DK163478B - Cosmetic Hair Care Containing A Cationic Polymer - Google Patents

Description

in

DK 163478B

BACKGROUND OF THE INVENTION The present invention relates to a hair care agent to provide enhanced shine and softness and to easier hair styling, comprising 5 (1) a cationic. polymeric film having a molecular weight between 500 and 15,000 and consisting of repeating units of formula - A - Z - (I) 10 wherein A represents a group containing amino groups and Z represents one or two divalent groups selected from unsubstituted alkylene groups and α 1 alkylene groups, substituted by one or more hydroxy 1 groups, of which divalent groups at least one is interrupted by one or more nitrogen atoms, (2) a quaternary ammonium salt of a polymer consisting of repeat units of formula (I), or 20 (3) a polymer comprising repeating units of formula (I) wherein the amino group is oxidized to form an amine oxide group.

From Danish Patent Specification No. 134,141, a hair care agent containing polymeric cationic film formers of the general formula -AZAZAZ- (I) 30 is known in which A represents ^ a group of two amine functions, preferably the group -N N-, and Z represents the symbol B or B ', where B and B', which are the same or different, denote a divalent group which is a straight or branched chain alkyl group containing up to 7 carbon atoms in the main chain and which is unsubstituted or substituted by one or more hydroxyl groups and may further contain oxygen, nitrogen and sulfur atoms, 1-3 aromatic and / or heterocyclic rings.

2

DK 163478B

the oxygen, nitrogen and sulfur atoms being present in the form of ether, thioether, sulfoxide, sulfone, sulfonium, amine, alkylamine, alkenylamine, benzylamine, amine oxide, amide, imide, , alcohol, estei and / or urethane groups.

5

The known hair care agents may further contain quaternary ammonium salts as well as the oxidation product of a polymer of the above formula.

The use of these polymers makes it possible to limit or modify the disadvantages that result from the general state or from sensitizing treatments, such as decolorization, permeability or staining.

The hair care agent of the present invention is property in that A denotes either the group: - NN - V_ / 20 or a mixture of the groups: / N-N, N - and -N N- \ -y iv- / ch 2 COOE or the groups formed by quaternization, and Z represents either the group B * or B1 ', and including at least once B1' or the group formed by beatinization or quaternization of B1 or the mixture of these groups, wherein B1 is a divalent group which is a straight or branched chain alkylene group containing up to 7 carbon atoms in the main chain which is unsubstituted or substituted by one or more hydroxyl groups and interrupted by one or more nitrogen atoms substituted by an alkyl chain advantageously containing 1-4 and preferably 4 carbon atoms, the alkyl chain being optionally interrupted by an oxygen atom and mandatory 3

DK 163478 B

carries one or more hydroxyl or carboxyl functions, and B1 represents a divalent group which is a straight or branched chain alkylene group containing up to 7 carbon atoms in the main chain substituted with a hydroxy 1 group and preferably a 2-hydroxypropylene -l, 3-diyl group.

These polymers, like the polymers known from the above disclosure, exhibit properties which make them suitable for care and conditioning of the hair. However, in addition to conditioning benefits, such as improved moisturizing, improved gloss, improved softness and light hair, the polymers used in hair care diets, according to the present invention, have improved compatibility with surfactants commonly used in hair care products. , 15 especially against an in on in surfactants.

The difference between the polymers used in the hair care agents known from Danish Patent Specification No. 134,141 and the polymers used in the hair care agents of the invention consists in the fact that the cationic polymer contained in the hair care agents of the invention always comprises the group βΐ and none of the the groups (A, B and B ') included in the polymer contained in said known hair care agents are equal to the group B1.

B 1 'is an alkylene group which is unsubstituted or substituted by one or more hydroxy 1 groups and is interrupted by one or more nitrogen atoms, said nitrogen atoms being substituted by an alkyl group optionally interrupted by an oxygen atom and containing one or more several hydroxyl and / or carboxyl groups. This means that B1 'represents an alkylene group interrupted by at least one nitrogen atom substituted by an alkyl group which must contain one or more hydroxyl and / or carboxyl groups. In the polymers known from said disclosure, the nitrogen atom capable of interrupting the alkylene chain of group B or B 'may be substituted by an alkyl group but not by an alkyl group containing one or more hydroxyl and / or carboxy groups.

4

DK 163478 B

Due to the presence of the group B * ', the cation contained in the hair care agents according to the invention has improved properties over the known polymers and has especially improved compatibility with other surfactants.

The measurement of this improved compatibility is done as follows.

A solution I containing 3.5 g of polymer and 125 g of a 40% lauryl sulfate solution of tri-ethanolamine is prepared, and up to 250 g is made up by the addition of distilled water.

25 g of this solution I are taken and a 10% solution of sodium chloride in water is added dropwise, until a cloudiness occurs.

The number of ml of sodium chloride solution added is then noted. The greater this amount, the greater the compatibility of the polymer 20 with the anionic surfactant.

As a control example, the compound of Example 1 is used in Danish Patent Specification No. 134,141, which compound is the preferred compound (and the one most commonly used in the embodiments).

With this known compound, the compounds of the following Examples 3, 6 and 7 have been compared.

30 The results obtained by comparison are shown in the table below.

Measurement of compatibility with anionic surfactant.

35 5

DK 163478 B

Compound ml added NaCl solution

Compound of Example 1 of Presentation 5 No. 134,141 (control compound) 4.1

Compounds contained in the hair care agent of the invention: Compound of Example 3 20

Compound of Example 6 17

Compound of Example 7 15 15

These comparative tests show that the compounds contained in the hair care agent of the invention have a compatibility with anionic surfactants which is four to five times as high as the compatibility preferred compounds of 20 in presentation specification No. 134,141.

The cosmetic hair care agent may further contain the oxidation product of a polymer consisting of repeating units of formula I, preferably obtained by hydrogen peroxide or by a peracid, or the quaternary ammonium salt of a polymer consisting of repeating units of formula I.

Furthermore, it has been found that cosmetic hair care agents containing a polymer consisting of repeating units of formula - A - Z - (I) can be improved by using quaternary ammonium salts of the said polymers obtained by quaternizing the basic groups with chloroacetic acid or a chloroacetate, e.g. sodium chloroacetate.

6

DK 163478 B

It has been found that the compatibility of the thus quaternized polymers has improved with the anionic surfactants commonly used in said hair care agents.

5

In particular, the preferred polymers for use in the hair care agent of the invention are polymers consisting of repeating units of the formula - A - Z - (I) 10, where A represents the group - NN and Z represents B * or B * and at least once represents group B1, including polymers consisting of repeating units of formula (I), wherein the nitrogen atom of B11 is substituted by a carboxymethyl group, a 2-5-15 hydroxyethoxyethyl group, a 1,3 dihydroxy-2-methyl-2-propyl group or a 1-hydroxy-2-methyl-2-propyl group.

The cation in spherical polymers contained in the hair care agent of the invention can be prepared by direct or indirect polycondensation.

The direct polycondensation consists of reacting piperazine and a hydroxylated amine such as diglycolamine or 2-amino-2-methyl-1-propane-1,3-diol, or an amino acid such as aminoacetic acid with an epihalohydrin such as epichlorohydrin or epi -bromohydri n, in aqueous medium, under addition of sodium to take up the released hydrogen acid, and then heated to a temperature between 80 and 90 ° C.

The indirect polycondensation consists initially of preparing an intermediate X, which is obtained by reaction of epihalogen hydrin with either piperazine, the hydroxylated amine and / or amino acid. This intermediate X is then reacted with another amine. Optionally, the epi halo hydrogen is added, a base such as sodium hydroxide added, and heated to a temperature between 80 and 90 ° C.

7

DK 163478 B

The usable amounts of piperazine, epihalohydrin and hydroxylated amine and / or amino acid depend on the order of the theme of B * and B * 'which one wishes to obtain in the final polymer.

5

The epihalohydrin and the mixture of piperazine, hydroxylated amine and / or amino acid are preferably present in equimolar amounts. For the mixture piperazine-hydroxylated amine and / or amino acid, this molar amount containing 10 contains between 90 and 50¾ piperazine and 10 to 50% hydroxylated amine and / or amino acid.

The polymers thus obtained can be oxidized by hydrogen peroxide or peracids, or as quaternized with known quaternizing agents, such as lower alkyl bromide, chloride, iodide, sulfate, mesylate or tosylate, preferably methyl, as described in the aforementioned Danish publication specification. -or the ethyl compound, or benzyl chloride or benzyl bromide.

20

A quaternization which has proved particularly advantageous in terms of the compatibility of the resulting polymer with anionic surfactants is the "betainization" of the compounds of formula I, which consists in the quaternization of 25 to 66% of the basic quaternizable groups with sodium. chloroacetate or chloroacetic acid. The yield from the turnover is generally between 60 and 100%.

The degree of "betaineization" can be defined as the ratio of the number of quaternized nitrogen equivalents to the total number of quaternizable nitrogen equivalents multiplied by 100.

The quaternization yield of the reaction can be defined by the ratio of the number of actually quaternized nitrogen equivalents to the number of equivalents used quaternizing agent multiplied by 100.

8

DK 163478 B

It has been found that only the two tertiary nitrogen atoms in group A are readily quaternizable. By betainization sequences corresponding to the formula 5 - A '- Z' - (II) / \ / - \ in which A 'is a mixture of the groups -N N- and - + N N-, V_ / | V_7' ch 2 are obtained And Z 'represents or βΐ', or the group obtained by betainization of B1 ', since it contains one or more basic nitrogen atoms which may have the formula

15 L

-N © - ch2 C00 ”20

It has been found that the polymers contained in the hair care agent of the invention and prepared according to any of the above methods are film-forming and having a relatively low molecular weight, i.e. a molecular weight of less than 15,000.

25

They are soluble in water or in aqueous-alcoholic medium.

They are especially useful for hair that is made sensitive after treatments, such as dyes, perms or stains, but can also be advantageously used for normal hair.

30

The polymers are incorporated in amounts of 0.1 to 5% and preferably 0.2 to 3% by weight of the agent in various cosmetic agents, such as lotions, creams or hair gels, as the main ingredient, and furthermore in shampoos, cosmetics, cosmetics and cosmetics. 35 fixative fixatives, staining agents, etc., counted as auxiliaries in the presence of other compounds such as anionic, cationic, nonionic, amphoteric or zwitterionic supernatants.

DK 163478 B

surfactants, oxidizing agents, synergistic active agents, foam stabilizers, sequencing agents, fats, thickeners, plasticizers, antiseptics, preservatives, dyes, perfumes and germicides. They can be used in admixture with other anionic, cationic, amphoteric or nonionic polymers.

Depending on the pH value in use, which is between 3 and 11, the polymers may be present in various agents in the form of 10 salts of inorganic or organic acids or in the form of free or quaternary bases.

Furthermore, the cosmetic hair care agents of the invention may be in the form of aqueous, aqueous-alcoholic or alcoholic solutions, creams, pastes, gels or powders. They may further contain a propellant and be contained in an aerosol container.

The hair care agent in the form of a hair shampoo may contain, without an anionic, cationic, nonionic, amphoteric and / or zwitterionic surfactant, one or more compounds consisting of repeating units of formula I as well as optionally synergistic foam stabilizers, sequestering agents, superficial agents. , thickeners, one or more cosmetics in spoon resins, plasticizers, dyes, perfumes, bactericides, preservatives and any other adjuvant commonly used in cosmetics.

The polymers of formula (I) further enable the preparation of 30 oncotic fluids, treatment creams, hair conditioners, anti-scaling lotions and other similar agents, characterized in that they contain one or more polymers of formula I and having a molecular weight as determined by vapor pressure lowering is between 500 and 15,000.

35

The following Examples A1 - A14 illustrate the invention further, while Examples 1-11 illustrate the preparation of the polymers which

DK 163478 B

used in the composition of the invention. The parts listed are parts by weight.

Example 1 First Step - Preparation of the Intermediate: E, E-Bis / β-hydroxy-γ-ehloro-propyl / diglycolamine of the formula.

C1CH2 - CHOH - CH2 - E - CHg - CHOH - CH2C1 CH9 10 1 2

ch2 - 0 - CH2 - CH20H

hereinafter referred to as intermediate X.

To a solution of 420 g of diglycolamine (4 moles) in 2700 g of water is added dropwise with stirring 740 g (8 moles) of epichlorohydrin over 1 hour at 10-15 ° C.

After 4 hours of stirring the reaction mixture at 20 ° C, the epoxide = groups have virtually disappeared.

20

Thus, a clear, very faint greenish solution with 30 $ solids is obtained.

The second step - preparing a polymer of type 25 - A - Z - / vii * wherein A represents -E_E-, Z represents B or B, B represents -CH2-CHOH-CH2-, B1 'represents -CH2-CHOH -0H2-E-CH2-CHOH-CH2-, and in which CH? In 2 ch2-o-ch2-ch2oh the ratio of the groups A / B ^ / B ^ is 4/1/3 (the molar ratios piperazine / diglycolamine / epichlorohydrin are 4/1/5).

35

To 775 g of piperazine hexahydrate (4 moles) is added while maintaining the temperature 20 ° C 965 g (1 mole) of a solution of the intermediate X prepared as above. 277 g (3 moles) of epichlorohydrin are then added, still at a temperature of 20 ° C. One is then added in

n DK 163478 B

over 1 hour 500 g (5 moles) of a 40 $ sodium hydroxide solution.

It is then heated to 80-90 ° C and kept at this temperature for 1 hour.

By adding 1130 g of water, a solution of 20 $ of active material is obtained.

Example 2

Direct preparation of a polymer of type - A - z in which the symbols A and Z have the same meaning as in Example 1, but where the distribution of piperazine and diglycolamine is statistical.

The ratio of the groups A / B1 / B1 is 4/1/3 as stated above.

The same molar amounts of piperazine, diglycolamine and epi = chlorohydrin are used as in Example 1, i.e. 4/1/5.

To 161 g of piperazine hexahydrate (0.83 mol) and 21 g of diglycolamine (0.2 mol) dispersed in 140 ml of water are added over one hour and at 20 ° C 92.5 g of epichlorohydrin (1 mol). One hour after the addition, 100 g of 40 $ sodium hydroxide (1 mol) is added dropwise and still at 20 ° C. It is then heated to 80-90 ° C, which is kept for 1 hour.

The reaction medium is then diluted with 227 ml of water to give 25 a 20 $ solution of active material.

The solution thus obtained is colorless and its viscosity measured at 25 ° C is 0.07 Pa.s.

Example 3

Preparation of a polymer of the type - A - Z - in which A represents and Z represents B1 ', B1' represents -CH2-CHOH-CH2-N-CH2-CHOH-CH2-OOH in ά ch2-o-ch2- CH 2 OH.

The ratio of the groups A / B ^ 'is 1/1.

The mole ratio of piperazine / diglycolamine / epichlorohydrin is 1/1/2.

12 DK 163478 B

To a solution of 1 mole (194 g) of piperazine hexahydrate in 742 g of water is added dropwise over 1 hour at 20 ° C with stirring and under a nitrogen atmosphere 1 mole of intermediate X prepared according to Example 1 in the form of a 30 $ solution ( 970 g).

5

After completion of the addition, the reaction mixture is bubbled with stirring at 20 ° C for 1 hour.

Then, at the same temperature and over 1 hour, 167.5 g of 10 $ 48 sodium hydroxide (2 moles) are added.

Stirring is continued for another hour at this temperature, after which the mixture is heated for 2 hours to 80-90 ° C.

By adding 1026.5 g of water, a clear and practically colorless polyamine solution with 10 $ active material is obtained.

Example 4 First Step - Preparation of a prepolymer P, mainly assigned to the formula:

- CH2 - CH0H - CH2 - Ή - CH2 - CH0H - 0Η £ - jTjIH

0Ho I 2

CH2 - O - CH2 - CH2OH

To a solution of 776 g (4 moles) of piperazine hexahydrate in 500 g of water is added using the procedure of Example 3 2 moles of the intermediate compound X of Example 1 in the form of a 30 $ solution (1955 g).

After completion of the addition, the reaction mixture is kept under stirring at 20 ° C for 1 hour.

35 Moles of sodium hydroxide in the form of a 48 $ solution (335 g) are then added at the same temperature and over 1 hour. Stirring is continued for another hour at this temperature, after which the mixture is heated for 2 hours to 80-90 ° C.

13 DK 163478 B

Thus, a clear solution of a prepolymer P of the above formula is obtained.

Second Step - Preparation of a Polymer of the Type - A - Z in Which 5 A 'represents -IT IT-, Z "represents B *' or B" * ", B ^" represents -CH2-CHOH-CH2-, and B1 denoted- CH2 - CHOH - CH2 - ΪΤ - CH2 - CHOH - CHg gh2 ch2 - o - ch2 - ch2oh 1 * 1 10 The pore ratio between groups A / B / B is 2/1/1.

The mole ratio of piperazine / diglycolamine / epichlorohydrin is 2/1/3.

To half of the solution of prepolymer P prepared as above (1835 g) (corresponding to 2 equivalents of secondary amine) is added dropwise and with stirring, 92.5 g of epichlorohydrin (1 mole).

After completion of the addition, the reaction mixture is kept under stirring at 20 ° C for 1 hour.

20

Then 83 g (1 mole) of 48 $ sodium hydroxide are added at the same temperature and over 1 hour.

Stirring is continued for another hour at this temperature, then the mixture is heated for 1 hour to 80-90 ° C.

By adding 2625 g of water, a clear and virtually colorless polyamine solution containing 10 $ of active material is obtained.

Example 5

Preparation of a polymer of the type - A - Z - wherein A represents -IT_T-, Z represents B1 or B1 ', B1' represents -CH2-CHOH-CH2-1T-CH2-CHOH-CH2-, 35 \ E2

CH2-0-CH2-CH20H

and B1 represents -CH2-CHOH-CH2-.

14 DK 163478 B

The ratio of groups A / B3 "/ B ^ is 4/1/3.

The relative molar ratio of piperazine / diglycolamine / epihalohydrin is 4/1/5.

5

To 394.5 g of solution of the prepolymer P described above and containing 0.43 equivalents of secondary amine are added with stirring 51 g of 1,3-bis-piperazino-propan-2-ol of the formula containing 0.43 equivalents of secondary amine, i.e. corresponding to 0.215 mol. The 1,3-bis-piperazino-2-propan-2-olene can be prepared by the method described in Example 15 of the previously mentioned Danish publication.

To this solution, 39.7 g (0.43 mole) of epichlorohydrin are added over 1 hour and at 20 ° C. The mixture is stirred for 1 hour at this temperature. It is then added at 20 ° G and over one hour 35.8 g · (0.43 20 moles) of 48 $ sodium hydroxide.

After stirring for 1 hour at the same temperature, the reaction mixture is heated to 80-90 ° C over 1 hour.

By adding 1099 g of water a clear polyamine solution containing 10 $ of active material is obtained.

Example 6 Preparation of a Polymer of the Type - A - Z wherein A represents -ff ff-, Z represents B1 or B3- ', B3- represents - CH2 - CHOH - CH2 - ff - CH2 - CHOH - CH2 -,

CHOOH - C - CHOHOH

2 in CH 2 and B 2 represent - CH 2 - CHOH - CH 2 ~.

The ratio of groups A / B ^ / B1 is 1 / 0.42 / 0.56, with groups B1 and B ^ being statistically distributed.

1 'DK 163478 B

This polymer is prepared by the direct procedure of Example 2 starting from piperazine (1.07 mol), 2-amino-2-methylpropane-1,3-diol (0.45 mol) and epichlorohydrin (1.5 mol) ).

209 g of piperazine hexahydrate (1.07 mol) and 47.2 g of 2-amino-2-10-methylpropane-1,3-diol are mixed in 250 ml of water. 139 g are added over a period of 1 hour at 20 ° C. (1.5 mole) of epichlorohydrin, then 150 g of 40 $ sodium hydroxide (1.5 mole) is added and heated to 80-90 ° C, which is kept for 1 hour.

After completion of the reaction, dilute with 760 ml of water, thus obtaining a clear solution containing 20 $ dry matter.

Example 7 Preparation of a polymer of the type - A - Z - in which A represents -ff ff-, Z represents B1 or B1 ', B1' represents - CH2 - CHOH - CH2 - N - CH2 - CHOH - 0¾ -, and B1 represents

CH2 - COOH

- 0H2 - CHOH - CH2 -.

The A / B ^ / 33 ^ group ratio is 1.2 / 0.8 / 0.4, with the groups B ^ and B ^ being statistically distributed.

The relative molar ratio of piperazine / aminoacetic acid / epichlorohydrin is 1.2 / 0.8 / 2.

60 g (0.8 mole) of amino acetic acid of the formula H2ff-CH2-C00H dispersed in 218 g of water are neutralized with 80 g of 40 $ sodium hydroxide (0.8 mole).

35

To the above solution is added 233 g (1.2 moles) of piperazine hexahydrate. Then, with stirring over 1 hour and at 15-20 ° C, 185 g (2 moles) of epichlorohydrin are added.

After 1 hour of stirring at this temperature, 200 g (2 moles) of 40 $ sodium hydroxide are still added at the same temperature.

Stirring is continued for another hour at 20 ° C and then for 1 hour at 80 ° C. The solution is cooled and adjusted to $ 25 active material by the addition of 124 g of water.

16

DK 163478 B

Thus, a clear, very faint yellow-colored solution is obtained.

Evaporating a dilute solution gives a durable and slightly sticky film.

5

Example 8

Preparation of a Betainized Polymer of the Type - Al - Ζ »Where A

/ "Λ + Λ ~ \ represents a mixture of the groups -N_If- and - E_I-, and Z 'represents 10 CHO in 2 COO" B1, ie - CH9 - CHOH - CEL and the groups obtained by betaineise of B, i.e. a mixture of groups 15 - CH2 - CHOH - CH2 - N - CH2 - CHOH - CH2 - ch2 - ch2 - 0 - ch2 - ch2oh ch2 - COO "and - CH2 - CHOH - CH2 - + H - CH2 - CHOH - CH2 - · 20 ch2 - ch2 - 0 - ch2 - ch2oh.

A polymer obtained by condensing a solution of 483 g (2.49 mole) of piperazine hexahydrate, 63 g (0.6 mole) of diglycolamine, 277.5 g (3 mole) of epichlorohydrin and 120 g (3 mole) of sodium hydroxide. The solution has a viscosity of 0.075 Pa.s at 25 ° C.

/ \

This starting polymer is of the type - A - Z - where A represents -Η H-, Z represents B1 or B1 ', B1' represents - CH '- CHOH - OHo - S - CH0 - CHOH - CH' -, and B1 represents 30 2 2 in 2 2 CH0 I d ch2 - 0 - ch2 - ch2oh and denotes 35 - CH2 - CHOH - CH2: The group ratio A / B ^ / B ^ is 2.4 / 0.6 / 1.8.

To 1005 g of said polymer containing 20% of active material with a total of 2.5 nitrogen equivalents is added 157.4 g (1.34 mole) of sodium monomer.

17 DK 163478 B

The quaternization range is 70-71 $ and the viscosity of the resulting compound is 0.067 Pa.s at 25 ° C. The degree of betaineization is 37.5%, i.e. that 37.5% of the basic nitrogen atoms are in the form ch2 - C00 "5 of -

Example 9 To 1005 g of cationic polymer with 20 $ active material used in Example 8 containing a total of 2.5 nitrogen equivalents is added 78.8 g (0.67 mole) of sodium monochloroacetate and heated to 85-100 ° C over 5-6 hours. The quaternization range is $ 71 and the viscosity after the reaction is 0.06 Pa.s at 25 ° C. The degree of betaineization is 15 19%.

The betaine polymer is of the same type as that of Example 8 and differs only in that $ 19 of the basic nitrogen atoms is in the form of - Ir -

20 I

ch2 - coo

Example 10

Quaternization with the dimethyl sulfate of the compound of Example 2, 25/1 in which A represents -H IT-, Z represents B or B, B represents - CH2 - CHOH - CH2 -, and B1 represents - CH2 - CHOH - CH2 - N - CH2 - CHOH - CHg -.

CHp - CHp - 0 - CH «- CH« - OH 30

The quaternized polymer consists essentially of the two following groups in the ratio 80/20: - if ~ H + - 0Eo - CHOH - CH0— \ _Λ 2 2 35 ηττ _

Owl3 S04CH3

18 DK 163478 B

±-3 SO 4 CH 3 "- ± 1 - CHo - CHOH - O

5 CH2 - 0 - CH2 - CH2 - OH

To 1082 g of aqueous solution containing 27 $ of the polymer prepared according to Example 2, wherein 80 $ of the sodium chloride has been removed by dialysis and containing 3.37 nitrogen equivalents, is added with stirring and at a temperature lower than 30 ° C 254. 5 g (2.02 mol) of dimethyl sulfate. After 3 hours of stirring at this temperature, the solution of 30 $ active material is adjusted by the addition of 485 g of water.

The film obtained by evaporation of an aqueous solution is durable and slightly sticky.

Example 11

Preparation of a Polymer Quaternized by Dimethyl 20 Sulfate and Consists of the Following Two Groups: CH 2 CH 2 SO 4 CH 5 - H 3 SO 4 CH 3 - / - V - CH

-p— / -r c- i c. i c. c

0H CH0 25 S04CH3 I ά

L ^ -5 J 0H2 - 0 - CH2 - CH £ 0H

in the ratio approx. 80/20.

To a mixture of 141 g (1.64 mole) of pipsrazine and 42 g (0.4 mole) of di = 30 glycolamine dissolved in 300 ml of methanol is added with stirring and over 1 hour at 20 ° C 185 g (2 mole) epichlorohydrin, after which the reaction mixture is heated for 30 minutes under reflux of the solvent.

During 2 hours while still warming under reflux of methanol, 360 g (2 moles) of a 30 $ sodium methylate solution in methanol are added. The sodium chloride is removed by filtration.

in

19 DK 163478 B

261 g of the above solution containing 0.942 nitrogen equivalents is heated under reduced pressure to remove the methanol. 200 ml of dimethylformamide are added.

To this new solution is added 119 g (0.942 mol) of methyl sulfate and then the reaction mixture is heated with stirring for 4 hours at 90 ° C.

By dropwise adding this solution to a large excess of acetone, the polymer is isolated in the form of a very hygroscopic powder.

10

The pill obtained by evaporation of an aqueous solution is transparent, durable and non-sticky.

Example A 1 15

Anionic Shampoo:

Compound of Example 5 .......................... 1 g of lauryl sulfate of triethanolamine ............... .......... 15 g 20 diethanolamide of coconut oil ............................. 3 g lactic acid up to pH 7.4 water until ............................................ 100 g

Example A 2 Anionic Shampoo:

Compound of Example 4 .......................... 1> 2 g disodium halvestersulfosuccinate of modified alkanoamide ........... ................................. 10 g of sodium lauryl ether sulfate condensed with 2.2 moles of ethylene oxide ...... .................................... 15 g of diethanolamide of coconut oil ......... .................... 4 g of water until .......................... .................. 100 g of pH is 7.

35

Example A 3

Shampoo:

DK 163478 B

Compound of Example 5 ......................... 0.75 g of 5 lauryl alcohol polyethoxylated with 12 moles of ethylene oxide .. 12 g of diethanolamide of coconut oil ... ......................... 4 g trimethylcetylammonium bromide ...................... .... 0.5 g citric acid up to pH 4 10 water until ................................... ........ 100 g

Example A 4 Shampoo: Compound of Example 3 ......................... 1 g of sodium lauryl ether sulfate condensed with 2.2 moles of ethylene oxide ..... ...................................... 10 g of alkylimidazoline of the formula ° ** 0Η2 - COO Ha 20 ΟίίΗ07 - C-TS (j'j oH 0 ^ 2 - ch2 - 0 - CH2 - COOTa 2 25 sold under the designation "Miranol C2M" ................. 2 g monoethanolamide of coconut oil ......................... 1.5 g lactic acid up to pH 7.5 water until ......... .................................. 100 g 30

Example A 5 Shampoo:

Compound of Example 4 ......................... 1.5 g of lauryl alcohol polyethoxylated with 12 moles of ethylene oxide. 8 g of the sodium salt of H- (H ', H'-diethylaminopropyl) -N-dodecylasparagine ...................................... 4 g of coconut oil diethanolamide ............................ 2 g of lactic acid up to pH 5

21 DK 163478 B

Example A 6

Anionic Shampoo:

Compound of Example 2 ......................... and 5 lauryl sulfate of triethanolamine ................ ........ 10 g of sodium lauryl ether sulfate ethoxylated with 2.2 moles of ethylene oxide ................................ ........... 10 g diethanolamide of coconut oil ............................ 3 g 10 water until. .......................................... 100 g pH = 8

Example A 7 15 Anionic Shampoo:

Compound of Example 8 1 g of lauryl sulfate of triethanolamine ........................ 10 g of sodium lauryl ether sulfate ethoxylated with 2.2 moles of 20 ethylene oxide ...... ..................................... 10 g of diethanolamide of coconut oil ........ .................... 3 g of water until .......................... ................. 100 g pH = 7.5 25

Example A 8 Anionic Shampoo:

Compound of Example 8 ........................ 0.75 g of sodium lauryl ether sulfate ethoxylated with 2.2 moles of ethylene oxide ......... .................................. 10 g oxide of lauryl dimethylamine (sold under the designation (Ammonyx 10 ") .. ....................................... 2 g 35 diethanolamide of coconut oil ..... ....................... 2.5 g of water until ..................... ...................... 100 g pH = 7.5

22 DK 163478 B

Example A 9

Eationic shampoo:

Compound of Example 2 ......................... 1.2 g of 5 lauryl alcohol polyethoxylated with 12 moles of ethylene oxide. 12 g of trimethylcetylammonium bromide (sold under the designation " Cetavlon ") ........................................... 1 g of diethanolamide off coconut oil ..................... 2 g 10 lactic acid up to pH 5 water until ........... ................................ 100 g

Example A 10 Shampoo:

Compound of Example 7 ......................... 1.5 g Compound of Formula 0 ^^ 25 ^ 2¾ ° ....... -6 g of compound of formula R-CHOH-CH 2 / CH 3 -CHOH-C 2 O 2 - H 20 where R represents an alkyl group of 9-12 carbon atoms. 5 g of oxide of lauryl dimethylamine (sold under the designation "Ammonyx: 10 ”) ......................................... 2 g of lactic acid until β 4 25 water until ........................................... 100 g

Example A 11 Shampoo: Compound of Example 7 ......................... 1 g lauryl sulfate of triethanolamine .......... .............. 15 g lauryl diethanolamide ................................ .. 3 g of water until ........................................... 100 g pH = 7.5 23

Example A12

Anionic Shampoo:

DK 163478 B

Compound of Example 10 ........................ 1> 5 g of 5 lauryl myristyl ether sulfate of monoethanolamine ethoxylated with 2.2 moles of ethylene oxide ..... ...................... 12 g of diethanolamide of coconut oil ....................... ..... 2.5 g of water until ....................................... .... 100 g 10 pH = 8

Example A 13 Anionic Shampoo: Compound of Example 10 ........................ Ig oxide of lauryl dimethylamine of formula CH * I 3 C12H25 "... ...................................... g 20 ch5 diethanolamides of coconut oil fatty acids ...... ........... 2 g of sodium lanrylmyris tyl ether sulfate ethoxylated with 2.2 moles of ethylene oxide ............................ ........... 8.5 g 25 water until ................................ ........... 100 g pH = 7.5

Example A 14 30 Cationic Shampoo:

Compound of Example 10 ........................ 2 g lauryl alcohol ethoxylated with 12 moles of ethylene oxide ...... 10 g diethanolamides of coconut fatty acids ... .................. 5 g of 35 lauryl dimethyl amine oxide ............................ .... 2.5 g of water until ........................................ ... 100 g pH = 5

Claims (14)

A hair care agent for achieving enhanced gloss and softness 5 and easier hair styling, comprising (1) a cationic polymer film maker having a molecular weight between 500 and 15,000 and comprising repeating units of the formula 2. A hair care product according to claim 1, characterized in that A represents - r \ - 20 'S- ^ and Z represents the group B1 or file' and at least once represents the group B1 '. Hair care product according to claim 1, characterized in that A denotes / - \ 9— \ -N N- and -N N - \ _7 M CH2 C00-30 and Z denotes βΐ and B1 and the group formed by betainization of B1. Hair care product according to claim 1, characterized in that A denotes F 1 - and / or - NN - | W Ml Jh, CH 3 iH 3 and Z denotes Bl or βΐ 'or the group formed by betainization of B or βΐ '. 20 5. Hair care product according to any one of claims 1-4, characterized in that the nine trogen atom in B1 * is substituted by a carboxymethyl 1 group, a 2-j8-hydroxyethoxyethyl group, a 1,3-dihydroxy-2-methyl- propyl-2 group or a 1-hydroxy-2-methyl-propyl-2 group. 15 Hair care product according to any one of claims 1-4, characterized in that the polymer comprising repeating units of formula (I) is obtained by polycondensation of piperazine, diglycolamine and epichlorohydrin. 20 Hair care product according to any one of claims 1-4, characterized in that the polymer consisting of repeating units of formula (I) is obtained by polycondensation of piperazine, 2-amino-2-methyl-propane-1,3-diol and epichlorohydrin. 25 Hair care product according to any one of claims 1-7, characterized in that it is in the form of an aqueous, alcoholic or aqueous-alcoholic solution, a cream, a paste, a gel or a powder or powder. 30 Hair care agent in the form of a hair shampoo according to any one of the preceding claims, characterized in that it further contains an anionic, cationic, nonionic, amphoteric and / or zwitterionic surfactant. 35 Hair care product according to any one of the preceding claims, characterized in that it further contains L DK 163478 B at least one auxiliary agent selected from synergistically active agents, foam stabilizers, sequestering agents, overfats, thickeners, plasticizers, antiseptics, preservatives, dyes. , perfumes, germicides and cosmetic resins. A - Z - (I) wherein A represents a group containing an amino group and Z represents one or two divalent groups selected from unsubstituted alkylene groups and alkylene groups substituted by one or more hydroxy 1 groups, of which divalent groups at least one is interrupted by one or more nitrogen atoms, (2) a quaternary ammonium salt of a polymer consisting of repeating 1 unit of formula (I), or (3) a polymer of repeating units of formula (I), wherein the amino group is oxidized to form an amine oxide group, characterized in that A represents either the group: - H - or a mixture of the groups: 30 / \ © / - \ -N N- and -N N- \ / iN -y - ch2 cooO or the groups formed by quaternization, and Z represents either the group B1 or B1, and including at least once B1 * or - 35 DK 163478 B in 1 is the group formed by beatinization or quaternization ring of βΐ 'or the mixture of these groups, where βΐ' is a div a single or branched chain alkylene group containing up to 7 carbon atoms in the main chain, 5 which is unsubstituted or substituted by one or more hydroxyl groups and interrupted by one or more nitrogen atoms which is advantageously substituted by an alkyl chain containing 4 and preferably 4 carbon atoms, the alkyl chain optionally being interrupted by an oxygen atom and obligatively carrying one or more hydroxyl or carboxyl functions, and B * denoting a divalent group which is a straight or branched chain alkylene group containing up to 7 carbon atoms in the main chain substituted by a hydroxy 1 group and preferably a 2-hydroxypropylene 1,3-diyl group. 15 Hair care product according to any one of the preceding claims, characterized in that it contains 0.1-5% by weight of the polymer, based on the total weight of the agent. 10 Hair care product according to any one of the preceding claims, characterized in that it has a pH value in the range 3-11. 15 The hair care agent of claim 1, characterized in that the polymer comprising repeating units of formula (I) is obtained by polycondensation of piperazine, aminoacetic acid and epichlorohydrin. 20 Hair care product according to claim 1, characterized in that the polymer consisting of repeating units of formula (I) is obtained by polycondensation of epichlorohydrin and a mixture of piperazine / hydroxylamine and / or amino acid, wherein the epichlorohydrin and the mixture are present in equimolar amounts. The molar amounts of piperazine constitute between 90 and 50% and the molar amounts of hydroxylamine and / or amino acid constitute between 10 and 50% of the mixture. 30 35