DE2839869A1 - POLYMERS DERIVED FROM POLYASPARAGIC ACID, THE PROCESS FOR THEIR MANUFACTURING AND COSMETIC PREPARATIONS CONTAINING THEM - Google Patents

Description

DR. BERG DIPL.-ING. SIAI'F DIPL.-ING. SCHWABE DR. DR. SANDMAIR

PATENTANWÄLTE PO Box 860245 8000 Munich 86

-8th-

Legal file: 29 4 6 3 1 5 · Pertember 1 <) 7

HtM / hm

L'OREAL Paris, France

Polymers derived from polyaspartic acid, processes for their preparation and cosmetic products containing them

preparations

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3 (089) 988272 Telegrams: Bank accounts: Hypo-Bank Munich 4410122850

988273 lU-RGSTAPFPATHNT Munich (BLZ 70020011) Swift Code: IIYPO DIi MM

988274 TI-XHX: "Wer. Vcrcinslraiik Munich 45.1100 (UL /. 70020270) 983310 0524560 BERG <I Postscheck Munich 65343-80S (BLZ 7OOI0OSO)

DESCRIPTION

The invention relates to derivatives of polyaspartic acid, a process for their preparation and their use in cosmetic preparations or cosmetic preparations containing these compounds.

The invention relates in particular to the polymers of the general type derived from polyaspartic acid Formula I.

H-

R-N- (CH ₂ ) _x -z m R'-NR "
CO
I. -CO- P. ^Θ ΟΜ® CO
I. I. B. I.
co NH-C ₂ H3 —Cn ■ NH-C, H-> -NH-C ₂ H ₃ -CO UNITS UNITS UNITS C A.

in the

Z is a mercapto group or a sulfo group in free form or in the form of an alkali metal or alkaline earth metal salt,

χ an integer with a value from 2 to 6, R a hydrogen atom or a low molecular weight alkyl group,

R ^{1 is} a hydrogen atom, a low molecular weight hydroxyalkyl group, an alkyl group with 1 to 18 carbon atoms or an alkenyl group with at most 18 carbon atoms,

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R ¹ 'is a hydrogen atom, a low molecular weight hydroxyalkyl group or a low molecular weight alkyl group, or R ¹ and R ¹ ' together with the nitrogen atom to which they are attached form a six-membered ring which can contain an oxygen atom or a nitrogen atom as a further hetero atom,

M is a hydrogen atom, an alkali metal atom or half an alkaline earth metal atom,
D is a group of the general formulas below

-N- (CH ₂ J _x -Z or -NR ¹¹ or -OM R R '

wherein R, x, Z, R ¹ , R ¹¹ and M have the meanings given above,

m is an integer with a non-zero value and

ρ and q are integers including zero so that the sum m + ρ + q has a value from 15 to 500 .

In the units A, B or C of the general formula I, the group of the formula -C ₉ H- can either be the group

- CH - CH ₉ - or the group CH

- CH mean.

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X-

The units A can either be units of the general formula

RN- (CH ₂ ) _χ - Z

CO - NH - CH - CH ₂ -CO-

or units of the general formula

RN- (CH ₉ ) - Z CO

- NH - CH - CO or mixtures of these units.

It should also be noted that in the case of the polymer of the general formula I, the ρ "units B" are identical or different could be.

In other words, for a polymer of the general formula I, the ρ can be units of the general formula

R ¹ -N-R ''

CO - NH-C ₂ H ₃ -CO-

more precisely reproduce the following units:

CO

NH-C ₂ H ₃ -CO-

R '-NR ¹ ' 2 ι 2

CO I

-NH -C ₂ H ₃ -CO

R '-N-R "η ι η

CO -NH -C ₃ H ₃ -CO

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wherein the substituents R ^1. ,, R ¹ , ·· - R ^{1 have} the meanings of the substituent R ¹ , the substituents R ¹ ^, R ¹ '... R ¹ ' have the meanings of the substituent R ¹¹ and p., p ₂ ... ρ integers such that the sum P ₁ + P ₂ + ·. · P is equal to ρ, and ρ is an integer having a value of 1 to 10 and preferably

with a value from 1 to 3. The polymers of the general formula I are in particular those in which −2− ^ 0.1.

p + q

If the substituent Z of the general formula I stands for a mercapto group or sulfo group in the salt form, it is preferably a sodium salt, a potassium salt, a magnesium salt, a calcium salt, a strontium salt or a barium salt. When the group R stands for a low molecular weight alkyl group, it is preferably an alkyl group having 1 to 4 carbon atoms, for example a methyl group, an ethyl group, an n-propyl group, an isopropyl group or an n-butyl group; when the groups R ¹ or R ″ represent hydroxyalkyl groups, they are preferably hydroxyalkyl groups having 2 to 4 carbon atoms, for example the β-hydroxyethyl group, the '^ -hydroxypropyl group or the 1-hydroxypropan-2-yl group; when the group R ^{1 represents} an alkyl group having 1 to 18 carbon atoms, it means in particular a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, a tetradecyl group, a hexadecyl group or an octadecyl group. When the group R ^{1 represents} an alkenyl group with

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Sf -

2 to 18 carbon atoms, it particularly means an oleyl group; when the group R ¹ 'has the meaning of a low molecular weight alkyl group, it preferably represents an alkyl group having 1 to 4 carbon atoms; if the groups R ¹ and R ¹ 'together with the nitrogen atom to which they are attached represent a six-membered ring, they preferably together represent a pentamethylene group, a 3-0xa-pentamethylene group or an N-methyl-3-aza-pentamethylene group ,

The various units of the general formula I can be in the L configuration, or in the D configuration are in the form of a mixture of the stereoisomers.

The invention also relates to a process for the preparation of the polymers of the general formula I, which thereby is characterized in that a polydehydroaspartic acid of the general formula II

II

where y is an integer with a value from 15 to 500,

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with an amine of the general formula III

.N- (CH ₉ ) -Z III

^{λ Χ}

in an amount of m , since an excess of the amine of the general formula Hl is used, and in the event that In _{1 has} a value less than y, the product obtained with one or more amines of the general formula IV

-R '

IV

converts and / or subjects the product obtained to hydrolysis with an alkali base or an alkaline earth base.

The products of general formula I, wherein Z is a Sulfo group can either be obtained directly by reaction with an amine of the general formula IHa

R.
HN IHa

which has been converted into a salt with an alkali base or an alkaline earth base, or by reacting with a

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Amine of the straightforward formula 11 Ib

HN- (CH ₀ ) -SH HIb,

which is optionally present in the salt form and by reacting the product obtained with a suitable one Oxidizing agents such as hydrogen peroxide in the presence of an organic acid can be formed.

The polydehydroaspartic acid can be prepared using procedures described in the literature. Fox et al (Analytical Method of Protein Chemistry, Vol. IV, page 127, edited by P. Alexander and HP Lundgreen, Pergamon Press) form the polydehydroaspartic acid by heating aspartic acid, optionally in the presence of phosphoric acid. KOVACS et al (J. Org. Chem. 26 (1961) 1081) form the polydehydroaspartic acid by heating (100 hours) aspartic acid in tetralin or in a vacuum. According to FR-PS 70.24831 one obtains the Polydehydroasparaginsäure by heating aspartic acid in the presence of phosphoric acid under vacuum at 170 to 200 ⁰ C to give ensures a constant renewal of the reaction mass surface.

The different methods of making polydehydroaspartic acid have a number of disadvantages:

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The polymerization in tetralin proceeds very slowly and, as a result of the longer heating, leads to higher temperatures Temperatures too strongly colored polymers; and allows the use of liquid or highly viscous acid catalysts (such as phosphoric acid or polyphosphoric acid) do not perform the reaction in a classical way Device to perform and makes the often difficult separation of the catalyst from the polymer as well as the Use of significant amounts of solvent is required.

It has now been found that if the polymerization is carried out in the presence of a solvent with a high boiling point, such as diphenyl ether, and a solid acidic catalyst in the form of an ion exchange resin, at a temperature of 200 to 230 ^° C. at normal pressure, within a short time Time (2 to 4 hours) and with practically quantitative yields a polymer corresponding to the polydehydroaspartic acid, which has a

Has very little coloration and desirably self-sustains.

The ion exchange resin must be sufficiently acidic to function effectively as a catalyst. Thus, strongly acidic ion exchange resins are used, such as the ion exchange resin Amberlite IR 120 H. As the "high boiling point solvent" is to be understood according to the invention, a solvent having a boiling point greater than 200 ⁰ C.

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This new process is also the subject of the invention and has a number of advantages over the procedures which are described in the literature references mentioned above.

The replacement of tetralin by diphenyl ether surprisingly leads to a significant acceleration
the course of the reaction. This enables a significant reduction in the heating time and thus leads to

less discoloration of the polymer obtained.

The use of a solid acid catalyst allows the polymerization to be carried out in conventional equipment and enables the polymer to be separated very easily by simply filtering the mixture of the polymer and the resin followed by dissolving the
Polymers in a small amount of a suitable solvent (such as dimethylformamide, N-methylpyrrolidone, etc.).

The solution obtained can be used as such, or the polymer can be precipitated using a non-solvent, for example for identification purposes.
This measure does not make it necessary to wash the polymer extensively in order to remove the acidic catalyst, as is the case with the method according to FIG
FR-PS 70.24831 is.

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Another advantage of the method according to the invention is to see that you can reuse the solvent and acid catalyst. So it has been shown that you can reuse the solvent and the catalyst five times without intermediate purification. Polyhydroaspartic acid are obtained in each case with corresponding yields and corresponding physical-chemical characteristics.

Various samples of polydehydroaspartic acid were used as starting materials for the preparation of the present invention Polymers are used that have been prepared by using one of the following methods:

METHOD A.

heated in a 3-liter flask equipped with a rotary evaporator, a mixture of 150 g of L-aspartic acid and 75cm of 85% orthophosphoric acid for 3 to 4 hours at a reduced pressure to 180 ⁰ C. After the reaction is allowed to cool and dissolve the obtained viscous syrup in 1 liter of dimethylformamide. Then 1 liter of water is slowly added to the solution obtained. The precipitate is filtered off, washed free of phosphoric acid and dried under reduced pressure for 24 hours at 150 ^° C. in a drying cabinet. In this way, 104 g of polydehydroaspartic acid are obtained in the form of a white product

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a viscosity number or a reduced viscosity of 25 ml / g (c = 0.5% in dimethylforraamide, t = 25 ⁰ C).

METHOD B

In an analogous manner to the method A, but by working at a temperature of 140 ° C instead of at a temperature of 180 ⁰ C, one obtains the Polydehydroasparaginsäure 95g with a viscosity number of 8ml / g (c = 0.5% in dimethylformamide, t = 25 ⁰ C).

METHOD C

In a 1 liter flask fitted with a Dean-Stark device is equipped, heated a suspension of

one
97 g of acidic ion exchange resin (which contains about 50% water and is commercially available under the name Harz IR120H) in 150 cm of tetralin to reflux. After the water has been distilled off, 50 g of L-aspartic acid are added and the mixture is heated for 30 hours under a nitrogen atmosphere, the azeotropic water / tetralin mixture being distilled off. It is then allowed to cool and filtered. The precipitate, which consists of a mixture of the resin and the polydehydroaspartic acid, is washed with hexane. After 400 cm of dimethylformamide have been added, the mixture is filtered and the polydehydroaspartic acid is precipitated by adding water to the piltrate. The precipitate is filtered off and dried under reduced pressure for 24 hours

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Pressure at 150 ⁰ C in this way, Man receives 31g PoIydehydroasparaginsäure in the form of a pale brown product with a viscosity number of 4ml / g (c = 0.5% in dimethylformamide, t = 25 ⁰ C).

METHOD D.

In a 500 ml flask having a Dean-Stark apparatus is equipped, heating a suspension of 50 g of L-aspartic acid and 50 g of previously dried resin IR 120H in 150 cm diphenyl ether progressively from 230 to 240 ⁰ C. The formed during the course of the polycondensation reaction water begins to distill from a temperature of 200 ⁰ C. The mixture is heated to a temperature between 230 and 240 ^° C. for 2 to 3 hours and then allowed to cool, after which it is filtered.

The precipitate containing the resin and the polydehydroaspartic acid is washed with benzene. After adding

3
200 cm of dimethylformamide is filtered and the polydehydroaspartic acid is precipitated from the filtrate by adding 500 cm of ethanol. The mixture is filtered this precipitate off, washed with ethanol and then with isopropyl ether and dried for 24 hours at reduced pressure and a temperature of 150 ⁰ C. This gives 33g Polydehydroasparaginsäure in Forme of a light beige product with a viscosity number of 10 ml / g (c = 0.5% in dimethylformamide, t = 25 ⁰ C).

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Using varying amounts of aspartic acid and IR resin, 12OH is formed under the same conditions the polymers given in Table I below:

TABLE I.

method

E F G

Weight ratio of dry resin to aspartic acid

Heating-up time

yield

0.1 0.5 0.25

8 hours 99%

3 hours 76%

2.5 hours 99%

Viscosity number *

12ml / g

* C = 0.5% in dimethylformamide, t = 25 ⁰ C.

These last-mentioned methods (Methods D, E ₇ F and G) illustrate the process for preparing erfxndungsgemäße Polydehydroasparaginsäure.

The polymers of general formula I have interesting Properties that make it possible to use them as auxiliaries or additives for cosmetic preparations and in particular for to use cosmetic preparations for treating the hair

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They can be used especially in shampoos, in waving lotions, in Rinse lotions before or after shampooing, between two shampooing processes, before or after Coloring or decolorization or after applying a permanent wave can be used in waving lotions, in Shaping lotions (also known as hairdressing lotions), in restructuring lotions or setting lotions, in Capillary creams that are used before or after dyeing or bleaching, before or after shampooing, or before or after applied to the application of a permanent wave, or used in dye preparations. In such preparations they have the ability to improve the fit of the hair, which in particular has fullness and looseness to lend.

The invention therefore also relates to cosmetic preparations, in particular cosmetic preparations for the treatment of the hair and the skin, which are characterized are that they are used as an additive or as an auxiliary at least one polymer of the general defined above Formula I included.

The preparations according to the invention preferably contain the polymer of general formula I in an amount of 0.1 to 10% by weight and preferably in an amount of 0.1 to 5% by weight.

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The preparations according to the invention are, for example:

a) Shampoos which in particular contain 3 to 50% by weight and preferably 3 to 20% by weight of an anionic, non-ionic, amphotheric, cationic or zwitterionic detergent contained in an aqueous carrier material;

b) waving lotions, in particular 0.1 to 5 wt .-% of a cosmetic resin contained in an aqueous or aqueous alcoholic carrier material;

c) Rinsing lotions (rinses), setting lotions, remedies

Structuring lotions or fixing lotions, or shaping lotions (hairdressing lotions).

In addition to the polymer of general formula I, these lotions contain lotions in aqueous or aqueous-alcoholic solution for example conditioning agents, film-forming polymers, etc.

d) Preparations or carrier materials for dyeing, in particular for oxidative dyeing. These preparations generally contain, in addition to the polymer of the general formula I, and oxidation dyes and / or direct dyes, various ingredients that enable the products to be processed into creams (for example soaps, fatty alcohols, emulsifiers, fatty acid amides, etc.) and an alkaline agent. There these staining preparations contain quaternary derivatives,

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they preferably have a pH of 8.5, the alkalizing agent being used, for example, in the Moment of use can add.

e) Bath preparations.

The cosmetic preparations according to the invention have on the other hand, the usual properties of such preparations, as described, for example, in the cosmetics specialist liter door are, for example in the HANDBOOK OF COSMETIC SCIENCE, by H.W. HIBBOTT (Pergamon Press 1963) and HARRY'S COSMETICOLOGY (Leonard HILL BOOKS, 1973).

The following examples serve to further illustrate the invention.
15th

EXAMPLE 1

Polymer of the general formula I, in which ρ = q = 0, χ = 2, Z = a mercapto group and R = H.

Dissolve 19.4 g of polydehydroaspartic acid, which one after Method A made in 100 cm dimethylformamide. The solution is degassed by introducing nitrogen and then add 15.4 g of cysteamine in 50 cm previously degassed dimethylformamide. One holds for 3 hours under one Nitrogen atmosphere and then add 200 cm of alcohol. Man

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- yt -

filtered and the resulting precipitate dried under reduced pressure. This gives 28 g of the polymer which is soluble in water in an alkaline medium.
5

Analysis: Calculated% C 41.37 H 5.74 N 16.09 found% 41.20 5.61 15.90

EXAMPLE 2

Polymer of the general formula I, in which ρ = q = 0,
χ = 2, Z = a sulfo group and R = H.

17.4 g of the polymer obtained according to Example 1 are suspended in 50 cm of acetic acid. Then you give 30cm

30% hydrogen peroxide and allowed to act for 4 days at room temperature. The acetic acid is then distilled off under reduced pressure at 40 ^° C. and
dries the polymer obtained. One receives in this
19g of a white hygroscopic powder.

EXAMPLE · '3

Polymer of the general formula I, in which ρ = q = 0,

χ = 2, Z = -SO ₃ Na and R = H.

29.1 g of the polydehydroaspartic acid prepared according to method A are dissolved in 150 cm of dimethylformamide. Then 4 3 _r 1 g of taurine sodium salt are added and heated during

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- VS -

15 hours at 15O ⁰ C. The suspension obtained is cooled and filtered from the polymer, which is dried after washing with alcohol under reduced pressure. In this way, 28 g of a pale colored powder are obtained which can easily be dissolved in water.

EXAMPLE 4

Polymer of the general formula I ₁ wherein q = 0, χ = 2, Z = SO ₃ Na, R '= the dodecyl group, R ^f ' = H, m / = 0.11 and R = H.

29.1 g of the polydehydroaspartic acid prepared according to method A are dissolved in 150 cm of dimethylformamide. One gives 5.5 g of n-dodecylamine added and the reaction mixture heated for 24 hours at 80 ⁰ C. Then, it 39,75g taurine sodium salt and heated for 8 hours at 150 ⁰ C. After filtration and washing with alcohol obtained one 63.5g of a water-soluble polymer.

in the same way, those in the table below are formed II specified polymers of the general formula I (where q = 0 and R = H)

-H-

-NH

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-NH

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. RV TABEL II Yield% Example· H R ". m / p 96 5 H C ₄ H ₉ 4th 81 6th ^C 18 ^H 37 9 83 7th H C \ _mm / ~ f tj _
υ λ ^ «τι a 1 50 8th H CH ₂ CH ₂ OH 0.11 64 9 H CH ₂ CH ₂ OH 0.25 60 10 H CH ₂ CH ₂ OH 0.43 55 11 H CH ₂ CH ₂ OH 0.67 64 12th CH ₂ CH ₂ OH 1 EXAMPLE 13

Polymer of the general formula I, in which p = q = O, x = 2, Z = -SO ₃ Na and R = CH ₃ .

9.7 g of the polydehydroaspartic acid raised according to method A are dissolved in 50 cm of dimethylformamide. The mixture is heated to 110 ⁰ C and then at this temperature 16.1 g of N-methyl-taurine · · z Natriumsal to. Man giving absolute rel ^ a homogeneous reaction mixture is stirred for 30 minutes at 110 ⁰ C and then abkühien l · äßt. The precipitated polymer is filtered off, washed with methanol and dried under reduced pressure. 22 g of a beige watery product are obtained.

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EXAMPLE 14

Polymer of the general formula I, in which m: ρ: q = 8: 1: 1, X = 2, Z = SO_.Na, R ¹ = a dodecyl group, R = R ¹¹ = H, M = Na.

Dissolve 29.1 g of PoIydehydroasparaginsäure obtained by the method A in 150cm dimethylformamide, 5.5 g of dodecylamine are added and the mixture is heated for 24 hours at 80 ⁰ C. is then added to 35.28 g of taurine sodium salt, and heating the Reaktxonsmischung for 8 hours to 15O ⁰ C. the mixture is filtered, the precipitate is washed with ethanol and then dissolve it in 150cm water containing 1.2 g sodium hydroxide.

The mixture is stirred for 4 hours at room temperature, the water is evaporated off under reduced pressure and 65 g of one are obtained light yellow colored polymer that is easily soluble in water.

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EXAMPLES OF COSMETIC PREPARATIONS EXAMPLE I

An anionic shampoo is prepared by mixing the following ingredients:

Sodium C ^ -C ^ -alkyl ether sulfate on the Based on 2.2 moles of ethylene oxide 12g

Hydroxypropyl methyl cellulose 0.4 g

Polymer of Example 3 3g

Triethanolamine up to a pH of 6

Water ad 100 g.

This shampoo makes it easier to comb out wet hair and ensures that the hair sits well after it has dried.

EXAMPLE II

An anionic shampoo is formed by mixing the following ingredients:

Sodium-C. _{--C 1.} -Alkyl ether sulfate on the

Based on 2.2 moles of ethylene oxide. 12 g

Hydroxypropyl methyl cellulose 0.4 g

Polymer of Example 4 3g

Triethanolamine up to a pH value of 8 water ad 100 g.

This shampoo makes it easier to comb out wet hair and ensures that the hair sits well after it has dried.

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- VZ -

EXAMPLE III

An anionic shampoo is formed by mixing the following ingredients: Sodium-C. _? -C ... -Alkyl ether sulfate on the

Based on 2.2 moles of ethylene oxide 12g

Hydroxypropyl methyl cellulose 0.4 g

Polymer of Example 12 3g

Triethanolamine up to a pH of

Water ad 100 g.

This shampoo makes it easier to comb out wet hair and gives the hair a good fit after drying.

EXAMPLE IV

A non-ionic shampoo is formed by mixing the following ingredients: Connection * 10 g

Lauric acid diethanolamide 3 g

Polymer of Example 4 5g

Triethanolamine up to a pH of 7

Water ad 100 g.

This shampoo makes it easier to comb out wet hair and gives the hair a good fit after drying.

* The compound corresponds to the following formula:

C, _n H__ - 0 - I CoH_. _n (CH ^ OH) IH, Λ λ Lo ^L Z JO 2 ^Λ η

where η has a statistical value of 4.

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EXAMPLE V - WELL LOTION

The preparation is made from the following components:
Polymer of Example 3 1.0 g

Vinyl acetate / crotonic acid copolymer (commercially available from Societe Hoechst under the designation TV 24 2) 1.0g

Trimethylcetylammonium bromide 0.1 g

Ethanol ad 50%

Fragrance
dye

Water ad 100 cm

The preparation has a spontaneous pH of 7.4.

Once applied and dried, this lotion gives the sensitized hair softness.

EXAMPLE VI - WELL LOTION

The preparation is made from the following ingredients:

Polymer of Example 6 1.0g

Vinyl acetate / crotonic acid copolymer

(available from Societe Hoechst under the designation TV 24 2) 1.0g

Trimethylcetylammonium bromide 0.1 g

Ethanol ad 10%

2-Amino-2-methyl-1-propanol up to a pH value of 8 water ad 100 cm.

The preparation has a pH of 8.

_B. . 909813 / 08A9

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EXAMPLE VII - HAIRDRESSING LOTION OR BRUSH LOTION The preparation is formed from the following ingredients:
Polymer of Example 3 0.3 g

Vinyl acetate / crotonic acid copolymer

(available from Societe Hoechst under the designation TV 242). 0.2 g

Trimethylcetylammonium bromide 0.2 g

Ethanol ad 50%

Fragrance
dye

Water ad 100 cm

The spontaneous pH is 7.5.

EXAMPLE VIII - HAIR LOTION OR BRUSH LOTION The formulation is formed from the following ingredients; Polymer of Example 6 0.3 g

Vinyl acetate / crotonic acid copolymer

(available from Societe Hoechst at the designation TV 242) 0.2 g

Trimethylcetylammonium bromide 0.2 g

Ethanol ad 50%

2-Amino-2-methyl-1-propanol up to a pH of 8.7 water ad 100 cm

The preparation has a pH of 8.7. Series 207

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Claims (1)

Γ- γ. Aηwn. tsaktF-: 29 - ¹ M PATENT CLAIMS (p. Polymers of the general formula I derived from polyaspartic acid H- R-N- (CH ₉ JZ m R. '-NO"
I. P. θ ©
OM
1 ₃ -co- - D CO
I.
NH-C H ₃ -CO- •Nile CO
-C ₂ H ₃ -CO I.
co q in the Z is a mercapto group or a sulfo group in free form or in the form of an alkali metal or alkaline earth metal salt, χ is an integer from 2 to 6, R is a hydrogen atom or a low molecular weight Alkyl group, R ^{1 is} a hydrogen atom, a low molecular weight hydroxyalkyl group, an alkyl group with 1 to 18 carbon atoms or an alkenyl group with at most 18 carbon atoms, R ^{11 is} a hydrogen atom, a low molecular weight hydroxyalkyl group or a low molecular weight alkyl group, or R ¹ and R ¹ 'together with the nitrogen atom to which they are bonded form a ring with 6 chain members, which can contain an oxygen atom or a nitrogen atom as a further heteroatom, Series 207 909813/0849 ORIGINAL INSPECTED M represents a hydrogen atom, an alkali metal atom or a half an alkaline earth metal atom, D a group of the general formulas below -N- (CH ₂ ) -ZR or -N-R '' R ¹ ΘΘ or -OM in which R, x, Z, R ", R ¹ 'and M are those given above Have meanings m is an integer with a non-zero value and ρ and q are integers including zero such that the sum of m + ρ + q has a value from 15 to 500, mean. Polymers according to claim 1, characterized in that the units of general formula R'-N-R " ϊ ° -NH-C ₂ H ₃ -CO- from η units of the general formula CO NH- C ₂ H ₃ -CO-- R '-NR ¹ ' 2, 2 CO I NH -C ₂ H ₃ -CO CO -NH -C ₂ H ₃ -CO- are formed in which Series 207 909013/0849 _ ο - the substituents R ¹ -, R ' _? ... R ^{1 have} the meanings of the substituent R ¹ , the substituents R ¹¹ - ,, R "" ... R ^{1r have} the meanings of the substituent R ¹¹ and P ₁ , p ₉ ... ρ are whole numbers, so that P ₁ + Pp + ... ρ is equal to ρ, and η is an integer with a value from 1 to 10 and preferably from 1 to 3. 3. Polymers according to one of the preceding claims, characterized in that when the substituent Z is a mercapto group or Sulfo group is in the salt form, it is preferably a sodium salt, a potassium salt, a magnesium salt, a calcium salt, a strontium salt or a barium salt. 4. Polymers according to one of the preceding claims, characterized in that the group R has the meaning of a low molecular weight alkyl group represents an alkyl group with 1 to 4 carbon atoms, 5. Polymers according to one of the preceding claims, characterized in that the groups R ¹ or R ″ represent a hydroxyalkyl group with 2 to 4 carbon atoms. 909813/0849 Series 20 7 6. Polymers according to one of claims 1 to 4, characterized in that when the groups R ¹ and R ¹ 'together with the nitrogen atom to which they are bonded represent a six-membered ring, they together represent a pentamethylene group, a 3 -Oxa-pentamethylene group or an N-methyl-3-aza-pentamethylene group. 7. A method for producing the polymers according to any one of the preceding claims, characterized characterized in that a polydehydroaspartic acid of the general formula II NH. II wherein y is an integer with a value from 15 to 500, with an amine of the general formula III R, N- (CH ₂ J _x -Z III in an amount of m moles of the amine per mole of the polydehydroaspartic acid converts, where m stands for an integer or a decimal fraction with a value of 1 up to y + 1, which can also be greater than y + 1, Series 207 909813/0849 when using an excess of the amine of the general formula III, and then, if m. has a value less than y, man the product obtained with one or more amines of the general formula IV R ¹
HN ^ ^IV implements ο and / or the product obtained from hydrolysis with a Subjects to alkali or alkaline earth base. 8. The method according to claim 7, characterized characterized in that for the preparation of a polymer of the general formula I, wherein Z is stands a sulfo group, the polydehydroaspartic acid either directly with an amine of the general formula IHa R.
H -N IHa, which has been converted into a salt with an alkali base or an alkaline earth base, or with an amine of the general formula IHb R.
H -N - (CH ₂ ) _χ -SH Series 207 909813/0849 which may optionally be in the salt form, and that in the reaction with the amine of the general Formula IHb brings the product obtained to reaction with an oxidizing agent. 9. The method according to claim 8, characterized in that one is used as the oxidizing agent Hydrogen peroxide is used in the presence of an organic acid. 10. Cosmetic preparations for the treatment of the hair, characterized in that they as an additive at least one polymer of the general formula I according to at least one of the claims to 6 included. 11. Preparations according to claim 10, characterized in that they are in the form of Shampoos, waving lotions, rinsing lotions, non-rinsing lotions to strengthen hair curl, restructuring Lotions, form lotions, preparations or carrier materials for colorants or in the form of Capillary creams are present. Series 207 909813/0849 12. Preparations according to one of claims 10 and 11, characterized in that they contain the polymer of the general formula I in an amount of 0.1 to 10% by weight. 13. Process for the preparation of polydehydroaspartic acid, characterized in that aspartic acid is heated in the presence of a solvent with a high boiling point and a solid acidic catalyst in the form of an ion exchange resin at normal pressure for 2 to 4 hours to a temperature of 200 to 230 ^° C. series 909813 / 08A9