio of cationic polymer to anionic polymer generally varies between 0.1 and 60, advantageously between ca. 0.4 and approx. 50, preferably between 0.4 and 20.

Where the agent also contains a solubilizing agent selected from surfactants or cosmetically acceptable solvents, this agent may be a single agent of the above type or a mixture of two or more agents of the above type in an amount of 0.1 to 0.1%. 70% and preferably an amount from 0.5 to 50% of the total weight of the composition according to the invention.

Preferably, the ratio of solubilizing agent to cationic and anionic polymers varies between 0.5 and ca. 200, especially between 0.5 and about 0.5. 50th

The compositions of the invention can be used as such to treat the hair or skin or can act as a "carrier" contained in cosmetics which further contain an appropriate amount of active compound and are intended for application to the skin, hair or nails for protection against influence from atmospheric substances as well as chemical radiation and to favor the effect of the whole additional active product which is intended for the skin, hair or nails.

The agents of the present invention are in the form of aqueous or aqueous-alcoholic solutions, creams, treatment liquids, gels, dispersions or emulsions.

further, they may contain one or more cationic polymers and one or more anionic polymers, adjuvants commonly used in the cosmetics, such as perfumes, colorants which may have the purpose of coloring either the agent itself or the hair or skin, preservatives, sequestering agents, thickeners, emulsifiers, plasticizers, synergistic agents, anionic, cationic, nonionic or amphoteric surfactants, nonionic or amphoteric polymers, and foam stabilizers, in accordance with the particular application.

When cosmetic agents such as those defined above are used to treat the hair, they may additionally be in the form of set lotions, hairstyling lotions or restructuring lotions.

The emulsifiers used in the compositions of the invention may be the aforementioned anionic and nonionic surfactants. The nonionic emulsifiers are present in an amount of 0.5 to 25% by weight, and preferably the above ethylene oxide containing or polyethylene oxide containing fatty alcohols are used.

The anionic emulsifiers are present in amounts between 0.5 and 15% by weight. Preferably, the above-mentioned optionally ethylene oxide-containing alkyl sulfates are used.

The polyepoxylated or polyglycerol-containing fatty alcohols are composed of fatty alcohols with linear or branched fat chain containing 8 to 18 carbon atoms, and most often contain 2-30 moles of ethylene oxide, preferably 2-10 or 1-10 moles of glycerol and preferably 1-6 moles of glycerol. polyglycerol-containing fatty alcohols are polyglycerol-containing stearyl alcohol or cetyl alcohol with 2 moles of glycerol.

The polyethoxylated or polyglycerol-containing fatty alcohols are present in amounts between 0.5 and 25%.

Among the fatty amides, mono- or diethanol = 15 amides of acids derived from coconut, lauric, oleic or stearic acid are preferably used in amounts between 0 and 10% by weight, preferably from 1 to 4% by weight.

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

The compositions of the invention may also be in the form of lotions which may be hair lotions or lotions for setting or lotions for hair brushing, non-rinse lotions for enhancing the hairline, cleansing lotions, rinse lotions, etc.

Hair lotion or brush lotions are meant lotions used after hair washing and which facilitate the setting of the hairstyle, which hair is done with damp hair by means of a brush, while drying the hair with the aid of a hair dryer.

74 DK 168059 B1

Non-cleansing lotions to strengthen the hairline are a lotion that is applied after hair washing and before hair removal. This lotion, which is not removed by rinsing, facilitates final hair removal and increases its shelf life.

These lotions generally comprise an aqueous, alcoholic or aqueous-alcoholic solution, at least one cationic polymer and at least one anionic polymer such as those listed above. They may further contain nonionic and amphoteric polymers as well as anti-wetting agents.

When the agents are in the form of gels, they contain thickeners, optionally in the presence of solvents. The thickening agents useful may be sodium alginate or gum arabic or cellulose derivatives such as methyl cellulose, hydroxyethyl cellulose, hydroxy propyl cellulose or hydroxypropyl methyl cellulose. Thus, a thickening of lotions can also be obtained with a mixture of polyethylene = glycol and the stearate or distearate of polyethylene glycol or with a mixture of phosphoric acid esters and amides.

The concentration of thickening agents may vary from 0.5 to 30%, preferably from 0.5 to 15% by weight. The pH value in cleansing lotions, also called rinse lotions, can range from 2 to 9.5.

When the above-mentioned agents are under aerosol form pressure, carbon dioxide gas, nitrogen gas, nitrous oxide gas or volatile hydrocarbons such as butane, isobutane and propane may be used as propellants, and preferably use chlorinated or fluorinated hydrocarbons (sold under the name "Freon" by the company Du Pont De Nemours), especially belonging to the class of fluorochlorohydrocarbons, such as dichlorodifluoromethane or Fréon 12, dichlorotetrafluoroethane or Fréon 114 and trichloro-monofluoromethane or Fréon 11. These propellants can be used alone or in combination, and in particular a mixture of Fréon can be used. 114 and Fréon 12, ranging from 40:13 to 80:20. As chlorinated hydro = 30 carbon may be mentioned methylene chloride.

The agents of the invention may furthermore be present as restructuring lotions and contain compounds which strengthen the keratin chains of the hair.

75 DK 168059 B1

For this purpose, compounds of the class of methylol derivatives are used, especially of the type disclosed in French Patents Nos. 1,527,085 and Nos. 1,519,979.

Finally, the combination of the invention may be used in agents for combing or undulating the hair, which further contain polymers, reducing agents such as sulfites, and thioglycolates used with neutralizing agents.

The perfumes which can be used in the agents are cosmetically acceptable perfumes and are present in amounts preferably between 0.1% and 0.5% by weight.

The dyes, which are intended to give the agents of the invention a color effect, are present in an amount of 0.01 to 0.5% by weight.

When the compositions of the invention are prepared for application to the skin, they may be in the form of lotions for use after shaving or in the form of toilet water or shaving cream.

Lotions for use after shaving and toilet water are in the form of an aqueous-alcoholic solution which preferably contains a lower alkanol comprising 1-4 carbon atoms, such as preferably ethanol or isopropanol, and containing the commonly used excipients such as emollients, wound healing means and perfumes.

In the case of toilet water, the perfumes are in greater quantities than those listed above and can be up to approx. 3% by weight according to the nature of the toilet water concerned.

When in the form of a shaving foam, it generally contains 25 soaps, optionally fatty acids, foam stabilizers and plasticizers such as glycerol.

It may be stored in an aerosol container in the presence of propellant according to well-known techniques.

DK 168059 B1 7 6

As stated above, the present compositions may also act as a carrier or matrix in the form of an aqueous or aqueous-alcoholic solution, a cream, a gel, a dispersion or an emulsion, for cosmetic agents for treating the skin.

The agents can also be used to treat the nails, in which case the combination of the invention not only allows fixation of the anionic polymers to nails, but in particular cures them and makes them more glossy, the agents being used in the presence of solvents and other commonly used agents. components.

The agents can be used to treat other keratin-containing materials such as wool.

The various adjuvants which may be used in the agents are well known and may be of the kind particularly described in connection with hair treatment agents.

The agents of the invention may be prepared and stored in various ways, as stated above.

An advantageous method of preparation, however, consists in the manufacture of lyophilized phona, which has the advantage of ensuring a better storage of the compositions according to the invention.

This method of preparation furthermore allows the preparation of the combination according to the invention to be made under conditions such as pH values different from those normally used for a good coupling to the keratin materials, under which conditions an undesirable precipitation is avoided. The method further allows the degradation to be alleviated due to aging (such as yellowing) of certain combinations.

Remarkable results have been obtained with detergents containing a cationic polymer selected from optionally cross-linked polyaminoamides, such as those listed in sections 7, 8, 9, 10 and 11, for various anionic polymers. Particularly preferred combinations are 30 such with grafted and optionally crosslinked crotonic acid group polymers or containing an additional other monomer other than vinyl acetate, with acrylic acid or methacrylic acid or sulfonic acid derivatives.

Another preferred embodiment of the invention consists in the combination of a cationic polymer selected from the polyalkyleneamines mentioned in section 12 with any of the anionic polymers, preferably those listed above.

Particularly advantageous results are obtained by combining the above preferred combinations with surfactants which are 10 weakly anionic or nonionic or mixtures of these two. Weakly anionic surfactants are understood to mean carboxylated derivatives such as alkyl polypeptidates, salts of lipoamino acids, alkyl polyglyceryl = carboxylates and carboxylic acids of polyglycols. The particularly preferred nonionic surfactants are the compounds of the formula: R 4 - CHOH CH 2 - 0 - (CH 2 -CHOH-CH 2 -O) p - H, mentioned above.

An advantageous embodiment of the invention consists in the combination of a strong substantive cationic polymer of the type of cyclopolymers or quaternary polymers mentioned in section 2 together with a anionic polymer, preferably with the preferred anionic polymers mentioned above.

An interesting way of accomplishing this is by combining the above polymers with an anionic surfactant, preferably the above sulfates, sulfonates, succinates, succinamates, acetates, phosphates and sarcosinates.

25

The combination of the invention also allows for interesting results to be obtained with less substantive cationic polymers belonging to cellulose ether polymers of the type mentioned in section 1 with acrylic acid or methacrylic acid groups as disclosed in French Patent No. 2,189,434, as mentioned in section 3, the vinylpyrrolidone = derivatives mentioned in sections 6 and 13 together with any anionic polymer, preferably with those containing in their chain sulfonic acid groups, crotonic acid groups, acrylic acid groups or methacrylic acid groups, and maleic anhydride derivatives. These combinations are interesting, especially for reducing the static electricity of the hair.

The cationic polymers of the type described in section 4 contain in their chain a group of two amino functions, such as piperazinyl, and enable properties that are of interest to hair performance when used in combination with an anionic polymer of the above indicated particular preferred type.

The anionic polymers preferred for the practice of the invention are thus containing a linear, non-crosslinked acrylic acid or methacrylic acid group, an optionally monoesterified or hydrolyzed maleic anhydride group, or a grafted and optionally crosslinked crotonic acid group, or those containing a further monomer, together with any of the above cationic polymers. The results are particularly significant in terms of softness of touch and volume.

When the anionic polymer is used in agents that are not intended to be rinsed, the lotion type for keeping the hair in shape, the lotion type for enhancing the hair set, the lotion type for use after shaving, toilet water or treatment for the nails, is obtained. particularly surprising results with agents containing as anionic polymer the polymers, acrylic acid derivatives or methacrylic acid derivatives listed in Section 13 in association with any cationic polymer, preferably crosslinked polyaminoamides, polyalkyleneamides, cyclopolymers and quaternized polymers of ionic type.

Interesting results are also obtained with copolymers of crotonic acid containing at least one monomer other than vinyl acetate or grafted and / or crosslinked derivatives or allyloxy acetic acid or vinyl acetic acid together with any of the cationic polymers, preferably those listed above.

Other interesting combinations according to the invention are those which an anionic polymer consists of a bipolymer vinyl acetate / crotonic acid together with cationic polymers selected from the cellulose ether derivatives mentioned in section 1, the cyclopolymers mentioned in section 2, the homo- or copolymers mentioned in section 3, the vinyl pyrrolidone derivatives mentioned in section 5 6, the polyalkyleneamines mentioned in section 12, the polymers containing in their chain vinyl pyridine groups or vinyl pyridinium groups, urea-formaldehyde resins, condensates of polyamine and epichlorohydrin, vinyl = benzylammonium homomers or copolymers or copolymers or copolymers.

The agents of the invention, which are especially intended for treating the hair, according to a variant of the invention can be made according to a two-step method.

This process is characterized in that, in a first step, a first agent containing an anionic polymer and cationic polymer of the above type is set, adjusted to a pH to avoid precipitation of the combination of anionic polymer with the cationic polymer, and in a second step without intermediate rinsing, apply another agent having a pH such that the two polymers precipitate on the hair when the second agent is applied to the fibers.

According to a preferred embodiment, the first agent has a pH between 8 and 12 and the second agent has a pH selected in such a way that, after mixing with the first agent on the hair, this pH is lower than 8 .

In particular, this embodiment of the process of the invention enables the use of combinations of cationic polymers and anionic polymers which, under the current pH conditions, are precipitated to a maximum.

In this case, it is possible to apply combinations at a different pH value in order to avoid the precipitation and to induce it on the hair in order to obtain an optimal precipitation of anionic polymers, which is the object of the invention.

The alkaline agents which may be used in the first agent are organic or inorganic bases of the above type. The acidifying agents which may be used in the second agent are organic or inorganic acids such as hydrochloric acid, citric acid, lactic acid, tartaric acid, phosphoric acid, etc.

It is also possible to apply the first agent to the hair at an acidic pH and then to increase the pH by a second agent containing a base on the hair to obtain the precipitation of the polymers on the hair.

Particularly interesting results are obtained with crosslinked polyaminoamides of the type described in sections 7, 8, 9, 10 and 11 as cationic polymers and crotonic acid derivatives as anionic polymers 10 in the first case, and with the above crosslinked polyaminoamides in association with maleic anhydride derivatives in the second case.

The fixation of the anionic polymers to the keratin-containing materials by means of a cationic polymer can according to the invention be carried out by a two-step process consisting of the application, preferably to 15 keratin fibers, of a first agent containing a cationic polymer of the above-mentioned type and then, optionally, after rinsing, applying an agent containing an anionic polymer, which treatment is preferably followed by a rinsing. In this case, the combination of cationic polymer and anionic polymer is formed on the 20 fibers themselves.

Other combinations which give advantageous results in a two step process are those for use in a first agent consisting of a cationic polymer derived from acrylic acid or methacrylic acid of the type set forth in the above section 3, and as anionic polymer. derivatives of acrylic acid or methacrylic acid listed in section 11, in particular the polymers referred to as "Reten" or "Catrex" sold polymers, or which, for use in the first agent as cationic polymer, comprise a cellulose ether derivative as defined in section 1, the polymers mentioned in section 4, the polyethylenamines of the type mentioned in section 12 30 or the polymers containing in their chain vinyl pyridine groups or vinyl pyridinium groups as listed in section 13 together with the above anionic polymers.

DK 168059 Bl 81

This application gives good results when using anionic or nonionic surfactants in the agents.

In an advantageous embodiment of the process, it is possible to vary the pH of the various agents in order to obtain the best conditions for the precipitation of each polymer and induce coupling of the anionic polymer to the fibers by the cationic polymer.

The present invention may be referred to as a method for fixing anionic polymers to a keratin material which is characterized by inducing the fixation of the anionic polymer in combination with a cationic polymer.

When the agent is in lyophilized form, the process of the invention consists in introducing the lyophilizate into the cosmetic carrier, which may contain the various aforementioned adjuvants, and applying the agent thus prepared to the keratin material. This method is of particular interest when the polymers tend to stain yellow in solution storage and when they are desired to be applied to a keratin material where such a feature is not desirable, such as on the skin or nails.

The following examples serve to illustrate the invention.

In the following examples, all the polymers are listed as active material. The amounts indicated are for polymers with 100% active material. In the following examples, the amounts of surfactant are expressed as percentages of active material.

The anionic polymers used in the following examples must in some cases be neutralized. This is the case when using the following examples in the following polymers: Resin 5 "26.13.10", resin "TV 242", "P", "P2", "P3", "Quadramer 5", "Gantrez" ES 225, "Gantrez" 425, resin "28-29-30", "EMA" 1325, being understood to have been neutralized to an extent which can be up to 100% soluble in aqueous medium, by means of alkaline substances such as ammonia, alkylamines, alkanolamines such as mono-, di- or triethanolamine or triisopro-panolamine or mixtures thereof, alkylalkanolamines, aminomethylpropanol, aminomethylpropanediol, sodium hydroxide or potassium hydroxide, sodium carbonate, or potassium which can be used, for example, to neutralize the above polymers are 2-amino-2-methylpropanol, 2-amino-1,3-propanediol, triethanolamine, triisopropanolamine and sodium hydroxide. The neutralization is carried out up to a pH of 7 to 10, most often between 7 and 9.

Said anionic polymers may also be previously solubilized in an anionic surfactant or solvent of the type disclosed in the specification. In this case, neutralization is unnecessary.

The polymers can also be used with plasticizers such as methyl celllosolve, methyl, dimethyl, diethyl, dibutyl and dioctyl phthalate, propylene, hexylene, polyethylene and polyalkylene glycol, propylene glycol dipole argonyl acetate acetate, polysiloxane glycol, glycerol triacetylate , octyl sebacate, acetyl tributyl citrate, isopropyl myristate, ethyl phthalyl ethyl glycolate and methyl phthalyl ethyl glycolate.

Table I relates to hair phrase lotions.

30 After applying these lotions to the hair shades, it is established that the dry hair is full, vibrant, inelectric and easier to hair.

83 DK 168059 B1

To the various ingredients listed in Table I, water is added in sufficient quantity to obtain 100 cc.

To the various aforementioned agents are generally added perfumes and dyes intended to improve the performance of said 5 agents.

By way of example, in agents 1-4, 10-15 and 20-40, approx. 0.1 g of dye and approx. 0.2 g of perfume.

The meaning of the abbreviations and the meaning of the trade names of the various examples of products used are given in the preceding description and below.

The numerous polymers used according to the invention are also described in more detail in "Cosmetic Ingredient Dictionary" published "The Cosmetic Toiletry and Fragance Association Inc.".

Surfactant and excipients.

ACSPO Mixture of cetylstearyl alcohol and cetylstearyl = alcohol reacted with 15 moles of ethylene oxide.

AES Sodium C 2 -C 4 alkyl ether sulfate reacted with 2.2 moles of ethylene oxide.

ALE 12 Lauryl alcohol which is polyepoxylated with 12 moles of ethylene oxide.

AST 12 14 C - 13 C4 alkyl sulfate of triethanolamine.

CIRE DE LANETTE E 10% sulfated cetylstearyl alcohol sold by the company Henkel.

DEHYTON AB 30 C ^-C ^ g alkyl dimethyl carboxymethylammonium: 25 hydroxide sold by Henkel.

EMPICOL STT The sulfosuccinate of cetylstearyl alcohol sold by the company MARCHON.

IMWITOR 960 K Auto-emulsifiable glycerol stearate sold by the company DYNAMIT NOBEL.

84 DK 168059 B1

CH, C00NA

MIRANOL C2M Ο ,, Η ,, “C“ NQ ^

N 2 CH 2 - CH 2 - O - CH 2 - C00NA

CH2

TA-1 RCHOH - CH20 f CH2 - CHOH - CH20 f H

wherein R represents a Cg-C ^₂ alkyl group, and n = 3.5 TA-2 nonionic surfactant based on polyglycerolized (4.2 moles) of laurine alcohol, for approx.

60% solution in active material.

Formula (statistical):

C12H25--0 "CH2 ~ CH - 0H

CH-OH

L-1 4.2 TA-3 Polyglycerolated fat diglycolamide.

r-co-nh-ch2-ch2-o-ch2-ch2 -t o-ch2-choh-ch2 f OH

3.5 R = natural amides of fatty acids with 12-18 carbon atoms.

DIVALIN SO Phosphoric acid esters of ethoxylated oleyl alcohol.

ACS 15 OE Cetylstearyl alcohol which is oxyethylenated with 15 moles of ethylene oxide.

LCC Lactate of N, N-diethylaminopolyoxyethyl carboxylate of coconut oil with 4 moles of ethylene oxide.

SIMULSOL 1951 D Cetylstearyl alcohol, oxyethylenated with 10 moles of ethylene oxide and sold by SEPPIC MONTANOIR.

ΑΚΥΡΟ RLM 100 Weak anionic surfactant of the formula R- (OCH2) -R- (OCH2CH2) x-OCH2COOH, where R is an 85 C 16 ~ C 14 alkyl group mixture and x equals 10 sold by the company CHEMY.

SANDOPAN DTC AC Trideceth-7-carboxylic acid of the formula:

5 CH3 (0Η2) η - CH2 (0CH2 - CH2) 6CH2 - COOH

which is sold by the company SANDOZ.

SANDOPAN DTC Sodium salt of trideceth-7-carboxylic acid.

10 MAYPON 4 CT Triethanolamine salt of the coconut oleic acid condensation product and animal protein hydrolyzate sold by the company STEPAN.

ELFAN OS 46 Olefin Sulfonate 15 CH 3 - (CH 2) 10 12 "CH = CH - CH 2 SO 3 Na + CH 3 - (CH 2) 10 _ 12 CH 2 - CH - CH 2 SO 2 Na

OH

sold by the company AKZO CHEMIE GmbH.

20 SETACIN 103 Spezial Hemisulfosuccinate of polyepoxylated sodium 5 * · laurine alcohol sold by the company ZSCHIMMER et SCHWARZ CHEMISCHE FABRIKEN.

SURFARON A 72 12 N 30 Aqueous solution of sodium lauryl sarcosinate at 25 density approx. 1,035 at 20 ° C and sold by the company PROTEX.

HOSTAPUR SAS-30 n-alkane sulfonates obtained by sulfoxidation of n-paraffins of 13-18 carbon atoms and a mean molecular weight of 328 sold by the company HOECHST.

LIPOPROTEOL LK Salt of the triethanolamine of lauryl keratinic acid sold by the company RHONE POULENC.

35 REMCOPAL 306 Octylphenol, oxyethylenated with 5.5 moles of ethylene oxide and sold by the company GERLAND.

REMCOPAL 349 Nonylphenyl oxyethylene with 9 moles of ethylene oxide and sold by the company GERLAND.

MYRJ 53 Polyoxyethylene stearate with 50 moles of ethylene oxide sold by the company Atlas or sold under the designation "PEG-50" stearate by the company ICI U.s.A.

SOMEPON ML 20 Oxyethylamide of fatty acid from sulphated coconut 5 sold by the company MONTANOIR.

NORANIUM M 2 C Dimethyldilaurylammonium chloride sold by the company CECA PROCHINOR.

10 emCOL E 607 L Ndauryl-colaminoformylmethylDpyridinium chloride sold by the company Witco or in the dictionary CTFA is called Lapyrium Chloride.

TWEEN 20 Polysorbate 20 or polyoxyethylene monolaurate 20.

15 ATLAS Sorbitan sold by the company Atlas.

EMPICOL 0091 Sodium laurine monoethanolamide sulfosuccinate sold by MARCHON.

20 AROMOX DMCD Oxide of coconut dimethylamine sold by the company AKZO CHEMIE.

PLURONIC L 62 Polycondensate of ethylene oxide and polypropylene = 25 glycol of the formula:

HO (CH2 - CH2 - Ofg-fCH - CH2O4- (CH2-CH2O) g H

ch3 sold by the company UGINE KUHLMANN.

AMPHOTERS 1 Surfactant of the formula: / 2 CH - CONH (CH -) - N i 2 2 3 \ R - NH - CH - COONa 35 wherein R represents a mixture of alkyl groups derived from coconut fatty acids.

AMPHOTENSID GB 2047 Is an alkylimidazoline sold by the company ZSCHIMMER and SCHWARZ.

AMPHOSOL DMC / MCA Acetyl dimethyldodecylammonium chloride sold by the company ICEVE VOREPPE.

87 DK 168059 B1 AROMOX DM 14 DW Means the compound of the formula:

C14H29 (CH3> 2 O)

5 sold by AKZO CHEMIE.

DERIPHAT 160 Means disodium N-lauryl-ft-iminopropionate sold by the company GENERAL MILLS.

10 STEINAPON AM B.13 Means an alkylamide of betaine of the formula: R - CO - NH- (CH2) 3-ft- (CH3) 2-CH2-COO "sold by the company REWO.

Anionic polymers.

15 28.29.30. The vinyl acetate / crotonic acid / vinyl neodecanoate terpolymer sold under the designation Résine "28.29.30" by the company NATIONAL STARCH.

20 FLEXAN 500 Sodium salt of polystyrene sulfonate having a molecular weight of approx. 500,000, under the designation "Flexan" 500 is sold by the company NATIONAL STARCH.

FLEXAN 130 Sodium salt of polystyrene sulfonate with a molecular weight of 100,000, which under the name "Flexan" 130 is sold by the company NATIONAL STARCH.

QUADRAMER 5 Copolymer of N-tert.-butyl acrylamide, acrylamide, acrylic acid and N-vinylpyrrolidone sold under the designation Quadramer 5 by the company AMERICAN CYANAMID.

GANTREZ ES 425 Monobutyl ester of poly (methyl vinyl ether / maleic acid) sold under the designation "Gantrez" ES 425 35 by the company GENERAL ANILINE.

EMA 1325 Copolymer of ethylene and the semibutyl ester of maleic anhydride, which under the designation "EMA 1325" is sold by the company MONSANTO.

P I Terpolymer of vinyl acetate, crotonic acid and allyl = dimethylpropanoate (77/8/15).

see DK 168059 B1 p 2 Copolymer of vinyl acetate / crotonic acid, allyldi = methyl propanoate and vinyl laurate (77/8/14/1).

P 3 Copolymer of vinyl acetate, allyl stearate and allyl = 5 oxyacetic acid (80.5 / 15 / 4.5).

RESINE TV 242 or ARISTOFLEX A Terpolymer of vinyl acetate, crotonic acid and poly = ethylene glycol sold by the company HOECHST.

10 VERSICOL K 11 Polymer of molecular weight methacrylic acid 10,000 and viscosity 1000 centipoise in 25% solution sold by the company ALLIED COLLOIDS.

15 VERSICOL E 5 Mixture of homo- and copolymers of acrylic acid with a viscosity of 16 centipoise in 25% solution and with a molecular weight of approx. 3500 sold by the company ALLIED COLLOIDS.

20 CARBOPOL 940 CARBOPOL 941 Carboxyvinyl polymer derived from high molecular weight acrylic acid sold by GOODRICH CHEMICALS.

PA-4 Copolymer of allyl acetate / maleic anhydride monoesterified with alcohol (50/50).

25 PA-5 Copolymer of isobutyl vinyl ether / maleic anhydride monoesterified with ethanol (50/50).

PA-6 Copolymer of butyl vinyl ether / maleic anhydride monoesterified with ethanol (50/50).

PA-7 Copolymer of allyl acetate / maleic anhydride amidified with dodecylamine and dibutylamine (50/50), PA PA-8 Terpolymer of allyl acetate / 2-ethylhexyl acrylate / maleic anhydride monoesterified with ethanol (47.4 / 2.6 / 50).

PA-9 Copolymer of isobutyl vinyl ether / allyl neoheptanoate / maleic anhydride monoesterified with ethanol (18.2 / 31.8 / 50).

89 DK 168059 B1 PA-10 Copolymer of allyl pivalate / maleic anhydride monoesterified with ethanol (50/50).

RETEN 421 High molecular weight polyacrylic electrolyte and 5 Brookfield viscosity LVF at 60 rpm at 1000 - 1500 centipoise sold by the company HERCULES.

26-13-14 Vinyl acetate / crotonic acid polymer with viscosity 800 centipoise at 22 ° C in 40% solution, acidity LO 1.16 mil equivalents per dry resin.

LIGNOSULPHONATE C 10 Calcium lignosulfonate with apparent density 0.48 and a pH in 5% solution of approx. 5.8.

L5 LIGNOSULPHONATE C 14 Calcium lignosulfonate with apparent viscosity 0.48 and a pH in 5% solution of approx. 8, sold by the company L'AVEBENE.

HYDAGEN F Sodium salt of polyhydroxycarboxylic acid sold 20 by the company HENKEL.

RETEN 423 High molecular weight polyacrylic electrolyte and

Brookfield viscosity LVF at 60 rpm at 3000-4000 centipoise sold by the company HERCULES.

25 EXTRACTION 8 Acrylic copolymer with flash point 40 ° C (TAG open cup) manufactured by CIBA GEIGY.

CYANAMER A 370 Modified polyacrylamide having a molecular weight of 30 200,000 and a specific viscosity of 3.7 - 0.5 sold by the company AMERICAN CYANAMID.

P-COL Colored polymer consisting of the compound sold under the designation "GANTREZ" ES 425 wherein a portion 35 of the carboxylic acid functions has been amidified with the primary amine of the dye: 0 nh (ch2) 3nh2 O NH CH3 90 DK 168059 B1

Cationic polymers.

MERQUAT 100 Homopolymer of molecular weight cimethyldiallyamminium chloride less than 100,000 sold under the name "Merquat" 100 by MERCK.

MERQUAT 550 Copolymer of dimethyldiallylammonium chloride and molecular weight acrylamide greater than 500,000 sold under the name "Merquat" 550 by the company MERCK.

CARTARETINE F 4 The copolymer adipine / dimethylaminohydroxypropyl = diethylenetriamine sold under the designation "Carta-rétine" F 4 by the company SANDOZ.

15 GAFQUAT 755 Copolymer of quaternary polyvinylpyrrolidone having a molecular weight of 1,000,000 marketed by the company GENERAL ANILINE.

20 GAFQUAT 734 Copolymer of quaternary polyvinylpyrrolidone with a molecular weight of 100,000 marketed by the company GENERAL ANILINE.

AZA-1 Cationic polycondensate of piperazine / diglycolamine / epichlorohydrin in the molar ratio 4/1/5 as described in Example 2 of French Patent No. 2,280,361.

AZA-2 Cationic polycondensate of piperazine / diglycolamine / epichlorohydrin in the 1/1/2 molar ratio as described in Example 3 of French Patent No. 2,280,361.

AZA-3 Cationic polycondensate of piperazine / diglycolamine / epichlorohydrin in the molar ratio 2/1/3 as described in Example 4 of French Patent No. 2,280,361.

AZA-4 Cationic polycondensate of piperazine / diglycolamine / epichlorohydrin in the molar ratio 4/1/5 as described in Example 5 of French Patent No. 2,280,361.

AZA-5 Cationic polycondensate of piperazine / 2-amino-2-methyl-1,3-propanediol / epichlorohydrin in the molar ratio 1.07 / 0.45 / 1.5 as described in Example 6 of French Patent No. 2,280,361.

DK 168059 B1 AZA-6 Cationic polycondensate of piperazine / epichloro = 1/1 molar hydrin as described in Example 1 of French Patent No. 2,162,025.

5 AZA-7 Cationic polycondensate of piperazine and pipera = zin bisisacrylamide in molar ratio 1/1 as described in Example 14 of French Patent No. 2,162,025.

PGR-1 Grafted and cross-linked copolymer of N-vinyl pyrro = 10 lidon / dimethylaminoethyl methacrylate / polyethylene = glycol / tetraallyloxyethane, quaternized with dimethyl sulfate, in the ratio 62/28/10 / 0.02 as described in Example 2 of French Patent No. 2,189. 434th

15

Polymers PGR-2 to PGR-16 are the polymers described in Examples 1 and 3-17 of French Patent No. 2,189,434.

G-14 Polymer with the group: CH3 Br “CH3 Br” CH2CH2COHN (CH2) 3- Kt CH3 CH2CH2COHN (CH2) 3 ~ Nt-CH3

25 r H C H

X5 2n5 __tH -Hl --- (ch2 ψ * «--- ^ ch2) τ-- CH3 Br" 1 CH3 Br "30! i2H5 n 35 92 DK 168059 B1 8 T ~ ri o>. * - <il Ai .5 5 c ω φ e 9U w τ '' ri S «s cu BS ^ i ° o ==== μλ g ^ w o .

m m lo vo m pr * λ '»» · * «· * ο. σ> σ> ct> co r · * '· ϊΓ ~~ - Q β ο β β β S ^ Ο ο ο ο ο W ®ρ mm in «η ιη,} -) Η Φ <ί --__: _ (Η Ό -3 u - g. Φ η w <η ο tP <w Λ c ο η • HH4J Λ ή C Ο) 01 Η +> ΜιΗ φ (0 03 • Θ-γΗ £ · Η £ 3 ΟΛνί · α3 ^ + J = = r- „r

W Χ3 W

60 ΙΟ Η ο ο 7 "κ" # ® φ Μ Η Tf φ 2Γ <8 Η ι_ι ° £ j * g ”g Elg s φ Η S Β C0 --------- —..... ................. — ....... ,. ,, -,, ,, ο 2 60 5 mm ιΛ «Λ« Λ lZ ¢ 4 “" * »·» »S Ο Ο Ο Ο Ο S3-- æ 13 w <φ S Λί sf 4 4 β Φ to .to add to ai .η Ρω ω ω ω 5 ζ ζ ζ ζ ο Μ Μ Η Η Η ω ω ω ω ω (0 Βί οί Ρί βί «„ <0 <. <1 <a »^ Η Η Η Η ω ρύ ρί αί 3 <<<ί bold

V Ο Ο ο V

> · - ------ 00 ΤΊ W υ ~ ι ΙΟ Ν ^ ^ ΓΠ * «. ^ Λ Λ * * <* ο ο ο ° ° = Η ο

φ CM

to <Γ tn «'Ρ ο ο> ο C η οί η η Ο ·« ι • ri σ> σ> α α> G cm ν η «η« ^ 00 00 ”00

CS CM to jg CM

ί ύ <jj * "(Η Ν Μ ^ Φ

Cfl ι— * aa - ^ 93 DK 168059 B1

Example 6

The following agent is prepared: "Gafquat" 755 ----------------------------------- 0.1 g

Polymer "28-29-30" ------------------------------ 0.1 g 5 Ethyl Alcohol ------ - until -------------------- 60%

Perfume ----------------------------------------- 0.5 g

Water --------- until -------------------------- 100 ml

This agent is used as a after shave lotion. Applied to the skin after shaving, it softens the skin.

Example 7

The following means are prepared:

Polymer K. Ia ------------------------------------- 0.5 g "Versicol" K. 11 ------------------------------------------------------------ 0.4 g pH is adjusted to 8.4 with hydrochloric acid 15 Water ------- until ------------------------------- 100 ml

This agent is used as a set lotion. After impregnating the hair with this lotion, wrap it around hair wrappers with a diameter of 15 to 30 mm, and then dry the hair by applying external heat. After removing the hair wrappers, you obtain a hair set that stays well with time, and the hair is otherwise inelectric and supple.

Example 8

The following means are prepared:

Medium S3: 25 G 14 -------------------------------------------- - 1 9

Monoethanolamine ----- until --------------------- pH 6.3

Water --------- until ---------------------------- 100 9 94 GB 168059 B1

Medium S4:

Resin TV 242, 100% neutralized --------------- 1 g of pH is adjusted to 6.4 with sodium hydroxide 5 Water ------- until -------- ---------------------- 100 g

By successively applying these two agents to the hair, it is observed that the dry hair is vibrant, easy to hair and that the durability of the hair cut is good.

The following agents are prepared:

Mean Sg: in "Cartarétine" F. 8 ------------------------------ 3 g "Gantres" ES 425 --- ----------------------------- 1 9 15 Neutralized to pH 5.5 with triethanolamine

Tartaric acid ----- until ---------------------------- pH 3 "TA-l" -------- -------------------------'------- 1 9

Water ------- until ----------------------------- 100 g

Average Sn: 20 _ 5% Monoethanolamine ------------------------------ 22 g pH 10.8 • Water ---- - until ------------------------------ 100 g Apply 20 ml of the agent Sg to soft, clean and damp hair.

After a few minutes of action, the agent S ^ q is applied. The application is done while massaging the hair to obtain a good mixture of two parts. Thus, a pH of 7 is obtained at which the two polymers present are deposited on the hair.

95 DK 168059 B1

You put your hair and dry it. The dried hair is hardened, vibrant, lustrous and full.

Examples 10 - 12

The following agents are prepared: 5 Eqs. 10 Ex. 11 Ex.12 "Cartarétine" F.8 ---------- 1.5 g ------- 6 g -------- 1.5 g "Gantrez" ES 425 ----------- 0.5 g ------- 3 g -------- 0.5 g

Neutralized to pH 7.5 with triethanolamine 10 "TA-1" --------------------- 0.5 g ------- 3 g - ------

Tartaric acid --- until --------- pH 3 ------- pH 3 -------- pH 3

Water ---- until ----------- 100 g ------- 100 g ------- 100 g

The agents are lyophilized.

Example 13 The same agent is prepared as follows: "Cartarétine" F. 8 --------------------------------- 1.5 g "28.29.30" ----------------------------------------- 0.5 g

Neutralized to pH 8 with triethanolamine

Sodium hydroxide ----- until ----------------------- pH 9.9 20 Water ------ until ------- -------------------------- 100 g

The agent is lyophilized. At the time of use, 0.5 g of the lyophilisates of Examples 10, 12 or 13 are introduced into 25 g of water and applied to the hair. The hair thus treated, after drying, is alive and well with time. 0.12 g of the lyophilisate of Example 11 is introduced into 25 g of water and applied to the hair. Similar results are noted.

96 DK 168059 B1

Iglrgempal 14 - 16

A hair set with a good shelf life is obtained over time with virtually no powdering effect using the following agents (Table X) applied to moistened and dried hair according to usual methods: Z Anionic "" Cationic ΓΓΤ Solution Alcohol ~ Polymer ”polymer% g polymer% g nd% & 14 Gantrez 1 Gafquat 1 Ethyl = 10 ° 8.3 ES 425 734 .. alcohol 15" 1 Claw 1 "70 ° 9.2 16" 1 Cartarétine 1 "10 ° 8 , 9 F8

Water is added in sufficient quantity to 100 g.

Examples 17 - 19

The agents listed in the following table are prepared: Z ~ I Anionic Γ7 Cationic JT Surface Solution 'polymer ° g pollen ° g active * 9 agent pt ______ agent____' 17 Gantrez 1 Cartarétine 1 Ethylal = 8.9 ES 425 F8 carbon, 10 % 18 28-29-39 0.5 Cartarétine 0.5 TA-1 0.5 "50% 9.5 F4 19 P3 0.25 Cartarétine 0.5" 50% 9.5 F4

Each of the agents is applied to the nails and after 10 minutes of drying and after a few minutes, it is hardened.

Claims (15)

97 DK 168059 B1 Patent claims. 1. IAAAIIIN r2_n_R4s2 - «- S4 <* 6 4® X9 - i · X-wherein R 1 is hydrogen or CH 3, A is a straight or branched alkyl group having 1-6 carbon atoms or a hydroxyalkyl group having 1-4 carbon atoms, R2 , R 3 and R 4, which are the same or different, represent an alkyl group of 1 to 18 carbon atoms or a benzyl group, R 5 and R 9 represent hydrogen or alkyl of 1-6 carbon atoms and X is halogen or methosulfate; (D) cationic polymers selected from polymers of the formula A-Z-A-Z- wherein A represents a group having two amine groups and preferably / ~ λ A method of treating hair, skin and nails with a composition based on a mixture of a component A containing a cationic polymer and a component B containing an anionic polymer having a molecular weight of 500 to 5,000 .000, wherein the cationic and anionic polymer is present in a solvent and in a proportion of 0.01 to 10% by weight, based on the total weight of the agent, characterized by applying the agent to the hair, skin or nails, the anionic polymer present in the component is selected from polymers having structural units derived from the following acids, their salts or acid derivatives: (a) sulfonic acid, (b) phosphoric acid, (c) crotonic acid derivatives selected from: - the grafted polymers of vi new esters and esters of acrylic acid or methacrylic acid, alone or in admixture, copolymerized with the crotonic acid, grafted onto polyalkylene glycols whose terminal 20 OH groups are optionally etherated or esterified, or grafted on to azotated polyalkylene glycol oxides; the grafted and crosslinked polymers obtained by copolymerizing a nonionic monomer, crotonic acid, polyethylene glycol and a crosslinking agent; 25. the terpolymers derived from: crotonic acid, vinyl acetate, an allyl or methallyl ether of the formula I1 Ro - C - C - O - CH2 - C = CH2 (11) I II I ch3 o R 'wherein 98 DK 168059 B1 R 'represents a hydrogen atom or a -CH3 group, RX represents a saturated, straight or branched hydrocarbon chain having 1 to 6 carbon atoms, and R2 represents either the -CH3 group or the group -CH (CH3) 2; 5. the tetra and pentapolymers obtained by copolymerizing: «crotonic acid, • vinyl acetate or vinyl propionate, * an allyl or methallyl ester of formula (11), 10. a monomer selected from: - a vinyl ether of formula CH2 = CH - 0 - R3 wherein R3 represents an alkyl group, - a fatty acid chain of fatty acid chain of formula R4 - C - O - CH = CH2 II 0 wherein R4 represents a straight chain alkyl group of 7 to 11 carbon atoms, - an allyl or methyl ester of formula : R5 - C - 0 - CH2 - C = ch2 II I O is R 'wherein R' is a hydrogen atom or a methyl group and R 5 is an alkyl group; - the terpolymers of vinyl acetate, crotonic acid and of vinyl esters 20 of an aliphatic saturated monocarboxylic acid branched at the α position containing at least 5 carbon atoms in the carboxy group; 99 DK 168059 B1 - copolymers obtained by copolymerization of: - esters of unsaturated alcohols and saturated short chain acids, esters of saturated alcohols with unsaturated acids, esters of crotonic acid, esters of long chain acids and unsaturated alcohols, esters of unsaturated acids and a saturated or unsaturated alcohol having 8 to 18 carbon atoms or a lanolin alcohol, alkyl vinyl ethers, alkyl allyl ethers, alkylmethallyl ethers, alkylcrotyl ethers and the α-olefins; - copolymers of crotonic acid with ethylene, vinylbenzene, vinylmethyl ether and acrylamide and water-soluble salts thereof; - the copolymers of vinyl acetate / crotonic acid with acrylic or methacrylic acid esters or an alkyl vinyl ether; - the copolymers of vinyl acetate / crotonic acid and a monomer selected from long carbon chain vinyl, allyl and methalyl esters, (d) acrylic or methacrylic acid, the polymer being selected from: - graft copolymers obtained by grafting of vinyl esters, acrylic or methacrylic acid esters, individually or in admixture 20 and copolymerized with acrylic or methacrylic acid, on a etherified or esterified polyalkylene glycol, or on an oxide of a nitrogen-containing polyalkylene glycol; the grafted and crosslinked polymers obtained by copolymerization of a nonionic monomer, acrylic or methacrylic acid, polyethylene glycol and a crosslinking agent; - ter-, tetra-, penta- and higher polymers of a monomer of the formula R 1 R 2 II CH 2 = C - C - NH - C - (CH 2) n - CH 3 (15) II In o R 3 wherein R 1, R 2 and R 3 are hydrogen or methyl and n is 0 or is an integer from 1 to 10; - a water-soluble monomer of the formula R 'R 4 - CH = C - (CH 2) m - CON - Z - OH (16) r 5 wherein R' represents hydrogen or methyl, Z represents a straight-chain or branched alkylene group, which is optionally substituted with one or two hydroxymethyl groups, m has the value 0 or 1, R4 is hydrogen or -CORg (R6 = OH or -NH-R7, R7 means hydrogen or -Z-OH), R5 means hydrogen or methyl when m = 0, or R4 and R5 mean -CORg when m = 1; -acrylic or methacrylic acid, optionally together with one or more copolymerizable monomers; N-tert-butyl acrylamide, N-isopropylacrylamide / acrylamide, methacrylamide / acrylic and methacrylic acid / N-vinylpyrrolidone ter polymers; water-soluble polymers of acrylic and methacrylic acid and copolymers of acrylic or methacrylic acid with a monoethylenically unsaturated monomer; polyacrylamides containing carboxylate groups; and 20 - copolymers of 40 to 90 mole% of new 1 py r ro lidon, 40 to 50 mole% vinyl ester and 20 to 30 mole% of acrylic or methacrylic acid; (e) ethylene α-α-carboxylic acid, (f) allyloxyacetic acid, methallyloxyacetic acid, 3-allyloxy-propionic acid, allylthioacetic acid, allylaminoacetic acid, vinylacetic acid, vinyloxyacetic acid, crotyloxyacetic acid, 3-butene-acetic acid, 3-butene-acetic acid, , 10-undecenoic acid, allyl malonic acid, maleamic acid, itaconamic acid or N-mono- or N-dihydroxyalkyl-maleamic acid or itaconamic acid, with the exception of anionic homopolymers of acrylic acid cross-linked with an allyl ether of sucrose or pentaerythritic then, the treated keratin material is not rinsed. Process according to claim 1, characterized in that the polymer according to (d) in claim 1 is composed of acrylic or methacrylic acid and an additional monomer selected from ethylene, vinyl acetate, vinylbenzene, vinyl methyl ether, acrylamide and water-soluble salts thereof or copolymer of acrylic acid or methacrylic acid in the form of its alkali salt and vinyl alcohol. Process according to claim 1, characterized in that the pH of the agent is adjusted such that the composition of anionic and cationic polymer does not precipitate and that the pH of the hair is modified at a further step to produce a precipitation of the composition of anionic polymer / cationic polymer on the hair. The agent for use in the process of claims 1 to 3, comprising a component A containing a cationic polymer and a component B containing an anionic polymer having a molecular weight of 500 to 5,000,000, the cationic and anionic polymer is present in a solvent and in a proportion of 0/01 to 10% by weight, based on the total weight of the agent, characterized in that the agent can be applied to the hair, skin or nails and that the anionic polymer present in component B is selected from polymers having structural units derived from the following acids, their salts or acid derivatives: (a) sulfonic acid, (b) phosphoric acid, (c) crotonic acid derivatives selected from: - grafted polymers of vinyl esters and esters of acrylic or methacrylic acid, alone or in admixture, and copolymerized with crotonic acid, grafted onto polyalkylene glycols whose terminal OH groups are optionally etherified or esterified, or grafted CH2, R3 represents CH3, C2H5 or \ asssyS R4 is the group CH3 or C2H5, X- is selected from Cl, Br, J, Q1 / 2 SO4, HSO4 and CH3SO3, and M is a monomeric group obtained by heteropolymerization using a copolymerizable vinyl monomer, and (e) the homopolymer of di methyl-d in allylamammonium chloride and copolymer: 1. the dimer of dimethyl-diallylammonium chloride and acrylamide. 5 -N H-. and Z represents the symbol B or B ', which may be the same or different and is an optionally substituted with hydroxyl groups of 1 kylene group which may otherwise contain oxygen, nitrogen and sulfur atoms and 1-3 aromatic and / or 10 heterocyclic rings. ; polymers of the formula -A-Zi-A-Zi- wherein A is as defined above and 1 \ denotes the symbol Bj or B'i and at least once B'i, where B1 is an alkylene or hydroxyalkylene group, and B is an all kylene group optionally substituted by one or more hydroxy groups and optionally interrupted by one or more nitrogen atoms which is substituted by an alkyl chain optionally interrupted by a nitrogen atom and optionally having one or more hydroxy groups. and / or carboxy groups; and polymers of the formula -A'-Z'-A * -Z * -, wherein A 'represents a mixture of the groups: 20 __ j-1 -N N- and - + N N- \ - / j \ _ / CH 2 C00-25 and Z 'have the meaning given for Bj, B, B' and B'i, and the quaternary ammonium salts and the oxidation products of -AZAZ and -A-Zi-A-Zi-, (e) the quaternary polymers: 30 1 35 on the basis of the repetition structure of the formula: 112 * DK 168059 B1 Ri R3 1. vO - N - A - N - B-- 2nX © 1Θ I® r2 r4 n 5 wherein Rj, R2 # R3 and R4 which are may be the same or different, means aliphatic, alicyclic or aryl aliphatic groups having a maximum of 20 carbon atoms or lower hydroxyaliphatic groups, or R 1, R 2, R 3 and R 4 together or separately form heterocyclic rings with the nitrogen atoms to which they are attached, another heteroatom which may be different from the nitrogen atom or wherein R 1, R 2, R 3 and R 4 form the group 16 / - CH 2 - CH \ R * 4 2Q wherein R 3 represents hydrogen or a lower alkyl group and R 4 is o 00 r'6 II II II / -CN, - C - OR15, - C - R'5, -C - N VR 6 0 0 II II -C - 0 - R'7 - D or - C - NH - R'7 - D 30 wherein R * 5 represents a lower alkyl group, R'g represents hydrogen or a lower alkyl group, R ' 7 is alkylene and D is a quaternary ammonium group, with A and B being polymethylene groups having 2-20 carbon atoms which may be straight or branched, saturated or unsaturated and optionally in the main chain may have one or more aromatic moieties. rings or one or more groupings DK 168059 B1 113 - CH2 - Y - CH2 - wherein Y represents 0, S, SO, SO2, - S - S - N R'8 5 r, 9 0 OI II II - N® - χθ - CH -, -NH-C-NE ", - C - N - IIIR 'g, OH R'8 10 O n or - C - O - R 'is hydrogen or a lower alkyl group, R'is a lower alkyl group, or A and Rj and R3 form a piperazine ring together with the two nitrogen atoms to which they are attached, B also -CH 2 -Q 2 H 2 and X 2 are one of an organic or inorganic acid derived anion, or II. with the repeating groups R1 Ri II I1 - N - A - N - (CH,) CO - B - OC - (CH,) „- | e © | e 9 2 n. 2 n 30. xix R2 2 * wherein A means a straight or branched, saturated or unsaturated alkylene or hydroxyalkylene group, B means: 1 a glycol residue of the formula -O-Z-0-, wherein Z is a straight-chain or branched hydrocarbon group or a group of the formula CH 2 -CH 2 -O- ^ CH 2 -CH 2 - or --CH 2 -CH 2 -O- - CH 2 -CH- CH 3 y CH 2 wherein x and y denote an integer 1-4, denoting a particular and uniform polymer inserted (ii) a bis-secondary diamine group, such as a piperazine derivative of the formula / \ -N N-15 \ - / (iii) a bis-primary diamine group wherein Y is a straight-chain or branched hydrocarbon group or the divalent group -CH2CH2-SS-CH2 -CH2-, or (iv) a urea group of the formula -NH-CO-NH-, denotes an alkyl a group of 1-4 carbon atoms, R2 is a straight or branched hydrocarbon group of 1-12 carbon atoms, the group R2 may also mean methylene groups linked to each other and together with A when A represents an ethylene group and the two nitrogen atoms form a divalent group derived from piperazine of formula 35 / "λ -N N- v_y DK" denotes a halide and especially bromide or chloride, and n means the number 1 or an integer between 3 and 10; (f) copolymers derived from N-vi ny1 pyrroli don of the formula: «V Mt ·» r 'ίο | I-i-CH-CH 2 - CH 2 - <—— H—— z I J a P J n L (<f = 0, y L J 0-R2-Ne (R3) 2 R4X “15 wherein n is between 20 and 99 mol%, m is between 1 and 80 mol%, p means 0 to 50 mol%, n + m + p = 100, y means 0 or 1, R 1 is hydrogen or CH 3, R 2 represents -CH 2 -CHOH-CH 2 - or c x h 2 x 'wherein x varies between 2 and 18, R 3 means CH 3, C 2 H 5 or CH 2 -, ύ R 4 represents CH 3 or C 2 H 5, X is Cl, Br, J, 1/2 SO 4, HSO 4 or CH 3 SO 4, and M is a monomer group obtained by hetero-polymer in series, (g) optionally cross-linked polyaminoamides, (h) optionally alkoxylated or alkylated polyalkyleneamines, (i) polymers containing in their chain vinylpyridine or vinylpyridine groups, (j) urea-formaldehyde resins, (k) condensates of polyamine and epichlorohydrin, (l) vinyl benzylammonium homo- or copolymers, 5 (m) quaternary polyureas, (n) dye polymers formed from a mixture of cationic, water-soluble polymers with secondary or tertiary amino groups or quaternary ammonium groups, either part of or serves for the direct or indirect attachment of compounds which carry chromophores or chromogenic aryl groups or arylal in in groups, provided that when the main chain has amino groups which form part of the aforementioned carrier compounds, it necessarily has at least 15 additional at least 10% aliphatic amino groups relative to the chain's total number of amino groups. R 15 represents hydrogen or COOH, and R 5 represents hydrogen or CH 3 when p = 0, or R 8 represents hydrogen, and R 10 COOH when p = 1 - a monomer formed from maleic anhydride and optionally 10 other monomers, (g ) stained polymers based on maleic anhydride paint. Agent according to claim 4, characterized in that the polymer of ethylene-α- / 3-carboxylic acid is selected from: (a) copolymers with compounds capable of polymerization and containing a = C = CH 2 group selected from vinyl esters, vinyl ethers with C 1 -C 4 alkyl groups, phenyl-vinyl derivatives and acrylic acid, (b) C 1 -C 8 semi or semesters of the above copolymers, (c) copolymers with an olefin of 2 to 4 carbon atoms partially esterified with an alkanol; D) copolymers with an allyl or methalyl ester monomer esterified with an aliphatic alcohol or amidified with an aliphatic, cyclic or heterocyclic amine, or terpolymers with an allyl or methalyl ester and an acrylamide or 5 methacrylamide, whose anhydride groups are mono-esterified or monoamidated, even 11 copolymer in series with α-defines, vinyl ethers, acrylic or methacrylic acid esters and optionally acrylic or methacrylic acid or N-vinylpyrrolidone; E) ter, tetra and pentapolymers of: - a monomer of the formula: R1 R2 I I CH2 = c - C - NH - C - (CH2) n - CH3 (15) 15. ii I 0 R3 wherein R 1, R 2 and R 3 are hydrogen or methyl and n has the value 0 or is an integer from 1 to 10, 20 - a water-soluble monomer of the formula: R 1 R 4 - CH = C - (CH 2) m - CON - Z - OH (16) R5 wherein R 'is hydrogen or methyl, Z is a straight or branched alkylene group optionally substituted with 1 or 2 hydroxymethyl groups, m = 0 or 1, R4 represents the hydrogen or -CORg wherein Rg is OH or -NH -R7, R7 is hydrogen or -Z-OH, and R5 is hydrogen or CH3 when m = 0 or R4 is hydrogen and R5 is -CORg wherein Rg has the meaning given above when m = 1; -maleic anhydride, (f) polymers obtained by polymerization of: - a monomer of formula (15), - a monomer of formula: 107 CH 16 - CH = C - (CH 2) p - CONH 2, r 16 wherein 5 On azotated polyal chylene Tycoal oxides; the grafted and crosslinked polymers obtained by copolymerizing a nonionic monomer, crotonic acid, polyethylene glycol and a crosslinking agent; - terpolymers derived from crotonic acid, vinyl acetate, an allyl or methallyl ether of formula I1 r2 - c - c - o - ch2 - c = CH2 (11) I Π I CH3 o R 'wherein R' means a hydrogen atom or a Represents a saturated, straight or branched hydrocarbon chain having 1 to 6 carbon atoms; and r 2 means either the -CH 3 group or the group -CH (CH 3) 2; - tetra- and pentapolymers obtained by copolymerization of: • crotonic acid, • vinyl acetate or vinyl propionate, • an allyl or methallyl ester of formula (11), • a monomer selected from: - a vinyl ether of formula CH2 = CH - 0 - R3 wherein R3 represents an alkyl group, - a fatty acid chain of fatty acid chain of formula 103 wherein R4 means a straight chain alkyl group having 7 to 11 carbon atoms, - an allyl or methyl ester of formula: R5 - C - O - CH2 - C = CH2 II I 0 R 'wherein R * represents a hydrogen atom or a methyl group and R5 represents an alkyl group; terpolymers of vinyl acetate, crotonic acid and of vinyl esters of an aliphatic saturated monocarboxylic acid branched at the α-position and containing at least 5 carbon atoms in the carboxy group; 10. copolymers obtained by copolymerization of: - esters of unsaturated alcohols and saturated short chain acids, esters of saturated alcohols of short chain and unsaturated acids, esters of crotonic acid, esters of long chain acids and unsaturated alcohol, esters of unsaturated acids and a saturated or unsaturated alcohol of 8 to 18 carbon atoms or a lanolin alcohol, all alkyl vinyl ethers, alkyl allyl ethers, alkyl methallyl ethers, alkyl crotyl ethers and α-olefins; - copolymers of crotonic acid with ethylene, vinylbenzene, vinylmethyl ether and acrylamide and water-soluble salts thereof; 20. copolymers of viacetate / crotonic acid with acrylic or methacrylic acid esters or an alkyl vinyl ether; - copolymers of vinyl acetate / crotonic acid and a monomer selected from long carbon long vinyl, allyl and methalyl esters; (D) acrylic or methacrylic acid, the polymer being selected from: - graft copolymers obtained by grafting vinyl esters, acrylic or methacrylic acid esters, individually or in admixture 5 and copolymerized with acrylic or methacrylic acid, on a -ethered or esterified polyalkylene glycol, or on an oxide of a nitrogen-containing polyalkylene glycol; grafted and crosslinked polymers obtained by copolymerization of a nonionic monomer, acrylic or methacrylic acid, polyethylene glycol and a crosslinking agent; - ter-, tetra-, penta- and higher polymers of a monomer of formula R 1 R 2 I I CH 2 -C-C-NH-C- (CH 2) n - CH 3 (15) 0 R 3 wherein R 1, R 2 and R 3 are hydrogen or methyl and n has the value 0 or is an integer from 1 to 10; - a water-soluble monomer of the formula R * R4 - CH = C - (CH2) m - CON - Z - OH (16) R5 2Q wherein R 'represents hydrogen or methyl, Z represents a straight-chain or branched-chain alkylene group optionally is substituted by one or two hydroxymethyl groups, m has the value 0 or 1, R4 is hydrogen or -CORg (R® = OH or -NH-R7, R7 means hydrogen or -Z-OH), R5 represents hydrogen or methyl, when m = 0, or R4 is hydrogen and R5 is -COR5 when m = 1; -acrylic or methacrylic acid, optionally together with one or more copolymerizable monomers; B1 N-tert-butyl acrylamide, N-isopropyl acrylamide / acrylamide, methacrylamide / acrylic and methacrylic acid / N-vinylpyrrolidone ter polymers; water-soluble polymers of acrylic and methacrylic acid and copolymers of acrylic or methacrylic acid with a monoethylenically unsaturated monomer; polyacrylamides containing carboxylate groups; and - copolymers of 40 to 90 mol% vinylpyrrolidone, 40 to 50 mol% vinyl ester and 20 to 30 mol% acrylic or methacrylic acid; (E) ethylene α- / 3-carboxylic acid, (f) allyloxyacetic acid, methallyloxyacetic acid, 3-allyloxy-propionic acid, allyl thioacetic acid, allylaminoacetic acid, vinylacetic acid, vinyloxyacetic acid, crotyloxyacetic acid, 4-butene acid, 3-butene acid, 10-undecenoic acid, allyl malonic acid, maleamic acid, itaconamic acid or N-mono- or N-dihydroxyalkyl-maleamic acid or itaconamic acid, with the exception of anionic homopolymers of acrylic acid cross-linked with an allyl ether of sucrose or pentaerythritis . Agent according to claim 4, characterized in that the anionic polymer is selected from: (a) grafted and cross-linked copolymers obtained by copolymerization of: - at least one non-ionic monomer, 20. allyloxyacetic acid or vinylacetic acid, - polyethylene glycol and a crosslinking agent; (b) copolymers obtained by copolymerization of: - an ester of unsaturated alcohol and saturated short chain carboxylic acid, or of esters of unsaturated short chain alcohols and unsaturated acids, - an unsaturated acid selected from 3- butenoic acid, 4-pentenoic acid, 10-undecenoic acid, allylmalonic acid, allyloxyacetic acid, crolyloxyacetic acid, methallyloxyacetic acid, 3-allyloxypropionic acid, allylthiacetic acid, allylaminoacetic acid and we new oxyacetic acid or acetic acid or acetic acid in acetic acid, esters of the above unsaturated acids and a saturated or unsaturated, straight or branched alcohol, (c) tetra or pentapolymers obtained by copolymerization: - of allyloxyacetic acid, - of vinyl acetate or vinyl propionate, - a monomer selected from: a vinyl ether of formula 5 CH 2 = CH-O-r 3 wherein R 3 represents an alkyl group, a vinyl ester of fatty acid chain of formula R 4 -C-O-CH = CH 2 II 0 wherein R 4 represents a straight-chain alkyl group having 7 to 11 carbon atoms; and an allyl or methalyl ester of the formula r5-c-o-ch2-c = ch2 11 11 R 'wherein R' is a hydrogen atom or a methyl group and R5 is an allyl group; (D) copolymers obtained by copolymerizing: - at least one monomer of formula (15); - N-mono- or di-hydroxyalkylmaleamine or itaconamine acid, - N-vinylpyrrolidone or acrylates or methacrylates of the formula ch2 = c - coo (ch2 - ch2 - o) je R "(17) R 'wherein R 'is hydrogen or methyl, 1 = 3 or A, and R "is methyl or ethyl and optionally another monomer; DK (e) copolymers obtained by copolymerizing: - at least one monomer of formula (15), as defined in claim 5, - maleamic and itaconamic acid, - monomers of formula (16) as defined in claim 5, or 5 of formula (17), as defined above, and optionally additional monomers. Agent according to claim 4, characterized in that the anionic polymer is selected from polymers having at least one sulfonic acid group, selected from salts of polystyrene sulfonic acid and salts of alkali or alkaline earth metals with sulfonic acids derived from lignin. An agent according to claim 4, characterized in that it contains as an anionic polymer a monoethyl ether, a mono-isopropyl ester or a monobutyl ester of poly (methyl vinyl ether / maleic acid), a copolymer of acrylic acid or methacrylic acid in the form of the alkali salt with vinyl alcohol, ter polymers of vinyl acetate, crotonic acid and vinyl ester of a saturated aliphatic monocarboxylic acid which is branched at the α position and has at least 5 carbon atoms in the hydrocarbon group, corresponding to the following formula, R 1 - 25 - R 3 - C - C - OH R 2 wherein R 1 and R 2 are an alkyl group and R 3 is hydrogen or an alkyl, alkyl aryl, aralkyl or aryl group. 30 An agent according to claim 4, characterized in that the cationic polymer is selected from: (a) quaternary cellulose ether levels; (B) water-soluble cyclopolymers selected from homo- or copolymers of the formula DK 168059 B1 110 Ί Γ / Cii2. --CH2-ac \ | κ- --ch2-r "c Nk ·· -. S * jli (2) (21) 10 wherein R" means hydrogen or methyl and R and R 'independently represent an alkyl group with 1-22 carbon atoms, a hydroxyalkyl group or an amidoalkyl group and wherein R and R 'together with the nitrogen atom to which they are attached may form one in a heterocyclic group such as piperidinyl or morpholinyl. compound with a cosmetically acceptable anion; (c) cationic homo- or copolymers derived from acrylic or methacrylic acid having groupings 20 R, R, R, -CS-C— _CH-C-or-_CH -4 - c = o c = o c = o I I I 25. O NH An agent according to claim 4, characterized in that the crosslinked polyaminoamide is selected from: (a) crosslinked polyaminoamides optionally alkylated and obtained by crosslinking a polyaminoamide produced by polycondensation of an acid foil A compound or an acidic compound with a polyamine, with a cross-linking reagent selected from epihalohydrin, deep oxide, dianhydride, unsaturated anhydride or bis-unsaturated derivative in an amount between 0.025 and 0.35 mol per amino group in the polyaminoamide , (B) water-soluble cross-linked polyaminoamides obtained by cross-linking a polyaminoamide of the above defined with a cross-linking reagent selected from I bishalohydrin, bis-azetidinium compounds, bishalogenacyl diamines and alkyl bishaloids, II oligomers obtainable by reacting a compound of group I or of epihalohydrin, deep oxides or bis-um related derivatives having a bifunctional compound which can react with these compounds, the III quaternization product between a group 5 I compound and group II oligomers having tertiary amino groups which can be alkylated with an alkylating agent in an amount of 0.025 to 0; 35 moles per amino group in the polyaminoamide; c) water-soluble polyaminoamide derivatives obtained by condensing polyalkylene polyamines with polycarboxylic acids and subsequent alkylation with bi-functional 11e reagents of formula R, Rj R ^ Rn \ / 2 \ / A - ca2 - N - B - N - CH2-A (x + 1) Q - + + x 20 where x means an integer between 0 and 7, A denotes a - CH - CH2 - or - CH - CH2 group, µl 0 OH R 3 R 3 is halogen, R 1 and R 2 represent a lower alkyl or hydroxyalkyl group, Q- is halogen, sulfate or methosulfate, B is an alkylene group or a -CH 2 -CH-CH 2 - or - (CH 2) γ- NH-CO-NH- (CH 2) γ group, OH 30 and γ are an integer between 1 and 4, and (d) polymers obtained by reaction of a polyalkylene-polyamine having two primary amino groups and at least one secondary amino group, with a dicarboxylic acid selected from diglycolic acid and aliphatic saturated dicarboxylic acids having 3-8 carbon atoms, the molar ratio of polyalkylene polyamine to DK 168059 B1 118 di carboxylic acid being between 0.8: 1 and 1.4: 1 and the resulting polyamide is reacted with epichlorohydrin in a molar ratio of epichlorohydrin to the secondary am of the polyamide in a neat group between 0.5: 1 and 1.8: 1. 5 An agent according to claim 4, characterized in that the cationic polymer is selected from: (a) quaternary cellulose ethers of the formula: 10 R R R * I I I ° χΐ 0 (1) RCell y wherein Rcell is the remainder of an anhydroglucose group, y means a number between ca. 50 to approx. 20,000 and each R independently of xO each other means a substituent of the following general formula: (CaH2a-O-) m- (CH2-CH-O-) n- (CbH2b-O-) p- (CcH2c) q -R * CH2 L1, .s R3 - N® * Ri φ (X) V r2 wherein a is an integer of the meaning 2 or 3, -.qb is an integer of the meaning 2 or 3, c is an integer of the meaning 1-3 is an integer of 0-10, n is an integer of 0-3, P is an integer of 0-10, q is an integer of 0 or 1, and R 1 is a group of the formula o II II II II -H, -C-OH, -CO-Na, -COK or -CO-NH 4, 119 UK lOBUBB B l with the proviso that when q equals zero , R 1 is -H, R 1 R 2 and R 3 are independently an alkyl, aryl, aralkyl, alkaryl, cycloalkyl, alkoxyalkyl or alkoxyaryl group, each of which may contain R 1, R 2 and R 3 up to 10 carbon atoms, with the proviso that when an alkoxyalkyl group is present, it has at least 2 carbon atoms separating o the oxygen atom from the nitrogen atom, and with the proviso that the total number of carbon atoms in the groups denoted by R 1, R 2 and R 3 is between 3 and 12, with R 1, R 2 and R 3 together with the nitrogen atom to which they are 16 attached, form one of the following groups: pyridine, α-methyl-pyridine, 3,5-dimethylpyridine, 2,4,6-trimethylpyridine, N-methylpiperidine, N-ethylpiperidine, N-methylmorpholine or N-ethylmorpholine, : 0 X is an anion, V is an integer equal to the valence of X, and the mean value of n for the anhydrogluco group of this cellulose ether is between 0.01 and ca. 1, whereby the mean value (m + n + p + q) of the anhydroglucose group of this cellulose ether is between ca. 0.01 and approx. 4, in '5 (b) vinyl pyrrolidone copolymers of the following formula [c -J-CH-CH.JU C Hi C - [MJ- (C_ ° i I Φ O - R, -N (Rj) j R ,, X "4n. * '> Where n is between 20 and 99, preferably between 40 and 90 mol%, and m is between 1 and 80, preferably between 5 and 40, 120 mol%, P is 0-50 mol%, and n + m + p = 100, means hydrogen or CH 3 , y represents 0 or 1, R 2 represents the group -CH 2 -CHOH-CH 2 - or C x H 2 x, where x = 2-18; Agent according to one or more of the preceding claims, characterized in that it further contains amphoteric or nonionic polymers. / 0 Agent according to one or more of the preceding claims, characterized in that it contains a surfactant in an amount of 0.1 to 70%. '5 Agent according to one or more of the preceding claims, characterized in that it is conditioned as an aerosol. An agent according to one or more of the preceding claims, characterized in that it is present as a lotion for hair conditioning. 35