WO2006106113A2

WO2006106113A2 - Use of copolymers containing polyisobutylene in shampoos and haircare products

Info

Publication number: WO2006106113A2
Application number: PCT/EP2006/061334
Authority: WO
Inventors: Volker Wendel; Darijo Mijolovic; Matthias KLÜGLEIN; Hubertus Peter Bell
Original assignee: Basf Aktiengesellschaft
Priority date: 2005-04-05
Filing date: 2006-04-05
Publication date: 2006-10-12
Also published as: DE102005015633A1; WO2006106113A3

Abstract

The invention relates to the use of copolymers in shampoos and haircare products. Said polymers are obtained by the copolymerisation of at least one ethylenically unsaturated dicarboxylic acid anhydride, derived from at least one dicarboxylic acid, with between 4 and 8 C atoms and at least one oligomer of branched or unbranched C3-C10 alkene, at least one oligomer having an average molecular weight Mn ranging between 300 and 5000 g/mol, preferably up to 1200 g/mol, or are obtained by the oligomerisation of at least 3 equivalents of C3-C10 alkene.

Description

Use of polyisobutene-containing copolymers in shampoos and hair care products

description

The present invention relates to the use of a) copolymers obtainable by copolymerization of

(A) at least one ethylenically unsaturated dicarboxylic acid anhydride derived from at least one dicarboxylic acid having 4 to 8 C atoms,

(B) at least one oligomer of branched or unbranched C ₃ -C ₁₀ alkene, wherein at least one oligomer has an average molecular weight M _n in the range of 300 to 5000 g / mol, preferably up to 1200 g / mol, or by oligomerization is obtainable from at least 3 equivalents of C ₃ -C ₁₀ -alkene,

(C) optionally at least one α-olefin having up to 24, preferably having up to 16 C atoms,

(D) optionally at least one further ethylenically unsaturated comonomer other than (A), (B) and (C), if appropriate, reaction with

(E) at least one compound of general formula Ia, Ib, Ic or Id

in which

A ^{1 is} C ₂ -C ₂₀ alkylene, identical or different, R ¹ C-C ₃₀ -alkyl, linear or branched, phenyl or hydrogen, n is an integer from 1 to 200, optionally followed by contacting with water, optionally mixed with b ) of at least one oligomer of branched or unbranched C ₃ -C ₁₀ alkene, where at least one oligomer has an average molecular weight M _n in the range from 300 to 5000 g / mol, preferably up to 1200 g / mol, or by oligomerization of at least 3 Equivalent C ₃ -C ₁₀ -alkene is available, in shampoos and hair products.

Furthermore, the present invention relates to shampoos and hair care products containing the aforementioned components a) and optionally b). The invention accordingly relates to compositions for cleaning and / or care of the hair.

The invention further relates to hair care preparations containing the abovementioned components a) and optionally b), wherein the hair care agent is selected from the group consisting of pretreatment agents, hair conditioners, hair conditioners, hair balsams, Ieave-on hair treatments, rinse-off hair treatments, hair lotions, pomades, Hairdressing creams, hairdressing lotions, hairdressing gels, top fluids, hot oil treatments and foam cures.

Other bathing, showering or washing preparations are not the subject of this invention. Also cosmetic or dermatological compositions with a sun protection factor (SPF) of at least 4, determined by the COLI PA method, are not the subject of this invention.

State of the art

Hair care products are used primarily to improve the dry and wet combability, the feel, the gloss and the appearance of the hair and to give the hair antistatic properties.

A shampoo should foam and cleanse the hair well, be mild and well-tolerated, as well as convenient and comfortable to use, it also has to help with the care of the hair or the removal of hair and scalp problems. These additional effects and the self-evident cleansing effect are characteristic of a modern shampoo.

Shampoos are expected to have sufficient cleansing power with not too strong a defatting effect and at the same time adequate mildness. It is important that the cleaning power and the other desired surfactant properties are given both in soft and in hard water. Shampoos must be well tolerated by skin and mucous membranes and must therefore not be aggressive under normal conditions of use. Good cleaning performance does not have to be linked to heavy foaming. Nevertheless, the amount and quality of the shampoo shampoo during washing are important criteria for the consumer to be met by the shampoos.

The viscosity of shampoos must be chosen so high that it flows out of the bottle sufficiently quickly and can be spread well and easily on the hair. On the other hand, it should not be so thin liquid that it is out of hand and from the head runs down. Cleaning and foaming power, skin compatibility, thickenability and hydrolytic stability of the individual ingredients of shampoos are highly dependent on the pH value. The ingredients used in shampoos should develop these properties in the neutral and weakly acidic pH range (pH 5-7) optimally, but also show no significant performance losses outside this pH range. The selected ingredients of the shampoos must be chemically stable and compatible with all other formulation ingredients, so z. B. no impairments or segregations take place.

Hair care products, which also include most shampoos, are tailored to a particular hair quality or to a specific hair or scalp problem. For this purpose, additional special auxiliaries are needed. This includes the group of conditioning agents. Conditioners are auxiliaries that are absorbed by the hair and remain on the hair after the rinsing process. They improve the combability, feel and shine of the hair. With certain types of hair (fine hair) or overdosage, however, the conditioners can also lead to undesirable weighting of the hair. In terms of formulation, this means that the use of conditioning agents always has to pay attention to a balanced balance between conditioning performance and hair thinning. Furthermore, when using conditioning agents, care must be taken to ensure that the regular use of the product does not lead to a steadily increasing amount

Conditioner on the hair leads (build-up effect). Difficulties are often the provision of products with a complex property profile. Such complex property profiles often require the use of many different ingredients in a preparation, which in turn implies the danger of incompatibility with one or more of these ingredients in the consumer.

task

The object of the present invention was to eliminate or at least reduce the aforementioned deficiencies of the prior art. Accordingly, there is a need for well-tolerated shampoos and hair products which simultaneously provide the hair with good sensory properties such as elasticity, a pleasant feel and volume, without having a good conditioning and cleansing effect from an unsatisfactory greasy and / or sticky appearance of it treated hair is accompanied. Shampoos and hair care products with the abovementioned properties should be developed on the basis of as few starting materials as possible, since with agents of the prior art, the large number of necessary components leads in part to skin irritations, allergic reactions or other incompatibilities. In particular, in the field of children and baby shampoos and hair products is a Need for compositions with the lowest possible number of different ingredients.

Solution to the Problem The above objects are achieved by the use of a) copolymers obtainable by copolymerization of

(E) at least one compound of general formula Ia, Ib, Ic or Id

in which

A ¹ C ₂ -C ₂ o-alkylene, the same or different,

R ^{1 is} C ¹ -C ₃₀ -alkyl, linear or branched, phenyl or hydrogen, n is an integer from 1 to 200, if appropriate subsequently in contact with water, optionally mixed with

b) at least one oligomer of branched or unbranched C ₃ -C ₀ -AIken, wherein at least one oligomer having an average molecular weight M _n in the range from 300 to 5000 g / mol, preferably up to 1200 g / mol or by oligomerization of at least 3 equivalents of C ₃ -C- | _{0 is} available,

in shampoos and hair products. A preferred embodiment of the invention are shampoos which simultaneously have conditioning properties. Another preferred embodiment of the invention are shampoos which simultaneously have setting properties.

Copolymer a) is present in the compositions according to the invention in an amount of from 0.1 to 15% by weight, preferably from 1 to 10, particularly preferably from 2 to 6% by weight, based on the weight of the composition. If the copolymer is mixed with oligomer b) in the composition, the weight ratio of oligomer b) to copolymer a) in one embodiment of the invention is preferably from 1:10 to 3: 1, particularly preferably from 1: 5 to 2: 1 and most preferably from 1: 2 to 1.5: 1.

Copolymer a) Copolymer a) is obtainable by preferably free-radical copolymerization of

(A) at least one ethylenically unsaturated dicarboxylic acid anhydride derived from at least one dicarboxylic acid having 4 to 8 C atoms, for example maleic anhydride, itaconic anhydride, citraconic anhydride, methylmalonic acid anhydride, preferably itaconic anhydride and maleic anhydride and very particularly preferably maleic anhydride;

(B) at least one oligomer of branched or unbranched C ₃ -Ci ₀ - alkene, wherein at least one oligomer has an average molecular weight M _n in the range of 300 to 5000 g / mol, preferably up to 1200 g / mol or by oligomerization of at least 3 equivalents of C ₃ -C ₁₀ -alkene lent is,

(E) at least one compound of general formula Ia, Ib, Ic or Id

where A ^{1 is} C ₂ -C ₂ o-alkylene, identical or different,

R ^{1 is} C ₁ -C ₃₀ -alkyl, linear or branched, phenyl or hydrogen, n is an integer from 1 to 200, where the carboxyl groups of the copolymer a) may be at least partially esterified or amidated, and optionally subsequent contact with water ,

Oligomers (B) or b)

Suitable oligomers (B) and b) are oligomers of propylene or unbranched or preferably branched C ₄ -C 10 -olefins, where at least one oligomer has an average molecular weight M _n in the range from 300 to 5000 g / mol, preferably up to at 1200 g / mol or is obtainable by oligomerization of at least 3 equivalents of C ₃ - C 10 -alkene.

Examples which may be mentioned are oligomers of propylene, isobutene, 1-pentene, 2-methylbutene-1, 1-hexene, 2-methylpentene-1, 2-methylhexene-1, 2,4-dimethylhexene, diisobutene (mixture from 2, 4,4-trimethylpentene and 2,4,4-trimethyl-2-pentene), 2-ethylpentene-1, 2-ethylhexene-1 and 2-propylheptene-1, 1-octene, 1-decene and 1-dodecene Most preferred are oligomers of isobutene, diisobutene and 1-dodecene.

The oligomers (B) or b) have an ethylenically unsaturated group which may be in the form of a vinyl, vinylidene or alkylvinylidene group. Co-oligomers of the abovementioned olefins with one another or with up to 20 wt .-%, based on (B) or b), vinylaromatics such as styrene and α-methylstyrene, CrC ₄ -alkylstyrene such as 2-, 3- and 4 Methylstyrene and 4-tert-butylstyrene are suitable.

Particularly preferred oligomers (B) or b) are oligopropylene and oligoisobutenes having an average molecular weight M _n up to 1200 g / mol, preferably in the range of

300 to 1000 g / mol, more preferably of at least 400 g / mol, especially preferably of at least 500 g / mol, for example as determined by gel permeation chromatography (GPC).

In one embodiment of the present invention, oligomers (B) and b) have a polydispersity M _w / M _π in the range from 1.1 to 10, preferably to 5 and particularly preferably from 1.5 to 1.8.

In one embodiment of the present invention, oligomers (B) and b) have a bimodal molecular weight distribution with a maximum of M _n in the range of 500 to 1200 g / mol and a local maximum of M _n in the range of 2000 to 5000 g / mol , Oligomer (B) may be the same or different from oligomer (b). In one embodiment of the present invention, oligomer (B) and oligomer (b) are the same.

Oligomers of C ₄ olefins are preferably suitable as oligomer b). In one embodiment of the invention, the oligomers b) are hydrogenated oligomers of C ₄ olefins. Also particularly preferred as oligomers b) are, optionally hydrogenated, oligomers of 3, 4, 5, 6, 7 or 8 C ₄ -olefin molecules.

Comonomer (C)

Alpha-olefins having up to 16 carbon atoms and used as comonomer (C) are selected from propylene, 1-butene, isobutene, 1-pentene, 4-methylbut-1-ene, 1-hexene, diisobutene (mixture from 2 , 4,4-trimethyl-1-pentene and 2,4,4-trimethyl-2-pentene), 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene and 1-hexadecene; particularly preferred are isobutene, diisobutene and 1-dodecene.

Preparation of Copolymer a) The copolymer a) (A), (B) and optionally (C) used according to the invention can be copolymerized with one another for the preparation of the copolymer. It is also possible to copolymerize with one another for the preparation of inventive copolymer a) (A), (B) and, if appropriate, (C) and react with (E) or (A), (B) and, if appropriate, (C) and optionally a further comonomer ( D) copolymerize with one another, or (A) and (B) and optionally (C) and optionally a further comonomer (D) copolymerize with each other and optionally with (E) implement.

If it is desired to use a copolymer a) whose carboxyl groups are at least partially esterified or amidated, the compound (E) selected is at least one compound of the general formula Ia to Id, preferably Ia,

where the variables are defined as follows:

A ¹

Alkylene, for example

in the

R ^{1 is} phenyl,

hydrogen

preferably methyl. n is an integer in the range of 1 to 200, preferably 4 to 20.

Of course, the groups A ¹ can only be different if n is a number greater than 1 or if different compounds of the general formula I a to I d are used.

Particular examples of compounds of general formula Ia are

Methylendgruppenverschlossene polyethylene glycols of the formula

with m = 1 to 200, preferably 4 to 100, particularly preferably 4-50 - methyl end-capped block copolymers of ethylene oxide, propylene oxide and / or butylene oxide having a molecular weight M _n of 300 to 5000 g / mol Methyl end-capped random copolymers of ethylene oxide, propylene oxide and / or butylene oxide having a molecular weight M _n of 300 to 5000 g / mol

Alkoxyiierte C ₂ - to C ₃₀ alcohols, in particular fatty alcohol alkoxylates, oxoalko holalkoxylate or Guerbet alcohol alkoxylates, wherein the alkoxylation can be carried out with ethylene oxide, propylene oxide and / or butylene oxide, examples are

C ₃ -C ₅ -oxo-alcohol ethoxylates having from 3 to 30 ethylene oxide units C ₃ -oxoalcohol ethoxylates having from 3 to 30 ethylene oxide units, - C ₁₂ -C ₄ -fatty alcohol ethoxylates having from 3 to 30 ethylene oxide units, C ₁₀ -oxoalcohol ethoxylates having from 3 to 30 ethylene oxide units, Cio-guerbet alcohol ethoxylates with 3 to 30 ethylene oxide units,

C 9 -C 10 oxo alcohol alkoxylates having 2 to 20 ethylene oxide units, 2 to 20 propylene oxide units and / or 1 to 5 butylene oxide units; C ₁₃ -C ₅ oxo alcohol alkoxylates having 2 to 20 ethylene oxide units, 2 to 20 propylene oxide units and / or 1 to 5 butylene oxide units;

C ₄ -C ₂ o-Alcohol ethoxylates with 2 to 20 ethylene oxide units.

Preferred examples of compounds of the formula Ib are methylene- _terminated polyethyleneglycolamines of the formula H ₂ N- (CH ₂ CH ₂ O) _nI- CH ₃ with m = 1 to 200, preferably 4 to 100, particularly preferably 4 to 50.

If it is desired to react with compound Id, compound Ic can be reacted with alkylating agents such as, for example, halides or sulfates of the formula R ¹ -Y with Y selected from CI, Br and I or (R ¹ J ₂ SO ₄ or the Alkylierungsagenzien obtained compound Id with Y, SO ₄ ^{2 '} or R ¹ -SO ₄ ^" as a counterion.

In one embodiment of the present invention, mixtures of different components (E), for example of the formula Ia, are used. In particular, it is possible to use those mixtures of compounds of the formula Ia in which, based in each case on the mixture, at least 95 mol%, preferably at least 98 mol%, up to a maximum of 99.8 mol% R ¹ for C ₁ -C ₃₀ -AIk ^ is and at least 0.2 mol% and at most 5 mol%, preferably at most 2 mol% of hydrogen.

In one embodiment of the present invention, for the preparation of the copolymer a) used according to the invention, the reaction mixture is contacted after the preferably free-radical copolymerization and, if appropriate, the reaction with (E) with water, the water still containing Bronsted acid or, preferably, Bronsted acid. Base may contain. Examples of Brønsted acids are sulfuric acid, hydrochloric acid, tartaric acid and citric acid. Examples of Brønsted base are alkali metal hydroxides such as NaOH and KOH, alkali metal carbonate such as Na ₂ CO ₃ and K ₂ CO ₃ , alkali metal hydrogencarbonate such as NaHCO ₃ and KHCO ₃ , ammonia, amines such as trimethylamine, triethylamine, diethylamine, ethanolamine, N, N-diethanolamine, N, N, N-triethanolamine, N-methylethanolamine.

In another embodiment of the present invention, it is possible to contact with water already during the preferably free-radical copolymerization.

Monomers (D)

The monomer or monomers (D) which can optionally be used to prepare copolymer (a) used according to the invention are different from (A), (B) and (C). Preferred monomers (D) are:

C ₃ -C ₈ carboxylic acids or carboxylic acid derivatives of the general formula II

Carboxylic acid amides of the formula III,

non-cyclic amides of the general formula IV a and cyclic amides of the general formula IV b

CrC ₂ o-alkyl vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl propyl ether, n-butyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl ether or n-octadecyl vinyl ether; N-vinyl derivatives of nitrogen-containing aromatic compounds, preferably N-vinylimidazole, 2-methyl-1-vinylimidazole, N-vinyloxazolidone, N-vinyltriazole, 2-vinylpyridine, 4-vinylpyridine, 4-vinylpyridine-N-oxide, N-vinylimidazoline , N-vinyl-2-methylimidazoline, α, β-unsaturated nitriles such as acrylonitrile, methacrylonitrile; alkoxylated unsaturated ethers of the general formula V,

Esters and amides of the general formula VI,

unsaturated esters of general formula VII

vinylaromatic compounds of the general formula VIII

Phosphate-, phosphonate-, sulphate- and sulphonate-containing comonomers such as [2- {(meth) acryloyloxy} -ethyl] -phosphate, 2- (meth) acrylamido-2-methyl-1-propanesulfonic acid; α-olefins, linear or branched, having 18 to 40 carbon atoms, preferably having up to 24 carbon atoms, for example 1-octadecene, 1-eicosene, Ci-C ₂₂ H ₄₄ , Ot-C ₂₄ H ₄₈ and mixtures of the aforementioned α-olefins , The variables are defined as follows:

R ² , R ^{3 are} identical or different and selected from unbranched or branched C ₁ -C ₅ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl Butyl, n-pentyl, iso-pentyl, sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, more preferably C ₁ -C ₄ -alkyl such as methyl, ethyl, n-propyl, iso-propyl , n-butyl, iso-butyl, sec-butyl and tert-butyl; and especially hydrogen;

R ^{4 is} identical or different and C 1 -C ₂₂ -alkyl, branched or unbranched, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-butyl Pentyl, isopentyl, sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-dodecyl, n-

eicosyl; particularly preferably C _r C ₄ alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-butyl, sec-butyl and tert-butyl; or more preferably hydrogen; R ^{5 is} hydrogen or methyl, x is an integer in the range of 2 to 6, preferably 3 to 5; y is an integer selected from 0 or 1, preferably 1; a is an integer in the range of 0 to 6, preferably in the range of 0 to 2;

R ⁶ , R ^{7 are} identical or different and selected from hydrogen, unbranched or branched C 1 -C ₁₀ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert. Butyl, n-pentyl, iso-pentyl, sec-pentyl, neo-pentyl, 1,2-

Dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, n- Nonyl, n-decyl, preferably

AlkyI such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl, most preferably methyl;

X is oxygen or NR ⁴ ; R ⁸ [A ³ -O] _n -R ⁴ , R ⁹ selected from unbranched or branched Ci-C ₂₀ alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec. Butyl, tert-butyl, n-pentyl, iso-pentyl, sec-pentyl, neo-pentyl, 1, 2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, n-eicosyl; preferably C 1 -C ₁₄ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl , neo-pentyl, 1, 2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-dodecyl, n-tetradecyl , and in particular hydrogen or methyl;

R ¹⁰ , R ¹¹ are each independently hydrogen, methyl or ethyl, preferably R ¹⁰ and R ^{11 are} each hydrogen;

R ^{12 is} methyl or ethyl; k is an integer in the range from 0 to 2, preferably k = 0,

A ² , A ^{3 are} identical or different and C ₂ -C ₂ o-alkylene, for example - (CH ₂ ) ₂ -,

-CH ₂ -CH (CH ₃ ) -, - (CH ₂ ) ₃ -, -CH ₂ -CH (C ₂ H ₅ ) -, - (CH ₂ J ₄ -, - (CH ₂ ) ₅ -, - ( CH ₂ ) ₆ -, preferably C ₂ -C ₄ -alkylene, in particular - (CH ₂ J ₂ -, -CH ₂ -CH (CH ₃ ) - and - (CH ₂ ) ₃ -;

A ⁴ C-pCzo-alkylene, for example -CH ₂ -, -CH (CH ₃ )., -CH (C ₆ H ₅ ) -, -C (CH ₃ ) ₂ -,

- (CHz) ₂ -, -CH ₂ -CH (CH ₃ ) -, - (CHz) ₃ -, -CHz-CH (C ₂ H ₅ ) -, - (CHz) ₄ -, - (CH ₂ ) ₅ -, - (CH ₂ ) ₆ -, preferably C ₂ -C ₄ alkylene; in particular - (CH ₂ ) ₂ -, -CH ₂ -CH (CH ₃ ) - and - (CHz) ₃ -, or in particular a single bond.

The remaining variables are defined as above.

Examples of selected compounds of the formula III are (meth) acrylamides, such as acrylamide, N-methylacrylamide, N, N-dimethylacrylamide, N-ethylacrylamide, N-

Propylacrylamide, N-tert-butylacrylamide, N-tert-octylacrylamide, N-undecylacrylamide or the corresponding methacrylamides.

Exemplary selected compounds of the formula IV a are N-vinylcarboxamides such as N-vinylformamide, N-vinyl-N-methylformamide, N-vinylacetamide or N-vinyl-N-methylacetamide; Exemplary selected representatives of compounds of formula IV b are N-vinylpyrrolidone, N-vinyl-4-piperidone and N-vinyl-ε-caprolactam. Exemplary selected compounds of formula VI are (meth) acrylic acid esters and amides such as N, N-dialkylaminoalkyl (meth) acrylates or N, N-dialkylaminoalkyl (meth) acrylamides; Examples are N, N-dimethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl acrylate, N ₁ N- diethylaminoethyl methacrylate, N, N-dimethylaminopropyl acrylate, N ₁ N- dimethylaminopropyl methacrylate, N, N-diethylaminopropyl acrylate, N ₁ N- diethylaminopropyl methacrylate, 2- (N , N-dimethylamino) ethyl acrylamide, 2- (N ₁ N-dimethylamino) ethyl methacrylamide, 2- (N ₁ N-diethylamino) ethyl acrylamide, 2- (N ₁ N-diethylamino) ethyl methacrylamide, 3- (N, N-dimethylamino) propylacrylamide and 3- (N ₁ N-dimethylamino) propylmethacrylamide.

Illustratively selected compounds of the formula VII are vinyl acetate, allyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate or vinyl laurate.

Exemplary selected vinylaromatic compounds of the general formula VIII are α-methylstyrene, para-methylstyrene and in particular styrene. Very particular preference is given to using as comonomer (D): acrylic acid, 1-octadecene, methacrylic acid, methyl acrylate, methyl methacrylate, acrylamide, vinyl n-butyl ether, vinyl isobutyl ether, styrene, N-vinylformamide, N-vinylpyrrolidone, 1-vinylimidazole and 4-vinylpyridine.

With regard to (A), (B), optionally (C) and, where appropriate, (D), the copolymers a) may be block copolymers, alternating copolymers or random copolymers, alternating copolymers being preferred.

In one embodiment of the present invention, the anhydride groups of copolymer a) after the polymerization are completely or partially hydrolyzed and optionally neutralized. In one embodiment of the present invention, the anhydride groups of copolymer a) after the copolymerization are present as anhydride groups.

In one embodiment of the present invention, the molar ratios of copolymer used in erfϊndungsgemäß a)

(A) in the range from 5 to 60 mol%, preferably 10 to 55 mol%, (B) in the range from 1 to 95 mol%, preferably 5 to 70 rnol%,

(C) in the range of 0 to 60 mol%, preferably 10 to 55 mol%,

(D) 0 to 70 mol%, preferably 1 to 50 mol%, in each case based on copolymer, wherein the sum of (A), (B), (C) and (D) gives 100 mol%, and

(A) in the range of 0 to 50 mol%, preferably 1 to 30 mol%, particularly preferably 2 to 20 mol%, based on all carboxyl groups of the copolymer.

In one embodiment, a weight ratio of oligomer b) to copolymer a) is selected in the range from 0.1: 1 to 100: 1, preferably from 0.5: 1 to 10: 1. In another embodiment, a weight ratio of oligomer (b) to copolymer a) is selected in the range from 1: 1 to 100: 1, preferably from 10: 1 to 50: 1.

The copolymers a) used according to the invention and their mixtures with oligomer b) are described in the German patent applications with the file references DE 10353557.8, DE 10355402.5 and DE 10345094.7, to which reference is made in its entirety.

In one embodiment of the present invention, the copolymers a) of (A), (B) and optionally (C) and (D) used according to the invention have an average molecular weight M _w in the range from 1000 g / mol to 50,000 g / mol, preferably 1,500 g / mol to 25,000 g / mol, determined, for example, by gel permeation chromatography using dimethylacetamide as solvent and polymethyl methacrylate as standard.

Copolymers a) of (A), (B) and optionally (C) and (D) and (E) used according to the invention may relate to (A), (B) and optionally (C) and (D) block copolymers, alternating copolymers or random copolymers, preference being given to alternating copolymers.

The polydispersity M _w / M _n of the present invention as used copolymers of (A) Copoiymerisat a), (B) and optionally (C) and (D) and (E) is in the Aligemeinen in the range of 1, 1 to 20, preferably from 2 to 10.

In one embodiment of the present invention, copolymers of (A) ₁ (B) and optionally (C) and (D) and (E) according to the invention have Kik values according to Fikentscher in the range from 5 to 100, preferably 8 to 30 (measured according to H. Fikentscher at 25 ⁰ C in cyclohexanone and a Polyrηerkonzent- ration of 2 wt .-%).

In one embodiment of the present invention, copolymers a) used according to the invention may comprise unpolymerized comonomer (B), for example in proportions of from 1 up to 50% by weight, based on the total weight of copolymer a).

For the preparation of copolymers of (A), (B) and optionally (C) and (D) and (E) used according to the invention as copolyimisate a) one starts from (A), (B) and optionally (C) and (D ), which are preferably copolymerized with each other radically and optionally reacted with (E). The reaction with (E) may, if desired, be carried out before, during and after the copolymerization. During or preferably after the copolymerization, it is possible to contact with water. However, it is also possible to dispense with the contact with water for the production of Copoiymerisat a) used in the invention.

In a specific embodiment of the present invention, a free radical copolymerization of (A), (B) and optionally (C) and (D) is carried out first and then reacted with (E). In another specific embodiment of the present invention, the radical copolymerization of (A), (B), and optionally (C) and (D) is carried out in the presence of the entire amount or proportions of the compound (E) to be used.

In another specific embodiment of the present invention, first (A) and optionally (D) are reacted with (E) and then free-radically copolymerized with (B) and optionally (C).

If a reaction of copolymer of (A), (B) and optionally (C) and (D) with (E) or a free-radical copolymerization in the presence of (E) is desired, then the total amount of (E) is calculated such that starting from a complete reaction of (E) and up to 50 mol%, preferably 1 to 30 mol%, particularly preferably 2 to 20 mol% (E), based on all carboxyl groups of the copolymer used. In the context of the present invention, the term "all carboxyl groups contained in the polymer" is understood as meaning those carboxyl groups of copolymerized comonomers (A) and optionally (D) which are present as anhydride, as C ₁ -C ₄ -alkyl ester or as carboxylic acid ,

The free-radical copolymerization is advantageously started by initiators, for example peroxides or hydroperoxides. Di-tert-butyl peroxide, tert-butyl peroctoate, tert-butyl perpivalate, tert-butyl per-2-ethylhexanoate, tert-butyl permaleinate, tert-butyl perisobutyrate, benzoyl peroxide, diacetyl peroxide, succinic peroxide, Chlorobenzoyl peroxide, Dicyclohexylperoxiddicarbonat, exemplified. The use of redox initiators is also suitable, for example combinations of hydrogen peroxide or sodium peroxodisulfate or one of the abovementioned peroxides with a reducing agent. Suitable reducing agents are, for example, ascorbic acid, tartaric acid, Fe (II) salts such as FeSO ₄ , sodium bisulfite, potassium bisulfite.

Suitable initiators are also azo compounds such as 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2-methylpropionamidine) dihydrochloride and 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile).

In general, initiator is used in amounts of 0.1 to 20 wt .-%, preferably 0.2 to 15 wt .-%, calculated on the mass of all comonomers.

The copolymerization can be carried out in the presence or absence of solvents and precipitants. Suitable solvents for the radical copolymerization are polar acid anhydride inert solvents such as e.g. Acetone, tetrahydrofuran and dioxane. Suitable precipitants are, for example, toluene, ortho-xylene, meta-xylene and aliphatic hydrocarbons.

In a preferred embodiment, one works without solvent or in the presence of only small amounts of solvent, ie 0.1 to a maximum of 10 wt .-%, based on total weight of comonomers (A), (B) and optionally (C) and (D). Suitable solvents are understood to be inert substances under the conditions of copolymerization and esterification or amide formation, in particular aliphatic and aromatic hydrocarbons such as, for example, cyclohexane, n-heptane, isododecane, benzene, toluene, ethylbenzene, xylene as isomer mixture, meta-xylene, ortho -xylene. If one works in the reaction with (E) without acidic catalyst or dispensed with the reaction with (E), then the radical Copoiymerisation and optionally reaction with (E) in solvents selected from ketones such as acetone, methyl ethyl ketone, or cyclic or non-cyclic ethers such as tetrahydrofuran or di-n-butyl ether.

The copolymerization and optionally the reaction with (E) is preferably carried out with exclusion of oxygen, for example in a nitrogen or argon atmosphere, preferably in a stream of nitrogen.

For the radical copolymerization and, if appropriate, the reaction with (E) it is possible to use customary apparatuses, eg. As autoclave and boiler.

The order of addition of the comonomers can be made in various ways.

In one embodiment, a mixture of (E) and (A) is added and initiator is added and simultaneously (B) and optionally (C) and (D). It is preferred to add (B) and optionally (C) and optionally (D) in the manner of a feed process.

In another embodiment, a mixture of (E) and (A) is provided and initiator and simultaneously (B) and optionally (C) and (D) in the manner of a feed process, wherein initiator, (B) and optionally (C ) and (D) are each dissolved in (E).

In another embodiment, a mixture of (E) and (A) is provided and gives initiator and (B), (C) and (D) in the manner of a feed process, wherein the feed rates of (B), (C) and (D) are chosen differently.

In another embodiment, a mixture of (E) and (A) is provided and gives initiator and (B), (C) and (D) in the manner of a feed process, wherein the feed rates of (B), (C) and (D) are chosen the same.

In another embodiment, (A) and, if appropriate, (D) are added and initiator and (B) and, if appropriate, (C) are added in the manner of a feed process and are then reacted with (E), if appropriate. In another embodiment, (A) is introduced and initiator, (B) and optionally (C) and (D) are added in the manner of a feed process and subsequently reacted with (E), if appropriate. In another embodiment, (A) and (B) are introduced, and initiator and, if appropriate, (C) are added in the manner of a feed process and are then reacted with (E), if appropriate.

In another embodiment, (B) and optionally (C) and (D) are added and initiator and (A) added in the manner of a feed process and subsequently reacted with (E), if appropriate.

In another embodiment, (B) and, if appropriate, (C) are added and initiator (A) and, if appropriate, (D) are added in the manner of a feed process and are then reacted with (E) if appropriate. In another embodiment, (B) and, if appropriate, (D) are added and initiator (A) and, if appropriate, (C) are added in the manner of a feed process and are then reacted with (E) if appropriate.

In another embodiment, (A), (B) and optionally (C) and (E) are added, and initiator and (D) are added in the manner of a feed process. (A), (B) and optionally (E) may also be presented in a solvent.

In one embodiment, additional initiator is added during the addition of (B), (C) and optionally (D).

In one embodiment, additional initiator is added during the addition of (A) and optionally (D). In one embodiment, the temperature for the copolymerization of (A), (B) and optionally (C) and (D) in the range of 80 to 300 ⁰ C, preferably 90 to 200 ⁰ C.

The pressure is for example in the range of 1 to 15 bar, preferably 1 to 10 bar.

It is possible to use regulators, for example C ₁ to C ₄ -aldehydes, formic acid and compounds containing organic SH groups, such as 2-mercaptoethanol, 2-mercaptopropanol, mercaptoacetic acid, tert-butylmercaptan, n-dodecylmercaptan. Polymerization regulators are generally used in amounts of from 0.1 to 10% by weight, based on the total mass of the comonomers used. Preference is given to working without the use of controllers.

It is possible during the copolymerization to add one or more polymerization inhibitors in small amounts, for example hydroquinone monomethyl ether. Polymerization inhibitor can be advantageously with (B) and optionally dosed (C) and (D). Suitable amounts of polymerization inhibitor are 0.01 to 1 wt .-%, preferably 0.05 to 0.5 wt .-%, calculated on the mass of all comonomers. The addition of polymerization inhibitor is particularly preferred when the copolymerization is carried out at temperatures above 80 ° C.

After completion of the addition of (A), (B) and optionally (C) and (D), optionally (E) and optionally initiator can be allowed to react. The duration of the free radical copolymerization is generally 1 to 12 hours, preferably 2 to 9 hours, particularly preferably 3 to 6 hours.

The duration of the reaction with (E) can be 1 to 12 hours, preferably 2 to 9 hours, particularly preferably 3 to 6 hours. If the preparation of (a) is carried out by copolymerizing (A), (B) and optionally (C) and (D) in the presence of the total amount of (E), the reaction time is from 1 to 12 hours in total , preferably 2 to 10 hours, more preferably 3 to 8.

One can carry out the reaction with (E) in the absence or also presence of catalysts, in particular acidic catalysts such as e.g. Sulfuric acid, methanesulfonic acid, p-toluenesulfonic acid, n-dodecylbenzenesulfonic acid, hydrochloric acid or acidic ion exchangers.

In a further variant of the process described, the reaction with (E) is carried out in the presence of an entraining agent which forms an azeotrope with water which may be formed during the reaction.

In general, under the conditions of steps (E) described above, all or part of the carboxyl groups of the anhydrides (A) and optionally the carboxyl groups of (D) will react. Generally, less than 40 mole% will remain as unreacted (E). It is possible to separate unreacted (E) from copolymer obtainable by the preparation process according to the invention by methods known per se, such as, for example, extraction.

In one embodiment, the further step of separating unreacted (E) from the copolymers produced can be dispensed with. In this embodiment, copolymers are used together with a certain percentage of unreacted (E) for the treatment of fibrous substrates.

The above-described copolymerization of (A) ₁ (B) and optionally (C) and (D) gives copolymers. The resulting copolymers can be subjected to purification by conventional methods, for example, reprecipitation or extractive removal of unreacted monomers. If a solvent or precipitant has been used, it is possible to remove it after completion of the copolymerization, for example by distillation.

In the context of the present invention, the copolymer prepared as described above can be contacted with water, specifically the amount of added water is calculated so as to obtain a dispersion according to the invention which has a water content in the range from 30 to 99.5% by weight. , Have based on the total mass of aids. In one embodiment, after the radical copolymerization and, if appropriate, the reaction with (E) with water, the water may still contain Bronsted acid or preferably Bronsted base. Examples of Bronsted acids are sulfuric acid, hydrochloric acid, tartaric acid and citric acid. Examples of Bronsted base are alkali metal hydroxides such as, for example, NaOH and KOH, alkali metal carbonates such as Na ₂ CO ₃ and K ₂ CO ₃ , alkali metal hydrogencarbonate such as NaHCO ₃ and KHCO ₃ , ammonia, amines such as, for example, trimethylamine, triethylamine, diethylamine, Ethanolamine, N, N-diethanolamine, N ₁ N ₁ N-triethanolamine, N-methylethanolamine. The concentration of Bronsted acid or preferably Bπzmsted base is generally from 1 to 20% by weight, based on the sum of water and Brønsted acid or water and Bronsted base.

It is already possible to add water during the free-radical copolymerization, but it is preferred to add water only toward the end of the free-radical copolymerization. If the free-radical copolymerization and the reaction with (E) have been carried out in the presence of solvent, it is preferable first to remove solvents, for example by distilling off and only then to contact with water.

By contacting with water, which may optionally contain Bronsted acid or preferably Bronsted base, the carboxylic acid anhydride groups present in the copolymer can be partially or completely hydrolyzed.

After contacting with water, which optionally Bronsted acid or, preferably, can include Bronsted-base, can be preferably allowed to react to 100 ⁰ C, at temperatures ranging from 20 to 120 ⁰ C _1, and for a period of 10 minutes to 48 hours. In one embodiment of the present invention, sets of water, wherein the water or, preferably, may contain Bronsted acid Bronsted base, at 50 to 100 ⁰ C before and are added by a feed method, if appropriate, at 50 to 120 ⁰ C heated copolymer to.

In a further embodiment of the present invention, copolymer at 50 to 120 ⁰ C before and are added by a feed method, the optionally up to 100 ° C was heated to 50 water, the water may still contain Bronsted acid or preferably Bronsted base.

In one embodiment of the present invention, a mixture of water, wherein the water may still contain Bronsted acid or preferably Bronsted base and nonionic surfactant, at 50 to 100 ⁰ C before and gives in the manner of a feed optionally to 50 bis 120 ⁰ C heated copolymer too. Suitable nonionic surfactants are, for example, multiply, preferably 3 to 30 times, alkoxylated C ₁₂ -C ₃₀ alkanols. In another embodiment, copolymer at 50 to 120 ⁰ C before and are added by a feed method, the optionally 50 to 100 ⁰ C heated mixture to water, said water still contain Bronsted acid or preferably Bronsted base and nonionic surfactant As a non-ionic surfactant is, for example, several times, preferably 3 to 30-fold aikoxyliertes Ci ₂ -C ₃₀ alkanol in question.

The copolymers described above are usually in the form of aqueous dispersions or aqueous solutions or in bulk. Aqueous dispersions and solutions of copolymers described above are also the subject of the present invention. From novel aqueous dispersions and solutions, copolymers according to the invention can be isolated by methods known per se to those skilled in the art, for example by evaporation of water or by spray-drying.

Shampoos and hair products

The shampoos according to the invention containing copolymer a), optionally mixed with oligomer b), have washing activity without the addition of further surfactants.

In a preferred embodiment of the invention, the shampoos and hair care compositions according to the invention in addition to copolymer a), which is optionally mixed with oligomer b), further contain at least one oil and / or fat phase.

In a preferred embodiment of the invention, the shampoos and hair care compositions according to the invention in addition to copolymer a), which is optionally mixed with oligomer b), further comprise at least one surfactant.

In a preferred embodiment of the invention, the shampoos and hair care compositions according to the invention in addition to copolymer a), which is optionally mixed with oligomer b), further contain at least one oil and / or fat phase and a surfactant.

Surfactants Surfactants which can be used are anionic, cationic, nonionic and / or amphoteric surfactants.

Advantageous washing-active anionic surfactants for the purposes of the present invention are acylamino acids and their salts, such as

Acylglutamates, in particular sodium acylglutamate sarcosinates, for example myristoyl sarcosine, TEA lauroyl sarcosinate, sodium lauroyl sarcosinate and sodium cocoyl sarcosinate, sulfonic acids and their salts, such as

Acyl isethionates, for example sodium or ammonium cocoyl isethionate

Sulfosuccinates, for example dioctyl sodium sulphosuccinate, disodium laureth sulphosuccinate, disodium lauryl sulphosuccinate and disodium undecylenamido MEA sulphosuccinate,

Disodium PEG-5 Laurylcitratsulfosuccinat and derivatives, and sulfuric acid esters, such as

Alkyl ether sulfate, for example sodium, ammonium, magnesium, MIPA, TIPA laureth sulfate, sodium myreth sulfate and sodium C _12-I3 pareth sulfate, alkyl sulfates, for example sodium, ammonium and TEA lauryl sulfate. Further advantageous anionic surfactants are

Taurates, for example sodium lauroyl taurate and sodium methyl cocoyl taurate,

Ether carboxylic acids, for example sodium laureth-13 carboxylate and sodium PEG-6 cocamide carboxylate, sodium PEG-7-olive oil-carboxylate-phosphoric acid ester and salts, such as, for example, DEA-oleth-10 phosphate and dilaureth-4 phosphate, Alkyl sulfonates, for example sodium coconut monoglyceride sulfate, sodium C _12-U olefin sulfonate, sodium lauryl sulfoacetate and magnesium PEG-3 cocamide sulfate,

Acylglutamates such as di-TEA-palmitoylaspartate and sodium caprylic / capric glutamate,

Acyl peptides, for example palmitoyl hydrolyzed milk protein, sodium cocoyl-hydrolyzed soy protein and sodium / potassium cocoyl-hydrolyzed collagen, as well as carboxylic acids and derivatives, such as

for example, lauric acid, aluminum stearate, magnesium alkoxide and zinc undecylate, ester carboxylic acids, for example, calcium stearoyl lactylate, laureth-6 citrate, and sodium PEG-4 lauramide carboxylate alkylarylsulfonates.

Advantageous washing-active cationic surfactants for the purposes of the present invention are quaternary surfactants. Quaternary surfactants contain at least one N atom covalently linked to 4 alkyl or aryl groups. For example, alkylbetaine, alkylamidopropylbetaine and alkylamidopropylhydroxysultaine are advantageous.

Further advantageous cationic surfactants in the context of the present invention are further

- alkylamines,

- Alkylimidazole and - ethoxylated amines and in particular their salts.

Advantageous washing-active amphoteric surfactants for the purposes of the present invention are acyl / dialkylethylenediamines, for example sodium acylamphoacetate, disodium alophphodipropionate, disodium alkylamphodiacetate, sodium acylamphohydroxypropylsulphonate, disodium acylamphodiacetate, sodium acylamphopropionate, and N-coconut fatty acid amidoethyl-N-hydroxyethylglycinate sodium salts. Further advantageous amphoteric surfactants are N-alkylamino acids, for example aminopropylalkylglutamide, alkylaminopropionic acid, sodium alkylimidodipropionate and lauroamphocarboxyglycinate. Advantageous washing-active nonionic surfactants in the context of the present invention are

Alkanolamides, such as cocamide MEA / DEA / MIPA,

Esters which are formed by esterification of carboxylic acids with ethylene oxide, glycerol, sorbitan or other alcohols, ethers, for example ethoxylated alcohols, ethoxylated lanolin, ethoxylated polysiloxanes, propoxylated POE ethers, alkyl polyglycosides such as lauryl glucoside, decyl glycoside and cocoglycoside, glycosides with an HLB Value of at least 20 (eg BeilSil ^® SPG 128V (Wacker)). Further advantageous nonionic surfactants are alcohols and amine oxides, such as cocoamidopropylamine oxide.

Preferred Shampoo Surfactants: Preferred anionic, amphoteric and nonionic shampoo surfactants are described, for example, in "Cosmetics and Hygiene from Head to Toe", Ed. W. Limbach, 3rd edition, Wiley-VCH, 2004, p.131-134, to which reference is made in full at this point.

Among the alkyl ether sulfates, sodium alkyl ether sulfates based on di- or tri-ethoxylated lauryl and myristyl alcohol are particularly preferred. They clearly outperform the alkyl sulfates with regard to their resistance to water hardness, colourability, low solubility and, in particular, skin and mucous membrane compatibility. They can also be used as sole washing raw materials for shampoos. Lauryl ether sulfate has better foam properties than myristyl ether sulfate, but it is inferior in mildness. Medium and especially higher alkyl ether carboxylates are among the mildest surfactants ever but exhibit poor foam and viscosity performance. They are often used in combination with alkyl ether sulfates and amphoteric surfactants in shampoos.

Sulfosuccinic acid esters (sulfosuccinates) are mild and, because of their poor thickenability, preference is given to using surfactants which are preferred only in neutral or well-buffered products only together with other anionic and amphoteric surfactants and, owing to their low hydrolytic stability.

Amidopropylbetaines are practically insignificant as sole washing raw materials, since their foaming behavior and their thickenability are only moderately pronounced. In contrast, these surfactants have an excellent skin and eye mucous membrane compatibility. In combination with anionic surfactants, their mildness can be synergistically improved. Preferred is the use of cocamidopropyl betaine.

Arnphotoacetates / amphodiacetates, as amphoteric surfactants, have a very good skin and mucous membrane compatibility and can have a hair-conditioning effect or increase the Pfiewerkirkung of additives. They are similar to the betaines used to optimize alkyl ether sulfate formulations. Most preferred are sodium cocoamphoacetate and disodium cocoamphodiacetate.

Alkyl polyglycosides are nonionic washing raw materials. They are mild, have good universal properties, but lather weakly. For this reason, they are preferably used in combination with anionic surfactants.

Sorbitan esters also belong to the nonionic washing raw materials. Because of their excellent mildness they are preferred for use in baby shampoos. As weak foaming agents, they are preferably used in combination with anionic surfactants. It is advantageous to choose the detergent surfactant (s) according to the invention from the group of surfactants which have an HLB value of more than 25, particularly advantageous are those which have an HLB value of more than 35. It is inventively advantageous if one or more of these surfactants in a concentration of 1 to 30% by weight, preferably in a concentration of 5 to 25% by weight and most preferably in a concentration of 10 to 20% by weight, respectively based on the total weight of the composition is used.

Polysorbate

Furthermore, according to the invention, polysorbates may advantageously be incorporated into the composition as washing-active agents.

In the context of the invention, advantageous polysorbates are the

Polyoxyethylene (20) sorbitan monolaurate (Tween 20, CAS No. 9005-64-5)

Polyoxyethylene (4) sorbitan monolaurate (Tween 21, CAS No. 9005-64-5)

Polyoxyethylene (4) sorbitan monostearate (Tween 61, CAS No. 9005-67-8) - polyoxyethylene (20) sorbitan tristearate (Tween 65, CAS No. 9005-71 -4)

Polyoxyethylene (20) sorbitan monooleate (Tween 80, CAS No. 9005-65-6)

Polyoxyethylene (5) sorbitan monooleate (Tween 81, CAS No. 9005-65-5)

Polyoxyethylene (20) sorbitan trioleate (Tween 85, CAS No. 9005-70-3).

Particularly advantageous are in particular

Polyoxyethylene (20) sorbitan monopaimitate (Tween 40, CAS No. 9005-66-7)

Polyoxyethylene (20) sorbitan monostearate (Tween 60, CAS No. 9005-67-8).

These are advantageously used according to the invention in a concentration of from 0.1 to 5% by weight and in particular in a concentration of from 1.5 to 2.5% by weight, based on the total weight of the composition, individually or as a mixture of a plurality of polysorbates.

Hair Care Products The aim of hair care is to preserve the natural state of the newly regrown hair over a long period of time and, if possible, to restore it in the event of loss. Radiant shine and a pleasant, smooth feel are considered features of natural, healthy hair. As a hair care product in the context of this invention, pretreatment agents, hair conditioners (hair conditioner, hair balsam), hair treatments, one distinguishes between the spa products that remain in the hair (Ieave-On) and those that are rinsed-off, hair lotions, Hair styling products such as pomades, styling creams, styling lotions, hair styling gels (hair gels, wet-look gels, glitter gels), top fluids, hot oil treatments and foam cures. The usual formulations known to those skilled in the hair care products mentioned are described in "Cosmetics and hygiene from head to toe", ed. W. Limbach, 3rd edition, Wiley- VCH, 2004, chap. 9.2, p.247-264, to which reference is made at this point. The ingredients present in addition to the copolymer and optionally oligomer b) in the hair care preparations are mentioned above and below and in some cases identical to those which may also be contained in the shampoos according to the invention.

Depending on the field of application, the hair care products can be applied as a spray, foam, gel, gel spray, cream, lotion or wax.

Hairsprays include both aerosol sprays and pump sprays without propellant gas. Hair foams include both aerosol foams and pump foams without propellant gas. Hair sprays and hair foams preferably comprise predominantly or exclusively water-soluble or water-dispersible components. If the compounds used in the hair sprays and hair foams according to the invention are water-dispersible, they can be used in the form of aqueous microdispersions with particle diameters of usually from 1 to 350 nm, preferably from 1 to 250 nm. The solids contents of these preparations are usually in a range of about 0.5 to 20 wt .-%. As a rule, these microdispersions do not require emulsifiers or surfactants for their stabilization.

Hair styling agents are as little subject matter of the present invention as hair fixatives which are not in the form of shampoos.

conditioners

The hair care compositions and shampoo compositions according to the invention contain conditioning agents in a preferred embodiment.

Conditioning agents which are preferred according to the invention are, for example, all compounds which are described in the International Cosmetic Ingredient Dictionary and Handbook (Volume 4, publisher: RC Pepe, JA Wenninger, GN McEwen, The Cosmetic, Dental and Fragrance Association, 9th edition, 2002) under Section 4 under the headings Hair Conditioning Agents, Humectants, Skin Conditioning Agents, Skin Conditioning Agents Emollient, Skin Conditioning Agents Humectant, Skin- Conditioning Agents-Miscellaneous, Skin Conditioning Agents-Occlusive, and Skin Protectans and all of the compounds listed in EP-A 934 956 (p.11-13) under "water-soluble conditioning agent" and "oil-soluble conditioning agent". Further advantageous conditioning substances are, for example, the compounds designated as polyquaternium according to INCI (in particular Polyquaternium-1 to Polyquaternium-56).

Suitable conditioning agents include, for example, polymeric quaternary ammonium compounds, cationic cellulose derivatives, chitosan derivatives and polysaccharides.

Conditioning agents which are advantageous according to the invention can be chosen from the compounds shown in Table 1 below. Table 1: Advantageous conditioning agent

Further inventively conditioners advantageous cellulose derivatives and quaternized guar gum derivatives catalyzed, especially guar hydroxypropylammonium (eg Jaguar Excel ^®, Jaguar C 162 ^® (Rhodia), CAS 65497-29-2, CAS 39421-75-5). Also, non-ionic poly N-vinylpyrrolidone / polyvinyl acetate copolymers (eg Lu viskol ^® VA 64 (BASF)), anionic acrylate copolymers (eg Luviflex soft ^® (BASF)), and / or amphoteric amide / acrylate / methacrylate copolymers (for example, Amphomer ^® (National Starch)) can be advantageously used according to the invention as a conditioner. Other possible conditioning agents are quaternized silicones.

thickener

For shampoos suitable thickeners are in "cosmetics and hygiene from head to toe", ed. W. Limbach, 3rd edition, Wiley-VCH, 2004, p.235-236 called, to which reference is made in full.

Consistency regulators make it possible to set the desired viscosity of shampoos. Thickeners, which increase the viscosity of surfactant micelles or swell the water phase, originate from chemically very different classes of substances. Suitable thickening agents for the compositions according to the invention are crosslinked polyacrylic acids and their derivatives, polysaccharides such as xanthan gum, guar-guar, agar-agar, alginates or tyloses, cellulose derivatives, eg. As carboxymethylcellulose or hydroxycarboxymethylcellulose, also higher molecular weight polyethylene glycol mono- and diesters of fatty acids, fatty alcohols, monoglycerides and fatty acids, polyvinyl alcohol and polyvinylpyrrolidone.

Suitable thickeners are also polyacrylates such as Carbopol ^® (Noveon), Ultrez ^® (Noveon), Luvigel EM ^® (BASF), Capigel ^® 98 (Seppic), Synthalens ^® (Sigma), the Aculyn ^® -. Trademarks of Rohm and Haas as Aculyn ^® 22 (copolymer of acrylates and methacrylic acid with stearyl (20 EO units)) and Aculyn ^® 28 (copolymer of acrylates and methacrylic acid with behenyl (25 EO units)). Suitable thickening agents are furthermore, for example, Aerosil types (hydrophilic Silicas), polyacrylamides, polyvinyl alcohol and polyvinylpyrrolidone, surfactants such as ethoxylated fatty acid glycerides, esters of fatty acids with polyols such as pentaerythritol or trimethylolpropane, fatty alcohol ethoxylates with concentrated hornolo distribution or alkyl oligoglucosides and electrolytes such as sodium chloride and ammonium chloride.

Particularly preferred thickening agents for the preparation of gels are ^® Ultrez 21, Aculyn ^® 28, Luvigel EM ^® and Capigel ^® 98th

In particular in the case of more highly concentrated shampoo formulations, substances which reduce the viscosity of the formulation, such as, for example, can be added to regulate the consistency. As propylene glycol or glycerol. These substances have little influence on the product properties.

preservative

As products with high water content shampoos must be reliably protected against contamination. The most important preservatives used for this purpose are urea condensates, p-hydroxybenzoic acid esters, the combination of phenoxyethanol with methyldibromoglutaronitrile and acid preservation with benzoic acid, salicylic acid and sorbic acid.

Shampoo concentrates with high levels of surfactants or polyols and low water contents can also be formulated preservative-free. The compositions of the invention may advantageously contain one or more preservatives. Advantageous preservatives for the purposes of the present invention are, for example, formaldehyde donors (such as, for example, DMDM Hydan- toin which is commercially available, for example under the trade name Glydant ^® (Lonza)), iodopropyl butylcarbamates (for example Glycacil-L ^®, Glycacil-S ^® (Lonza ) Dekaben ^® LMB (Jan Dekker)), parabens (p-hydroxybenzoic acid alkyl ester such as methyl, ethyl, propyl and / or butyl paraben), Dehydroacetic Acid (Euxyl® K 702 (Schulke & Mayr), phenoxyethanol, ethanol, benzoic acid. Also advantageously used are so-called preservative aids, such as, for example, octoxyglycerol, glycines, soya etc. The table below gives an overview of typical preservatives:

Preservatives or preservatives which are common in cosmetics are also advantageous, such as dibromodicyanobutane (2-bromo-2-bromomethylglutarodinitrile), phenoxyethanol, 3-iodo-2-propynyl butyl carbamate, 2-bromo-2-nitropropane-1,3-diol, imidazolidinyl urea, 5-chloro-2-methyl-4-isothiazolin-3-one, 2-chloroacetamide, benzalkonium chloride, benzyl alcohol, salicylic acid and salicylates.

It is particularly preferred if iodopropyl butylcarbamates, parabens (methyl, ethyl, propyl and / or butylparaben) and / or phenoxyethanol are used as preservatives.

Complexing agents: Since the raw materials and even the shampoos themselves are predominantly produced in steel equipment, the end products may contain iron (ions) in trace amounts. In order to prevent these impurities from adversely affecting the product quality via reactions with dyes and perfume oil constituents, complexing agents such as salts of ethylenediaminetetraacetic acid, nitrilotriacetic acid, iminodisuccinic acid or phosphates are added.

UV photoprotective filter: In order to stabilize the ingredients contained in the compositions of the invention such as dyes and perfume oils against changes by UV light, UV light protection filters such. As benzophenone derivatives are incorporated. Suitable for this purpose are all cosmetically acceptable UV light protection filters.

The compositions according to the invention contain UV photoprotective filters in an amount such that the SPF (LSF, determined by the COLIPA method) of the compositions is less than 4. Compositions having an SPF of at least 4 are not subject of this invention.

Antioxidants: An additional content of antioxidants is generally preferred. According to the invention, all antioxidants which are suitable or customary for cosmetic and / or dermatological applications can be used as antioxidants. the . The antioxidants are advantageously selected from the group consisting of amino acids (eg glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazoles (eg urocaninic acid) and derivatives thereof, peptides such as D, L-carnosine, D-camosine, L-carnosine. Camosin and its derivatives (eg anserine), carotenoids, carotenes (eg α-carotene, β-carotene, γ-lycopene) and their derivatives, chlorogenic acid and its derivatives, lipoic acid and its derivatives (eg dihydrolipoic acid), aurothioglucose, propylthiouracil and other thiols (eg thioredoxin, glutathione, cysteine, cystine, cystamine and their glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl, γ-linoleyl -, cholesteryl and glyceryl esters) and their salts, dilaurylthiodipropionate, distearylthiodipropionate, thiodipropionic acid and its derivatives (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) and Sulfoximinver- compounds (eg Buthioninsulfoximine, Homocysteinsulfoximin, Buthioninsulfo ne, penta-, hexa-, heptathionine sulfoximine) in very low tolerated dosages (eg pmol to μmol / kg), furthermore (metal) chelators (eg α-hydroxyfatty acids, palmitic acid, phytic acid, lactoferrin), α-hydroxy acids (eg , Citric acid, lactic acid, malic acid), humic acid, bile acid, bile extracts, bilirubin, biliverdin, EDTA, EGTA and their derivatives, unsaturated fatty acids and their derivatives (eg γ-linolenic acid, linoleic acid, oleic acid), folic acid and its derivatives, furfurylidene sorbitol and its derivatives, ubiquinone and ubiquinol and their derivatives, vitamin C and derivatives (eg ascorbyl palmitate, Mg ascorbyl phosphate, ascorbyl acetate), tocopherols and derivatives (eg vitamin E acetate), vitamin A and derivatives (vitamin A palmitate ) as well as coniferyl benzoate of benzoin resin, rutinic acid and its derivatives, α-glycosylrutin, ferulic acid, furfurylidene glucitol, camosine, butylhydroxytoluene, butylhydroxyanisole, nordihydroguaiacetic acid, nordihydroguajaretic acid, trihydroxybutyrophenone, uric acid and its derivatives, mannose and its derivatives, zinc and its derivatives ( eg ZnO, ZnSO ₄ ) selenium and its derivatives (eg selenium methionine), stilbenes and their derivatives (eg stilbene oxide, trans-stilbene oxide ) and the inventively suitable derivatives (salts, esters, ethers, sugars, nucleotides, nucleosides, peptides and lipids) of these drugs. The amount of the aforementioned antioxidants (one or more compounds) in the compositions is preferably from 0.001 to 30% by weight, more preferably from 0.05 to 20% by weight, especially from 0.1 to 10% by weight, based on the Total weight of the composition. If vitamin E and / or its derivatives are the antioxidant (s), it is advantageous to provide them in concentrations of from 0.001 to 10% by weight, based on the total weight of the composition.

If vitamin A, or vitamin A derivatives, or carotenes or their derivatives are the antioxidant (s), it is advantageous to provide them in concentrations of from 0.001 to 10% by weight, based on the total weight of the composition , Buffers: Buffers ensure the pH stability of the shampoo. Predominantly used are citrate, lactate and phosphate buffers.

Solubilizers: They are used to clearly dissolve nourishing oils or perfume oils and to keep them clear even in the cold. The most common solubilizers are ethoxylated nonionic surfactants, eg. B. hydrogenated and ethoxylated castor oils.

Germ-inhibiting agents: Furthermore, germ-inhibiting agents can also be used. These generally include all suitable preservatives having specific activity against Gram-positive bacteria, e.g. Triclosan (2,4,4'-trichloro-2'-hydroxydiphenyl ether), chlorhexidine (1,1'-hexamethylenebis [5- (4-chlorophenyl) biguanide), and TTC (3,4,4'-trichlorocarbanilide). Quaternary ammonium compounds are also suitable in principle and are preferably used for disinfecting soaps and washing lotions. Also numerous fragrances have antimicrobial properties. Also, a large number of essential oils or their characteristic ingredients such. Clove oil (eugenol), mint oil (menthol) or thyme oil (thymol), show a pronounced antimicrobial activity.

The antibacterial substances are usually used in concentrations of about 0.1 to 0.3 wt .-%.

Dispersant: When in the shampoo insoluble drugs, eg. B. Antischuppenwirk- substances or silicone oils, dispersed and kept in suspense in the long term, must dispersants and thickeners such. For example, magnesium aluminum silicates, Ben tonite, fatty acyl derivatives, polyvinylpyrrolidone or hydrocolloids, z. As xanthan gum or carbomers are used.

According to the invention, preservatives are contained in a total concentration of at most 2, preferably at most 1, 5 and particularly preferably at most 1% by weight, based on the total weight of the composition.

Oils, fats and waxes

In addition to the optionally contained oligomer b), the compositions according to the invention preferably contain further oils, fats or waxes.

A particular advantage of the present invention is that when copolymerisate a) is used, which in a preferred embodiment is mixed with oligomer b), the required amount of further oils, fats or waxes can be significantly lower than usual, the application properties at least as good or even better.

Ingredients of the oil and / or fat phase of the composition of the invention are advantageously selected from the group of lecithins and fatty acid triglycerides, namely the triglycerol esters of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids of a chain length of 8 to 24, in particular 12 to 18 carbon atoms. The fatty acid triglycerides can be selected, for example, advantageously from the group of synthetic, semisynthetic and natural oils, such as olive oil, sunflower oil, soybean oil, peanut oil, rapeseed oil, almond oil, palm oil, coconut oil, castor oil, wheat germ oil, grape seed oil, thistle oil, evening primrose oil, macadamia nut oil and such more. Other polar oil components can be selected from the group of esters of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids having a chain length of 3 to 30 carbon atoms and saturated and / or unsaturated, branched and / or unbranched alcohols of a chain length from 3 to 30 carbon atoms and from the group of esters of aromatic carboxylic acids and saturated and / or unsaturated, branched and / or unbranched alcohols having a chain length of 3 to 30 carbon atoms. Such ester oils can then be advantageously selected from the group isopropyl myristate, isopropyl palmitate, isopropyl stearate, isopropyl oleate, n-butyl stearate, n-hexyl laurate, n-decyl oleate, isooctyl stearate, isononyl stearate, isononyl isononanoate, 2-ethylhexyl palmitate, 2-ethylhexyl laurate, 2-hexyldecyl stearate, 2 Octyl dodecyl palmitate, oleyl oleate, oleylureacate, erucyl oleate, erucyl erucate dicaprylyl carbonate (Cetiol CC) and cocoglycerides (Myritol 331), butylene glycol dicaprylate / dicaprate and dibutyl adipate, as well as synthetic, semi-synthetic and natural mixtures of such esters, such as jojoba oil. Furthermore, one or more oil components can be advantageously selected from the group of branched and unbranched hydrocarbons and waxes, the SiI konöle, the dialkyl ethers, the group of saturated or unsaturated, branched or unbranched alcohols. Any mixtures of such oil and wax components are also advantageous to use in the context of the present invention. It may also be advantageous to use waxes, for example cetyl palmitate, as the sole lipid component of the oil phase.

According to the invention, the olefin component is advantageously selected from the group consisting of 2-ethylhexyl isostearate, octyldodecanol, isotridecyl isononanoate, isoeicosane, 2-ethylhexyl cocoate, C12-15-alkyl benzoate, caprylic capric acid triglyceride, dicaprylyl ether.

Mixtures of C 12-15 -alkyl benzoate and 2-ethylhexyl isostearate, mixtures of C 12-15 -alkyl benzoate and isotridecyl isononanoate and mixtures of C 12-15 -alkyl benzoate, 2-ethylhexyl isostearate and isotridecyl isononanoate are advantageous according to the invention.

Particular preference is given according to the invention to fatty acids triglycerides, in particular soybean oil and / or almond oil, as oils having a polarity of from 5 to 50 mN / m. Of the hydrocarbons, it is advantageous to use paraffin oil, squalane, squalene and in particular (optionally hydrogenated) polyisobutenes in the context of the present invention. Furthermore, the oil phase can advantageously be chosen from the group of Guerbet alcohols. Guerbet alcohols are named after Marcel Guerbet, who first described their production. They arise according to the reaction equation

by oxidation of an alcohol to an aldehyde, by aldol condensation of the aldehyde, elimination of water from the aldol and hydrogenation of allyl aldehyde. Guerbet alcohols are fluid even at low temperatures and cause virtually no skin irritation. Advantageously, they can be used as greasing, overfatting and also moisturizing ingredients in cosmetic compositions.

The use of Guerbet alcohols in cosmetics is known per se. Such spe- cies are usually characterized by the structure

out. R ₁ and R _{2 are} generally unbranched alkyl radicals. Advantageously according to the invention, the Guerbet alcohol or alcohols are selected from the group, where

R ₁ = propyl, butyl, pentyl, hexyl, heptyl or octyl and R ₂ = hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl or tetradecyl.

According to the invention preferred Guerbet alcohols are (commercially available, for example as lsofol ^® 12 (Condea)) 2-butyloctanol and 2-hexyl decanol (for example commercially available as iso- fol ^® 16 (Condea)).

Mixtures of Guerbet AIkoholen are according to the invention may advantageously be used such as mixtures of 2-butyloctanol and 2-hexyl decanol (for example as lsofol ^® 14 (Condea) commercially available).

Any mixtures of such oil and wax components are advantageous in

Use of the present invention.

Among the polyolefins, polydecenes are the preferred substances. The

Advantageously, the oil component may further comprise a content of cyclic or linear silicone oils or consist entirely of such oils, although it is preferred to use an additional content of other oil phase components in addition to the silicone oil or silicone oils. Low molecular weight silicones or silicone oils are generally defined by the following general formula

Higher molecular weight silicones or silicone oils are generally defined by the following general formula

where the silicon atoms may be substituted by identical or different alkyl radicals and / or aryl radicals, which are here generalized by the radicals R ₁ to R ₄ . However, the number of different radicals is not necessarily limited to 4, m may assume values of 2 to 200,000. Cyclic silicones which are advantageously used in accordance with the invention are generally defined by the following general formula

wherein the silicon atoms can be substituted with identical or different alkyl radicals and / or aryl radicals, which are here generalized by the radicals R ₁ to R ₄ . However, the number of different radicals is not necessarily limited to 4, n may assume values of 3/2 to 20. Broken values for n take into account that odd numbers of siloxyl groups may be present in the cycle. Phenyltrimethicone is advantageously chosen as silicone oil. Other silicone oils, for example dimethicone, hexamethylcyclotrisiloxane, phenyldimethicone, cyclomethicone (eg decamethylcyclopentasiloxane), hexamethylcyclotrisiloxane, polydimethylsiloxane, poly (methylphenylsiloxane), cetyldimethicone, behenoxydimethicone, are to be used advantageously in the context of the present invention. Also advantageous are mixtures of cyclomethicone and Isotridecylisononanoat, and those of cyclomethicone and 2-Ethylhexylisostearat.

However, it is also advantageous to choose silicone oils of a similar constitution to the compounds described above, whose derivatized organic side chains, while For example, polyethoxylated and / or polypropoxylated. These include, for example polysiloxane polyalkyl-polyether copolymers such as cetyl dimethicone copolyol. Advantageously, cyclomethicone (octamethylcyclotetrasiloxane) is used as the silicone oil to be used according to the invention.

Fat and / or wax components which can advantageously be used according to the invention can be selected from the group of vegetable waxes, animal waxes, mineral waxes and petrochemical waxes. Candelilla wax, carnauba wax, Japan wax, Esparto grass wax, cork wax, guaruma wax, rice germ oil wax, sugarcane wax, berry wax, ouricury wax, montan wax, jojoba wax, shea butter, beeswax, shellac wax, spermaceti, lanolin (wool wax), crepe fat, ceresin, ozokerite are advantageous, for example (Ground wax), paraffin waxes and micro waxes. Further advantageous fat and / or wax components are chemically modified waxes and synthetic waxes, such as Syncrowax ^® (glyceryl tribehenate), and Syncrowax ^® AW 1 C - waxes (C ₈ ₃₆ fatty acid) as well as Montanesterwachse, sasol, hydrogenated jojoba , synthetic or modified beeswaxes (z. B. dimethicone copolyol beeswax and / or C ₃ o _-5 o-alkyl beeswax), cetyl ricinoleates leate such as Tegosoft ^® CR, polyalkylene waxes, polyethylene glycol waxes, but also chemically modified fats such. Hydrogenated vegetable oils (for example hydrogenated castor oil and / or hydrogenated coconut fat glycerides), triglycerides such as hydrogenated soy glyceride, trihydroxystearin, fatty acids, fatty acid esters and glycol kolester such as C ₂ o- ₄ o-alkyl stearate, C ₂ o- ₄ o-Alkylhydroxystearoylstearat and / or glycol montanate. Other advantageous compounds are certain organosilicon compounds which have similar physical properties to the abovementioned fatty and / or wax components, for example stearoxytrimethylsilane. According to the invention, the fat and / or wax components can be used both individually and as a mixture in the compositions. Any mixtures of such oil and wax components are also advantageous to use in the context of the present invention.

Advantageously, the oil phase is selected from the group consisting of 2-ethylhexyl isostearate, octyldodanol, isotridecyl isononanoate, butylene glycol dicaprylate / dicaprate, 2-ethylhexyl cocoate, C _12-15 alkyl benzoate, caprylic capric acid triglyceride, dicaprylyl ether. Particularly advantageous are mixtures of octyldodecanol, caprylic-capric acid triglyceride, dicaprylyl ether, dicaprylyl carbonate, cocoglycerides, or mixtures of C _12-15 -alkyl benzoate and 2-ethylhexyl isostearate, mixtures of C ₁₂ -i ₅ alkyl benzoate and butylene glycol dicaprylate / dicaprate and mixtures from Ci ₂ .i ₅ -alkyl benzoate, 2-ethylhexyl isostearate and Isotridecylisononanoat. Of the hydrocarbons, paraffin oil, cycloparaffin, squalane, squalene, hydrogenated polyisobutene or polydecene are to be used advantageously in the context of the present invention. The oil component is also advantageously selected from the group of phospholipids. The phospholipids are phosphoric acid esters of acylated glycerols. Of the utmost importance among the phosphatidylcholines are, for example, the lecithins, which are distinguished by the general structure

characterized wherein R 'and R "are typically unbranched aliphatic radicals represented with 15 or 17 carbon atoms and up to 4 cis-double bonds. As according to the invention advantageous paraffin oil according to the invention Mercury Weissoel Pharma 40 from Merkur Vaseline, Shell Ondina ^® 917, Shell Ondina ^® 927, Shell Oil 4222, Shell Ondina 933 ^® from Shell & DEΞA OiI, pioneer ^® 6301 S, pioneer ^® 2071 (Hansen & Rosenthal) can be used.

Suitable cosmetically acceptable oil and fat components are described in Karl-Heinz Schrader, Fundamentals and Formulations of Cosmetics, 2nd edition, Verlag Hüthig, Heidelberg, p. 319-355, which is hereby incorporated by reference in its entirety.

The content of further oils, fats and waxes is at most 50, preferably 30, more preferably at most 20% by weight, based on the total weight of the composition. The amount of oligomer b) does not fall below the content of other further oils, fats and waxes.

The compositions according to the invention optionally contain, in addition to the abovementioned substances, the additives customary in cosmetics or dermatology, for example perfume, dyes, antimicrobial substances, lipid-replenishing agents, complexing and sequestering agents, pearlescing agents, plant extracts, vitamins, active ingredients, preservatives, bactericides, pigments, which have a coloring effect, thickeners, softening, moisturizing and / or moisturizing substances, or other conventional ingredients of a cosmetic or dermatological formulation such as alcohols, polyols, polymers, pH adjusting organic acids, foam stabilizers, electrolytes, organic solvents or SiIi - derivatives.

With regard to the said further ingredients known to the person skilled in the art for the compositions, reference is made to "Cosmetics and hygiene from head to toe", ed. W. Umbach, 3rd edition, Wiley-VCH, 2004, pages 123-128, whereupon at this point, reference is made in full. Ethoxylated glycerol fatty acid esters

The shampoos and hair-care preparations according to the invention optionally comprise ethoxylated oils selected from the group of the ethoxylated glycerol fatty acid esters, more preferably PEG-10 olive oil glycerides, PEG-11 avocado oil glycerides, PEG-11 cocoa butter glycerides, PEG-13 sunflower oil glycerides, PEG-15 glyceryl isosteate, PEG- 9 Coconut Fatty Acid Glycerides, PEG-54 Hydrogenated Castor Oil, PEG-7 Hydrogenated Castor Oil, PEG-60 Hydrogenated Castor Oil, Jojoba Oil Ethoxylate (PEG-26 Jojoba Fat Acids, PEG-26 Jojoba Alcohol), Glycereth-5 Cocoate, PEG-9 Coconut Fatty Acid Glycerides, PEG -7 glyceryl cocoate, PEG-45 palm oil glycerides, PEG-35 castor oil, olive oil PEG-7 ester, PEG-6 caprylic acid / capric acid glycerides, PEG-10 olive oil glycerides, PEG-13 sunflower oil glycerides, PEG-7 hydrogenated castor oil, hydrogenated palm oil glyceride PEG-6 Esters, PEG-20 corn oil glycerides, PEG-18 glyceryl olead cocoate, PEG-40 hydrogenated castor oil, PEG-40 castor oil, PEG-60 hydrogenated castor oil, PEG-60 corn oil giyceride, PEG-54 hydrogenated castor oil, PEG-45 palm oil glycerides, PEG-80 glyceryl cocoate, PEG-60 almond oil glycerides, PEG-60 "Evening Primrose" glycerides, PEG-200 hydrogenated glyceryl palmitate, PEG-90 glyceryl isostearate.

Preferred ethoxylated oils are PEG-7 glyceryl cocoate, PEG-9 coconut glycerides, PEG-40 hydrogenated castor oil, PEG-200 hydrogenated glyceryl palmat. Ethoxylated glycerol fatty acid esters are used in aqueous cleaning formulations for various purposes. Glycerol fatty acid esters with a degree of ethoxylation of about 30-50 serve as solubilizers for non-polar substances such as perfume oils. Highly ethoxylated glycerol fatty acid esters are used as thickeners.

drugs

It has been found that a wide variety of active ingredients with different solubilities can be incorporated homogeneously into the shampoos and hair-care preparations according to the invention. The substantivity of the active ingredients on the hair is higher from the described composition than from conventional surfactant-containing cleansing formulations.

According to the invention, the active ingredients (one or more compounds) can be advantageously selected from the group consisting of acetylsalicylic acid, atropine, azulene, hydrocortisone and its derivatives, for. B. hydrocortisone-17-valerate, vitamins of the B and D series, especially vitamin B1, vitamin B12, vitamin D, vitamin A or its derivatives such as retinyl palmitate, vitamin E or its derivatives such as tocopheryl acetate, vitamin C. and its derivatives such as ascorbyl glucoside but also niacinamide, panthenol, bisabolol, polydocanol, unsaturated fatty acids such as the essential fatty acids (commonly referred to as vitamin F), in particular γ-linolenic acid, oleic acid, eicosapentaenoic acid, docosahexaenoic acid and derivatives thereof , Chloramphenicol, caffeine, prostaglandins, thymol, camphor, squalene, extracts or other products of plant and animal origin, eg. As evening primrose oil, borage oil or currant seed oil, fish oils, cod liver oil but also ceramides and ceramide-like Compounds, frankincense extract, green tea extract, water-lily extract, licorice extract, witch hazel, antidandruff active ingredients (eg, selenium disulfide, zinc pyrithione, piroctone, olamine, climbazole, octopirox, polydocanol and their combinatins), complexing agents such as those from γ-oryzanol and calcium salts such as calcium panthotenate, calcium chloride, calcium acetate.

It is also to choose the active ingredients from the group of emollients advantageous, for example PurCellin, Eucerit ^® and Neocerit® ^®. The active ingredient (s) are furthermore advantageously selected from the group of NO synthase inhibitors, in particular when the compositions according to the invention are used for the treatment and prophylaxis of the symptoms of intrinsic and / or extrinsic aging and for the treatment and prophylaxis of the harmful effects of ultraviolet radiation on the hair should serve. Preferred NO synthase inhibitor is nitroarginine. Further advantageously, the active ingredient (s) are selected from the group comprising catechins and bile acid esters of catechins and aqueous or organic extracts from plants or plant parts which have a content of catechins or bile acid esters of catechins, such as the leaves of the plant family Theaceae, in particular of the species Camellia sinensis (green tea). Particularly advantageous are their typical ingredients (eg polyphenols or catechins, caffeine, vitamins, sugars, minerals, amino acids, lipids).

Catechins represent a group of compounds which are to be regarded as hydrogenated flavones or anthocyanidins and derivatives of "catechin" (catechol, 3,3 ', 4', 5,7-flavanpentaol, 2- (3,4-dihydroxyphenyl) -chroman Also, epicatecine ((2R, 3R) -3,3 ', 4', 5,7-flavanpentaol) is an advantageous active ingredient in the sense of the present invention.

Also advantageous are herbal extracts containing catechins, especially extracts of green tea, such as. B. extracts from leaves of the plants of the species Camellia spec, especially the teas Camellia sinenis, C. assamica, C. taliensis and C. inawadiensis and crosses of these with, for example, Camellia japonica.

Further preferred active substances are polyphenols or catechins from the group (-) - catechin, (+) - catechin, (-) - catechin gallate, (-) - gallocatechin gallate, (+) - epicatechin, (-) - epicatechin, (-) Epicatechin gallate, (-) - epigallocatechin, (-) - epigallocatechin gallate. Flavon and its derivatives (often collectively referred to as "flavones") are also advantageous active substances in the sense of the present invention.

Some of the more important flavones, which can also be used preferably in compositions according to the invention, are listed in Table 2 below.

Table 2: Flavones

In nature, flavones usually occur in glycosidated form. According to the invention, the flavonoids are preferably selected from the group of substances of the general formula

where Z ₁ to Z ₇ , independently of one another, are selected from the group consisting of H, OH, alkoxy and hydroxyalkoxy, where the alkoxy or hydroxyalkoxy groups may be branched and unbranched and have 1 to 18 C atoms, and where GIy is selected from the group of mono- and Oligoglycosidreste.

According to the invention, however, the flavonoids can also be chosen advantageously from the group of substances of the general formula

where Z ₁ to Z _{6 are} independently selected from the group consisting of H, OH, alkoxy and hydroxyalkoxy, where the alkoxy or hydroxyalkoxy groups can be branched and unbranched and have 1 to 18 C atoms, and wherein GIy is selected from the group of mono- and oligoglycoside radicals.

Preferably, such structures can be selected from the group of substances of the general formula

wherein Z ₁ to Z ₆ independently of one another as mentioned above and GIy ₁ , GIy ₂ and GIy ₃ independently represent monoglycoside or Oligoglycosidreste. GIy ₂ or GIy ₃ can also individually or together represent saturations by hydrogen atoms.

Preferably, GIy ₁ , GIy ₂ and GIy _{3 are} independently selected from the group of hexosyl radicals, in particular the rhamnosyl radicals and glucosyl radicals. However, other hexosyl radicals, for example allosyl, altrosyl, galactosyl, gulosyl, idosyl, mannosyl and talosyl, may also be advantageous to use. It may also be advantageous according to the invention to use pentosyl radicals.

Advantageously, Z ₁ to Z _{5 are} independently selected from the group H, OH, methoxy, ethoxy and 2-hydroxyethoxy, and the flavone glycosides correspond to the general structural formula

Most preferably, the flavone glycosides are selected from the group represented by the following structure.

wherein GIy ₁ , GIy ₂ and GIy _{3 are} independently monoglycoside or oligoglycoside residues. GIy ₂ or GIy ₃ can also individually or jointly represent saturations by hydrogen atoms. Preferably, GIy ₁ , GIy ₂ and GIy _{3 are} independently selected from the group of hexosyl radicals, in particular the rhamnosyl radicals and glucosyl radicals. However, other hexosyl radicals, for example allosyl, altrosyl, galactosyl, gulosyl, idosyl, mannosyl and talosyl, may also be advantageous to use. It may also be advantageous according to the invention to use pentosyl radicals.

For the purposes of the present invention, it is particularly advantageous to choose the flavone glycoside (s) from the group α-glucosylrutin, α-glucosylmyricetin, α-glucosylisoquercitrin, α-glucosylisoquercetin and α-glucosylquercitrin.

Other beneficial agents are sericoside, pyridoxol, vitamin K, biotin and flavorings.

In addition, the active ingredients (one or more compounds) can also be chosen very advantageously from the group of hydrophilic active ingredients, in particular from the following group: α-hydroxy acids such as lactic acid or salicylic acid or salts thereof, such as. Na lactate, Ca lactate, TEA lactate, urea, allantoin, serine, sorbitol, glycerin, milk proteins, panthenol, chitosan. Of course, the list of active substances or combinations of active substances which can be used in the compositions according to the invention should not be limiting. The active substances can be used individually or in any desired combinations with one another.

The amount of such active ingredients (one or more compounds) in the compositions according to the invention is preferably 0.001 to 30 wt .-%, more preferably 0.05 to 20 wt .-%, in particular 1 to 10 wt .-%, based on the total weight of the composition.

The above-mentioned and further active compounds that can be used in the compositions according to the invention are given in DE 103 18 526 A1 on pages 12 to 17, to which reference is made in full at this point.

pearlescent

Suitable pearlescent waxes are, for example: alkylene glycol esters, special ethylene glycol disterate; Fatty acid alkanolamides, especially coconut fatty acid diethanoamide; Partial glycerides, especially stearic acid monoglyceride; Esters of polybasic, optionally hydroxy-substituted carboxylic acids with fatty alcohols having 6 to 22 carbon atoms, especially long-chain esters of tartaric acid; Fatty substances, such as fatty alcohols, fatty ketones, fatty aldehydes, fatty ethers and fatty carbonates, which in total have at least 24 carbon atoms, especially lauron and distearyl ether; Fatty acids such as stearic acid, hydroxystearic acid or behenic acid, ring-opening products of olefin epoxides having 12 to 22 carbon atoms with fatty alcohols containing 12 to 22 carbon atoms. lenstoffatomen and / or polyols having 2 to 15 Kohlenπstoffatomen and 2 to 10 hydroxyl groups and mixtures thereof.

The compositions of the invention may further contain glitter and / or other effect substances (e.g., color streaks).

emulsifiers

In a preferred embodiment, the shampoos and hair care compositions according to the invention additionally contain emulsifiers. Examples of suitable emulsifiers are nonionic surfactants from at least one of the following groups:

(1) addition products of 2 to 30 mol of ethylene oxide and / or 0 to 5 moles of propylene oxide onto linear fatty alcohols having 8 to 22 C atoms, to fatty acids having 12 to 22 C atoms and to alkylphenols having 8 to 15 C atoms in the alkyl group;

(2) C12 / 18 fatty acid mono- and diesters of addition products of 1 to 30 moles of ethylene oxide with glycerol;

(3) glycerol mono- and diesters and sorbitan mono- and diesters of saturated and unsaturated fatty acids having 6 to 22 carbon atoms and their ethylene oxide addition products;

(4) alkyl mono- and oligoglycosides having 8 to 22 carbon atoms in the alkyl group and their ethoxylated analogs;

(5) addition products of 15 to 60 moles of ethylene oxide with oils, for example castor oil and / or hydrogenated castor oil;

(6) polyol and especially polyglycerol esters, e.g. Polyglycerol polyricinoleate, polyglycerol poly-12-hydroxy stearate or polyglycerol dimerate. Also suitable are mixtures of compounds from several of these classes of substances;

(7) addition products of 2 to 15 moles of ethylene oxide with castor oil and / or hydrogenated castor oil;

(8) partial esters based on linear, branched, unsaturated or saturated _C6 / ₂₂ - fatty acids, ricinoleic acid and 12-hydroxystearic acid and glycerol, polyglycerol cerin, pentaerythritol, dipentaerythritol, sugar alcohols (for example sorbitol), alkyl glucosides

(e.g., methyl glucoside, butyl glucoside, lauryl glucoside) and polyglucosides (e.g., cellulose);

(9) mono-, di- and trialkyl phosphates and mono-, di- and / or tri-PEG-alkyl phosphates and their salts; (10) wool wax alcohols;

(11) polysiloxane-polyalkyl-polyether copolymers or corresponding derivatives; (12) mixed esters of pentaerythritol, fatty acids, citric acid and fatty alcohol according to DE-PS 1165574 and / or mixed esters of fatty acids having 6 to 22 carbon atoms, methylglycose and polyols, preferably glycerol or polyglycerol and

(13) Polyalkylene glycols.

The addition products of ethylene oxide and / or of propylene oxide to fatty alcohols, fatty acids, alkylphenols, glycerol mono- and diesters and sorbitan mono- and diesters of fatty acids or to castor oil are known, commercially available products. These are homolog mixtures, whose average degree of alkoxylation corresponds to the ratio of the molar amounts of ethylene oxide and / or propylene oxide and substrate with which the addition reaction is carried out. C ₂ to C ₈ fatty acid monoesters and diesters of addition products of ethylene oxide onto glycerol are known from DE-PS 2024051 as refatting agents for cosmetic preparations. C ₈ to C ₈ alkyl mono- and oligoglycosides, their preparation and their use are known from the prior art. They are prepared in particular by reacting glucose or oligosaccharides with primary alcohols having 8 to 18 carbon atoms. With respect to the glycoside ester, both monoglycosides in which a cyclic sugar residue is glycosidically bound to the fatty alcohol and oligomeric glycosides having a degree of oligomerization of preferably about 8 are suitable. The degree of oligomerization is a statistical mean, which is based on a homolog distribution typical for such technical products.

Furthermore, zwitterionic surfactants can be used as emulsifiers. Zwitterionic surfactants are surface-active compounds which carry at least one quaternary ammonium group and at least one carboxylate and / or one sulfonate group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines, such as the N-alkyl-N, N-dimethylammonium glycinates, for example the Kokosalkyldimethylammoniumglyci-, N-acylaminopropyl-N, N-dimethylammoniumglycinate, for example cocoaminopropylaminodimethylammoniumglycinat, and 2-alkyl-3-carboxylmethyi -3- hydroxyethylimidazolines having in each case 8 to 18 carbon atoms in the alkyl or acyl group and Kokosacylaminoethylhydroxyethylcarboxy methylglycinat.

Particularly preferred is the fatty acid amide derivative known under the CTFA name Cocamidopropyl Betaine. Also suitable emulsifiers are ampholytic surfactants. Ampholytic surfactants are understood as meaning those surface-active compounds which, apart from a C ₈ to C ₁₈ -alkyl or -acyl group in the molecule, contain at least one free amino group and at least one -COOH and / or -SO 3 H group and are capable of forming internal salts , Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N- Alkylamidopropylglycine, N-alkyltaurines, N-alkylsarcosines, 2-Alkylaminopropionsäuren and Alkylaminoessigsäuren each having about 8 to 18 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and C ₁₂ to C ₁₈ acylsarcosine. In addition to the ampholytic, quaternary emulsifiers are also suitable, with those of the esterquat type, preferably methyl-quaternized difatty acid triethanolamine ester salts, being particularly preferred.

Optionally, the shampoos and hair care compositions of the invention may contain perfume oils. As perfume oils, for example, mixtures of natural and synthetic fragrances may be mentioned. Natural fragrances are extracts of flowers (lily, lavender, rose, jasmine, neroli, ylang-ylang), stems and leaves (geranium, patchouli, petitgrain), fruits (aniseed, coriander, caraway, juniper), fruit peel (bergamot, lemon, Orange), Roots (Macis, Angelica, Celery, Cardamom, Costus, Iris, Calmus), Woods (Pine, Sandal, Guajac, Cedar, Rosewood), Herbs and Grasses (Tarragon, Lemongrass, Sage, Thyme), Needles and twigs (spruce, fir, pine, pines), resins and balsams (galbanum, elemi, benzoin, myrrh, olibanum, opoponax). Furthermore, animal raw materials come into question, such as civet and Castoreum. Typical synthetic fragrance compounds are ester type products, ethers, aldehydes, ketones, alcohols and hydrocarbons. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, 4-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzylformate, ethylmethylphenylglycinate, allylcyclohexylpropionate, styrallylpropionate and benzylsalicylate. The ethers include, for example, benzyl ethyl ether, to the aldehydes, for example, the linear alkanals having 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronel IaI ₁ lilial and bourgeonate, to the ketones such as the ionones, cc-lsomethylionen and Me - Thylcedrylketon, the alcohols include anethole, citronellol, eugenol, isoeugenol, geraniol, linalool, phenylethyl alcohol and terioneol, the hydrocarbons include mainly the terpenes and balsams. Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance. Also essential oils of lower volatility, which are mostly used as aroma components, are suitable as perfume oils, eg sage oil, camomile oil, clove oil, meissen oil, mint oil, cinnamon oil, lime blossom oil, juniper berry oil, vetiver oil, oliban oil, galbanum oil, labolanum oil and lavandin oil. Preferably, bergamot oil, dihydromyrcenol, lilial, lyral, citronellol, phenylethyl alcohol, α-hexylcinnamaldehyde, geraniol, benzyl acetone, cyclamen aldehyde, linalool, Boisambrene ^® Forte, Ambroxan, indole, hedione, Sandelice, lemon oil, mandarin oil, orange oil, allyl amyl glycolate, Cyclover- tal, lavandin oil, muscatel sage oil, beta-damascone, geranium oil bourbon, cyclohexyl salicylate, Vertofix ^® Coeur, Iso-e-Super ^®, ^® Fixolide NP, Evemyl, Iraldein gamma, phenylethyl acetic acid, geranyl acetate, benzyl acetate, rose oxide, romillate, irotyl and floramate used alone or in mixtures.

Pigments Optionally, the shampoos and hair care compositions according to the invention also contain pigments.

The pigments are present in undissolved form in the product composition and may be present in an amount of from 0.01 to 25% by weight, particularly preferably from 5 to 15% by weight. The preferred particle size is 1 to 200 .mu.m, in particular 3 to 150 .mu.m, particularly preferably 10 to 100 .mu.m. The pigments are practically insoluble colorants in the application medium and may be inorganic or organic. Also inorganic-organic mixed pigments are possible. Preference is given to inorganic pigments. The advantage of inorganic pigments is their excellent light, weather and temperature resistance. The inorganic pigments may be of natural origin, for example made of chalk, ocher, umber, green soil, terraced terraza or graphite. The pigments may be white pigments, e.g. Titanium dioxide or zinc oxide to form black pigments, e.g. Iron oxide black, colored pigments such as e.g. Ultramarine or iron oxide red, to luster pigments, metallic effect pigments, pearlescent pigments, as well as fluorescent or Phosphoreszenzpigmente, preferably wherein at least one pigment is a colored, non-white pigment.

Suitable are metal oxides, hydroxides and oxide hydrates, mixed phase pigments, sulfur-containing silicates, metal sulfides, complex metal cyanides, metal sulfates, chromates and molybdates and the metals themselves (bronze pigments). Titanium dioxide (Cl 77891), black iron oxide (Cl 77499), yellow iron oxide (Cl 77492), red and brown iron oxide (Cl 77491), manganese violet (Cl 77742), ultramarines (sodium aluminum sulfosilicates, Cl 77007, Pigment Blue 29 ), Chromium oxide hydrate (C177289), iron blue (Ferric Ferro-Cyanide, CI7751 0), Carmine (Cochineal).

Particular preference is given to pearlescent and color pigments based on mica or mica which are coated with a metal oxide or a metal oxychloride, such as titanium dioxide or bismuth chloride, and optionally other coloring substances, such as iron oxides, iron blue, ultramarines, carmines, etc., and the color can be modified by varying Layer thickness can be determined. Such pigments are sold, for example under the trade names Rona ^®, Colorona ^®, Dichrona and Timiron ^® ^® (Merck).

Organic pigments include, for example, the natural pigments sepia, rubber belt, bone charcoal, brown Kasseler, indigo, chlorophyll and other plant pigments. Synthetic organic pigments include azo pigments, anthraquinoids, indigoids, dioxazine, quinacridone, phthalocyanine, isoindolinone, perylene and perinone, metal complex, alkali blue and diketopyrrolopyrrole pigments. In one embodiment, the composition according to the invention contains from 0.01 to 10, particularly preferably from 0.05 to 5,% by weight of at least one particulate substance. Suitable substances are, for example, substances which are solid at room temperature (25 ° C.) and in the form of particles. Suitable examples are silica, silicates, aluminates, clays, mica, salts, in particular inorganic metal salts, metal oxides, for example titanium dioxide, minerals and polymer particles.

The particles are present in the agent undissolved, preferably stably dispersed form and can be deposited in solid form after application to the application surface and evaporation of the solvent. Preferred particulates are silica (silica gel, silica) and metal salts, especially inorganic metal salts, with silica being particularly preferred. Metal salts are e.g. Alkali or alkaline earth halides such as sodium chloride or potassium chloride; Alkali or alkaline earth sulfates such as sodium sulfate or magnesium sulfate.

polymers

The compositions of the invention may further contain additional polymers.

Suitable polymers are, for example, cationic polymers with the name Polyquater- nium according to INCI, for example, copolymers of vinylpyrrolidone / N-vinylimidazolium salts (Luviquat ^® FC, Luviquat ^® HM, Luviquat ^® MS ₁ Luviquat ^® Care, Luviquat ^® Ultra Care), copolymers of N-vinylpyrrolidone / Dimethylaminoethylmethacryiat quaternized (11 Luviquat ^® PQ) with diethyl sulfate, a copolymer of N-vinylcaprolactam / N-vinylpyrrolidone / N-vinylimidazolium salts (Luviquat Hold ^®); cationic cellulose derivatives (Polyquaternium-4 and -10), acrylamidocopolymers (Polyquaternium-7) and chitosan. Suitable cationic (quaternized) polymers are also Merquat ^® (polymer based on dimethyldiallylammonium chloride), Gafquat ^® (quaternary polymers which are formed by reaction of polyvinylpyrrolidone with quaternary ammonium compounds), Polymer JR (hydroxyethylcellulose with cationic groups) and cationic polymers based on plants, For example, guar polymers, such as the Jaguar ^® brands Fa. Rhodia.

Other suitable polymers are also neutral polymers, such as polyvinylpyrrolidones, copolymers of N-vinylpyrrolidone and vinyl acetate and / or vinylpropionate and / or stearyl (meth) acrylate, polysiloxanes, polyvinylcaprolactam and other copolymers with N-vinylpyrrolidone, polyethyleneimines and their salts, polyvinylamines and their Salts, cellulose derivatives, polyaspartic acid salts and derivatives. These included a Luviflex® ^® Swing (partially hydrolyzed copolymer of polyvinyl acetate and Polyethylengly- kol, Messrs. BASF) or Kollicoat ^® IR.

Suitable polymers are also those described in WO 03/092640, in particular those as Examples 1 to 50 (Table 1, page 40 et seq.) And Examples 51 to 65 (Table 2, Page 43) (methacrylic acid amide copolymers, which are fully incorporated herein by reference.

Suitable polymers are also nonionic, water-soluble or wasserdispergierba- re polymers or oligomers, such as polyvinylcaprolactam, including Luviskol Plus ^® (BASF), or polyvinyl pyrrolidone and their copolymers, in particular with Vinylestern such as vinyl acetate, for example, Luviskol ^® VA 37 (BASF); Polyamides, for example based on itaconic acid and aliphatic diamines, as described, for example, in DE-A-43 33 238.

Suitable polymers are also amphoteric or zwitterionic polymers, such as those available under the names Amphomer ^® (National Starch) Octylacryla- mid / methyl methacrylate / tert-Butylaminoethylmethacryla ^ -hydroxypropylmethacrylat- copolymers and zwitterionic polymers, as described for example in German patent applications DE 39 29 973, DE 21 50 557, DE 28 17 369 and DE 37 08 451 are disclosed. Acrylamidopropyltrimethylammonium chloride / acrylic acid or methacrylic acid copolymers and their alkali metal and ammonium salts are preferred zwitterionic polymers. Further suitable zwitterionic polymers are methacroylethylbetaine / methacrylate copolymers, which are available under the name Amersette® ^® (AMERCHOL), and copolymers of hydroxyethyl methacrylate, methyl methacrylate, N, N-dimethylaminoethyl methacrylate and acrylic acid (Jordanian pon ^®).

Suitable polymers are also nonionic, siloxane-containing, water soluble or dispersible polymers, for example, polyether siloxanes, such as Tegopren ^® (Fa. Goldschmidt) or Belsil ^® (Fa. Wacker).

Also suitable are biopolymers, i. Polymers derived from naturally renewable resources and constructed from natural monomer building blocks, e.g. Cellulose derivatives, chitin, chitosan, DNA, hyaluronic acid and RNA derivatives.

Further preparations according to the invention comprise at least one further water-soluble polymer, in particular chitosans (poly (D-glucosamine)) of different molecular weight and / or chitosan derivatives.

Anionic polymers

Further polymers suitable for the preparations according to the invention are copolymers containing carboxylic acid groups. These are polyelectrolytes with a larger number of anionically dissociable groups in the main chain and / or a side chain. They are capable of forming polyelectrolyte complexes (symplexes) with the copolymers A). In a preferred embodiment, the polyelectrolyte complexes used in the agents according to the invention have an excess of anionogenic / anionic groups.

In addition to at least one of the abovementioned copolymers A), the polyelectrolyte complexes also comprise at least one acid group-containing polymer.

The polyelectrolyte complexes preferably contain copolymer (e) A) and acid group-containing polymers in a weight ratio of about 50: 1 to 1:20, particularly preferably from 20: 1 to 1: 5.

Suitable carboxylic acid group-containing polymers are e.g. obtainable by free-radical polymerization of α, β-ethylenically unsaturated monomers. In this case, monomers m1) are used which contain at least one free-radically polymerizable, α.β-ethylenically unsaturated double bond and at least one anionogenic and / or anionic group per molecule. Suitable polymers containing carboxylic acid groups are also polyurethanes containing carboxylic acid groups. Preferably, the monomers are selected from monoethylenically unsaturated carboxylic acids, sulfonic acids, phosphonic acids and mixtures thereof.

The monomers m1) include monoethylenically unsaturated mono- and dicarboxylic acids having 3 to 25, preferably 3 to 6, carbon atoms, which can also be used in the form of their salts or anhydrides. Examples thereof are acrylic acid, methacrylic acid, ethacrylic acid, α-chloroacrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid and fumaric acid. The monomers further include the half-esters of monoethylenically unsaturated dicarboxylic acids having 4 to 10, preferably 4 to 6, C atoms, e.g. of maleic acid, such as monomethyl maleate. The monomers also include monoethylenically unsaturated sulfonic acids and phosphonic acids, for example vinylsulfonic acid, allylsulfonic acid, sulfoethyl acrylate, sulfoethyl methacrylate, sulfopropyl acrylate, sulfopropyl methacrylate, 2-hydroxy-3-acryloxypropylsulfonic acid, 2-hydroxy-3-methacryloxypropylsulfonic acid, styrenesulfonic acid,

2-acrylamido-2-methylpropanesulfonic acid, vinylphosphonic acid and allylphosphonic acid. The monomers also include the salts of the abovementioned acids, in particular the sodium, potassium and ammonium salts and the salts with the abovementioned amines. The monomers can be used as such or as mixtures with one another. The stated proportions by weight are all based on the acid form.

Preferably, the monomer m1) is selected from acrylic acid, methacrylic acid, ethacrylic acid, α-chloroacrylic acid, crotonic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid and mixtures thereof, more preferably acrylic acid, methacrylic acid and mixtures thereof.

The abovementioned monomers m1) can each be used individually or in the form of any desired mixtures. In principle, the comonomers used for the preparation of the carboxylic acid group-containing polymers are the compounds a) to d) previously mentioned as components of the copolymer A), with the proviso that the molar proportion of anionogenic and anionic groups which contains the polymer containing carboxylic acid groups in a larger proportion increases is the mole fraction of cationogenic and cationic groups. In a preferred embodiment, the carboxylic acid group-containing polymers contain at least one monomer in copolymerized form, which is selected from the abovementioned crosslinkers d). Suitable and preferred crosslinkers d) are referred to.

Furthermore, the polymers containing carboxylic acid groups preferably contain in copolymerized form at least one monomer m2) which is selected from compounds of the general formula (VI)

In which

R ^{1 is} hydrogen or C _r C ₈ alkyl, Y ^{1 is} O, NH or NR ³ , and

R ² and R ³ independently of one another are C 1 -C ₃₀ -alkyl or C ₅ -C ₈ -cycloalkyl, where the alkyl groups are substituted by up to four nonadjacent heteroatoms or heteroatom-containing groups selected from O, S and NH can be interrupted. R ¹ in the formula VI is preferably hydrogen or C ₁ -C ₄ -alkyl, in particular hydrogen, methyl or ethyl. R ² in the formula VI is preferably C 1 -C ₈ -alkyl, preferably methyl, ethyl, n-butyl, isobutyl, tert-butyl or a group of the formula --CH ₂ -CH ₂ -NH-C (CHa) ₃ . If R ^{3 is} alkyl, then preferably C ₁ -C ₄ -A ^ yI, such as methyl, ethyl, n-propyl, n-butyl, isobutyl and tert-butyl. Suitable monomers m2) are methyl (meth) acrylate, methyl methacrylate,

Ethyl (meth) acrylate, ethyl ethacrylate, tert-butyl (meth) acrylate, tert-butyl ethacrylate, n-octyl (meth) acrylate, 1,1,3,3-tetramethylbutyl (meth) acrylate, ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, n-decyl (meth) acrylate, n-undecyl (meth) acrylate, tridecyl (meth) acrylate, myristyl (meth) acrylate, pentadecyl (meth) acrylate, palmityl (meth) acrylate, Heptadecyl (meth) acrylate, nonadecyl (meth) acrylate, arrachinyl (meth) acrylate, behenyl (meth) acrylate, lignocerenyl (meth) acrylate, cerotinyl (meth) acrylate, melissinyl (meth) acrylate, palmitoleinyl (meth) acrylate, oleyl (meth) acrylate, linolyl (meth) acrylate, Lino! Enyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate and mixtures thereof.

Suitable monomers m2) are furthermore acrylic acid amide, methacrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N- (n-butyl) (meth) acryiamide, N- (tert ButyI) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, piperidinyl (meth) acrylamide and morpholinyl (meth) acrylamide, N- (n-octyl) (meth) acrylamide, N- (1,1,3,3-tetramethylbutyl) (meth) acrylamide, N-ethylhexyl (meth) acrylamide, N- (n-nonyl) (meth) acrylamide, N- (n-decyl) (meth) acrylamide, N- (n-undecyl) (meth) acrylamide, N-tridecyl (meth) acrylamide, N-myristyl (meth) acrylamide, N-pentadecyl (meth) acrylamide, N-palmityi (meth) acrylamide, N-heptadecyl ( meth) acrylamide, N-nonadecyl (meth) acrylamide, N-arrachinyl (meth) acrylamide, N-behenyl (meth) acrylamide, N-lignocerenyl (meth) acrylamide, N-cerotinyl (meth) acrylamide, N-melissinyl ( meth) acrylamide, N-palmitoleinyl (meth) acrylamide, N-oleyl (meth) acrylamide, N-linolyl (meth) acrylamide, N-olenyl (meth) acrylamide, N-stearyl (meth) acrylamide and N-lauryl (meth) acrylamide.

Furthermore, the polymers containing carboxylic acid groups preferably contain, in copolymerized form, at least one monomer m3) which is selected from compounds of the general formula VII

(VII)

wherein

the sequence of the alkylene oxide units is arbitrary, k and I independently of one another are an integer from 0 to 1000, the sum of k and I being at least 5,

R ^{4 is} hydrogen, C _{r is} C ₃ o-alkyl or C ₅ -C ₈ -cycloalkyl, R ^{5 is} hydrogen or C ₁ -C ₆ -alkyl,

Y ^{2 is} O or NR ⁶ , wherein R ^{6 is} hydrogen, dC ₃ o-alkyl or C ₅ -C ₈ -cycloalkyl.

In formula VII, k is preferably an integer from 1 to 500, in particular from 3 to 250. Preferably, I is an integer from 0 to 100. R ⁵ is preferably hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl or n-hexyl, in particular for hydrogen, methyl or ethyl. Preferably, R ⁴ in the formula VII is hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, n-pentyl, n-hexyl, octyl, 2-ethylhexyl, decyl, lauryl, palmityl or stearyl. Preferably, Y ² in formula VII is O or NH.

Suitable polyether acrylates VII) are, for example, the polycondensation products of the abovementioned α, β-ethylenically unsaturated mono- and / or dicarboxylic acids and their acid chlorides, amides and anhydrides with polyetherols. Suitable polyetherols can easily be prepared by reacting ethylene oxide, 1,2-propylene oxide and / or epichlorohydrin with a starter molecule, such as water or a short-chain alcohol R ⁴ -OH. The alkylene oxides can be used individually, alternately in succession or as a mixture. The polyether acrylates VII) can be used alone or in mixtures for the preparation of the polymers used according to the invention. Suitable polyether acrylates II) are also urethane (meth) acrylates with alkylene oxide groups. Such compounds are described in DE 198 38 851 (component e2)), to which reference is made in its entirety. Examples of anionic polymers which are preferred as carboxylic acid-containing polymers are, for example, homo- and copolymers of acrylic acid and methacrylic acid and salts thereof. These also include crosslinked polymers of acrylic acid, such as those available under the INCI name Carbomer. Such crosslinked homopolymers of acrylic acid are available commercially for example under the name Carbopol ^® by the company Noveon. Also hydrophobically modified crosslinked polyacrylate polymers such as Carbopol ^® Ultrez 21 are preferably from Noveon.

Further examples of suitable anionic polymers are copolymers of acrylic acid and acrylamide and their salts; Sodium salts of polyhydroxycarboxylic acids, water-soluble or water-dispersible polyesters, polyurethanes and polyureas. Especially suitable polymers are copolymers of (meth) acrylic acid and polyether acrylates, wherein the polyether chain is terminated with a C _a -C ₃₀ -alkyl radical. These include, for example, acrylate / Beheneth ^ ö-methacrylate copolymers, which are available under the name Aculyn ^® from Rohm and Haas. Particularly suitable polymers are also copolymers of t-butyl acrylate, ethyl acrylate, methacrylic acid (for example, Luvimer ^® 100P, Luvimer ^® Pro55), copolymers of ethyl acrylate and methacrylic acid (eg Luviu- mer MAE ^®), copolymers of N-tert-butylacrylamide, ethyl acrylate, acrylic acid (Ultrahold ^® 8, Ultrahold ^® Strong), copolymers of vinyl acetate, crotonic acid and optionally further Vinylester (eg Luviset ^® brands), maleic anhydride copolymers, optionally reacted with alcohol, anionic polysiloxanes, for example carboxy, t- butyl acrylate, methacrylic acid (for example, Luviskol ^® VBM ), copolymers of acrylic acid and methacrylic acid with hydrophobic monomers, such as C ₄ -C ₃ O-alkyl esters of meth (acrylic acid), C ₄ -C ₃₀ -Alkylvinylester, C ₄ -C ₃₀ -alkyl and hyaluronic acid. Examples of anionic polymers are also vinyl acetate / crotonic acid copolymers, as are, for example, under the names Resyn ^® (National Starch) and Gafset ^® (GAF), and vinyl pyrrolidone / vinyl acrylate copolymers, available examples For example, under the trademark Luviflex ^® (BASF). Other suitable polymers are the commercially available under the name Luviflex VBM-35 ^® (BASF) vinylpyrrolidone / acrylate terpolymer and sodium sulfonate-containing polyamides or sodium sulfonate-containing polyester. Furthermore, for example, the group of suitable anionic polymers comprises Balance CR ^® (National Starch; Acrylate Copolymer), balance 0/55 ^® (National Starch; Acrylate Copolymer), Balance ^® 47 (National Starch; octylacrylamide / - acrylates / butylaminoethyl methacrylate copolymer ) Aquaflex ^® FX 64 (ISP; isobutylene / ethylmaleimide / hydroxyethylmaleimide copolymer) Aquaflex ^® SF-40 (ISP / National Starch; VP / vinyl caprolactam / DMAPA acrylates copolymer), Alliance ^® LT-120 (ISP / Rohm &Haas; acrylates / C1-2 succinate / hydroxyacrylate copolymer), Aquarez ^® HS (Eastman; PoIyester-1), and ^® Diaformer Z-400 (Clariant; methacryloylethylbetaine / methacrylate copolymer), ^® Diaformer Z-711 (Clariant; methacryloylethyl N oxide / methacrylate copolymer), ^® Diaformer Z-712 (Clariant; methacryloylethyl N-oxide / methacrylate copolymer), Omnirez ^® 2000 (ISP; monoethyl ester of poly (methyl vinyl ether / maleic acid in ethanol), Amphomer ^® HC (National Starch; acrylate / Octylacrylamid- copolymer), Amphomer ^® 28- 4910 (National Starch; Octyl acrylamide / acrylate / butylaminoethyl noethylmethacrylat copolymer), Advantage ^® HC 37 (ISP; terpolymer of Vinylcapro- lactam / vinylpyrrolidone / Dimethyiaminoethylmethacrylat), Advantage ^® LC55 and LC80 or LC A and LC E, Advantage ^® Plus (ISP; VA / butyl maleate / isobornyl acrylates copolymer), Aculyne ^® 258 (Rohm &Haas; acrylate / Hydroxyesteracrylat copolymer), Lu viset PUR ^® (BASF, polyurethane-1), and ^® Luviflex Siik (BASF), Eastman AQ ^® 48 (Eastman ) Styleze CC-10 ^® (ISP; VP / DMAPA Acrylates copolymer), Styleze ^® 2000 (ISP; VP / Acrylates / lauryl Methacrylate copolymer), DynamX ^® (National Starch; polyurethanes ne-14 AMP-Acrylates copolymer), Resyn XP ^® (National Starch; Acrylates / Octylacryl- amide copolymer), Fixomer ^® A-30 (Ondeo Nalco, polymethacrylic acid (and) Acrylami- domethylpropansulfonsäure), Fixate G-100 ^® (Noveon; AMP-Acrylates / allyl Methacrylate copolymer).

Suitable polymers containing carboxylic acid groups are also the terpolymers of vinylpyrrolidone, C 1 -C 10 -alkyl cycloalkyl and aryl (meth) acrylates and acrylic acid described in US Pat. No. 3,405,084. Suitable carboxylic acid group-containing polymers are furthermore the terpolymers of vinylpyrrolidone, tert-butyl (meth) acrylate and (meth) acrylic acid described in EP-A-0 257 444 and EP-A-0 480 280. Suitable polymers containing carboxylic acid groups are furthermore the copolymers described in DE-A-42 23 066, which contain at least one (meth) acrylic acid ester,

Contain (meth) acrylic acid and N-vinylpyrrolidone and / or N-vinylcaprolactam in copolymerized form. The disclosure of these documents is hereby incorporated by reference. The preparation of the abovementioned carboxylic acid group-containing polymers is carried out by known processes, for example the solution, precipitation, suspension or emulsion polymerization, as described above for the copolymers A).

Suitable carboxylic acid group-containing polymers are also polyurethanes containing carboxylic acid groups.

EP-A-636361 discloses suitable block copolymers having polysiloxane blocks and polyurethane / polyurea blocks having carboxylic acid and / or sulfonic acid groups. Suitable silicone-containing polyurethanes are also described in WO 97/25021 and EP-A-751 162. Suitable polyurethanes are also described in DE-A-42 25 045, which is incorporated herein by reference in its entirety.

The acid groups of the carboxylic acid group-containing polymers may be partially or completely neutralized. Then at least a part of the acid groups is present in deprotonated form, the counterions are preferably selected from alkali metal ions, such as Na ⁺ , K ⁺ , ammonium ions and their organic derivatives, etc.

Shampoo Types

Depending on the hair quality or scalp problem, additional requirements may be imposed on shampoos. The mode of action of the preferred shampoo types with the most important additional effects or important special objectives is described below.

For example, shampoos for normal or fast-greasy or damaged hair, antidandruff shampoos, baby shampoos and 2-in-1 shampoos (shampoo and conditioner in one) are preferred according to the invention. Shampoo for normal hair: hair washing is intended to rid the hair and scalp of the skin fat formed in sebaceous glands, the inorganic salts, water, sweat glands, urea and lactic acid, shed skin particles, environmental dirt, odors and possibly residues of hair cosmetic treatments. Normal hair means short to shoulder-length hair, which is only slightly damaged. Accordingly, the proportion of conditioning auxiliaries should be optimized for this type of hair.

Shampoos for fast greasy hair: increased fat production of the scalp sebaceous glands leads to a lank, unsightly hairstyle 1-2 days after shampooing. Oil and waxy skin fat constituents complicate the hair and reduce the friction of hair to hair and thus reduce the hairstyle hold. The actual hair cosmetic problem with fast greasy hair is therefore the premature collapse of voluminous hairstyles. To avoid this, one must prevent the hair surface from being weighted and becoming too smooth and supple. This is preferably due to the surfactant base of well-cleansing and especially unsubstantiated tively pronounced wash raw materials achieved. Additional care ingredients that would add to the skin fat, such as moisturizing substances or conditioning aids, are not used in shampoos for fast-greasy hair or used with great caution. Volume giving shampoos for fine hair can be formulated similarly.

Shampoos for dry, damaged hair. The structure of the hair in the course of hair growth by mechanical influences such as combing, brushing and above all Toupieren (combing the direction of growth), by the action of UV radiation or visible light and by cosmetic treatments such as perms, bleaching or dyeing changed. The cuticle of the hair has an increasingly strained appearance from root to tip; in extreme cases, it is completely worn away at the top, and the hair tips are split (hair splitting). Damaged hair can basically no longer be returned to the state of healthy hair growth. However, it is possible to come very close to this ideal state with regard to grip, gloss and combability by using shampoos according to the invention with possibly high contents of care substances (conditioners).

An even better effect than with a shampoo is achieved with a hair care composition according to the invention, for example in the form of a rinse or a treatment after shampooing.

2-in-1 shampoos according to the invention are especially highly nourishing shampoos, in which the additional benefit of care is provided equally to the basic benefits of cleaning as a "shampoo and rinse in one." 2-in-1 compositions according to the invention contain increased amounts Anti-dandruff shampoos: Anti-dandruff shampoos according to the invention have the advantage, in comparison to antidandruff hair wipers, that they reduce the formation of new visible dandruff and prevent them from long-term use by means of appropriate antidandruff agents, but also remove exfoliated dandruff after rinsing However, the wash liquor retains only a small but adequate proportion of the active ingredients on the scalp and hair There are various anti-dandruff active ingredients that can be incorporated into the shampoo compositions according to the invention, such as, for example, zinc pyrithione, K etoconazole, clotrimazole, bmbazole or piroctone olamine. In addition, these substances have a normalizing the Abschilferung effect. The basis of antidandruff shampoos is largely the formulation of shampoos for normal hair with good cleansing effect.

Baby shampoos: in a preferred embodiment of the invention, the shampoo preparations according to the invention are baby shampoos. These are optimally skin and mucous membrane compatible. Combinations of washing raw materials with Very good skin compatibility form the basis of these shampoos. Additional substances to further improve the skin and mucous membrane compatibility and the care properties are advantageously added, such. Nonionic surfactants, protein hydrolysates and panthenol or bisabolol. All the necessary raw materials and auxiliaries, such as preservatives, perfume oils, dyes, etc., will be chosen in terms of high compatibility and mildness.

Dry scalp shampoos: in another preferred embodiment of the invention, the shampoo formulations of the invention are shampoo for dry scalp. The primary goal of these shampoos is to prevent dehydration of the scalp, as dry scalp can cause itching, redness and inflammation. As with the baby shampoos, combinations of washing raw materials with very good skin compatibility form the basis of these shampoos. In addition, if necessary, moisturizers and humectants, such as. As glycerol or urea, are used. Due to the surprising moisturizing and moisturizing effect of copolymer a), which is optionally mixed with oligomer b), the addition of further lipid and humectants is not absolutely necessary, but can bring about further advantageous effects.

The shampoo compositions according to the invention may also be present as shampoo concentrates with increased surfactant contents of 20-30%. They are based on special wash raw material combinations and consistency regulators, which ensure the good spreadability and the spontaneous foaming power of even a small application quantity. A particular advantage is, for example, the ability to reach the yield of 200 ml of shampoo with a 100 ml bottle.

administration

It is advantageous if the cosmetic compositions according to the invention are stored in and / or used in a bottle or squeeze bottle. Accordingly, bottles or squeeze bottles which contain a composition according to the invention are also according to the invention.

Examples

The invention is illustrated by examples.

All reactions were carried out under an atmosphere of nitrogen unless otherwise specified.

The K values of the copolymers according to the invention were determined according to H. Fikentscher, Cellulose-Chemie, Volume 13, 58-64 and 761-774 (1932) in cyclohexanone at 25 ° C. and a polymer concentration of 2% by weight.

Preparation instructions for copolymer a)

206 g of polyisobutene having a molecular weight M _n of 550 g / mol and 185 g of diisobutene (mixture of 2,4,4-trimethyl-1-pentene and 2,4,4-trimethyl-2-pentene in a molar ratio of 80 : 20, determined by ¹ H-NMR spectroscopy) were placed in a 4 l kettle and heated to 110 ⁰ C in a gentle stream of nitrogen. After reaching the temperature of 110 ⁰ C was within 5 hours 184 g of maleic anhydride in liquid form as a melt of about 70 ⁰ C and within 5.5 hours 5.5 g tert-butyl peroctoate, dissolved in 25 g of diisobutene (mixture from 2,4,4-trimethyl-1-pentene and 2,4,4-trimethyl-2-pentene). The mixture was then reheated at 120 ⁰ C for one hour. Thereafter, the temperature was raised to 160 ⁰ C and distilled unreacted diisobutene.

The resulting reaction mixture was cooled to 90 ^° C. and mixed simultaneously with 2400 g of water and 140 g of 50% by weight aqueous sodium hydroxide solution. The mixture was then stirred for 4 hours at 90 ° C and then cooled to room temperature. Copolymer a) was obtained in the form of an aqueous dispersion which had a pH of 6.5 and a water content of 80% by weight. The K value was 14.7.

Mixing of copolymer a) and oligomer b)

Mixture 1:

A first mixture of copolymer a) with oligomer b) was prepared by mixing 90 g of polyisobutene (oligomer b)) having a molecular weight M _n of 550 g / mol with 10 g of the above-described dispersion of copolymer a) by stirring in a Beaker mixed. 61334

59

Mix 2:

A second mixture of copolymer a) with oligomer b) was prepared by mixing 90 g of polyisobutene (oligomer b)) having a molecular weight M _n of 1000 g / mol with 10 g of the above-described dispersion of copolymer a) by stirring in one Beaker mixed.

Two mixtures of copolymer a) and oligomer b) suitable for use according to the invention were thus obtained.

APPLICATION EXAMPLES The above-described mixtures 1 and / or 2 are used to prepare the compositions mentioned below. The quantities are each in wt .-%, unless otherwise stated.

The amount of mixture 1 and mixture 2 given in the tables is in each case the amount of copolymer a), ie without other components. The corresponding amount of oligomer b) is not given in the tables, but can be easily calculated from the compositions of the mixtures.

Examples A1 - A5: Clear shampoos

Examples A6 - A10: Clear conditioner shampoos

A11 - A17 shampoos

Ingredient A11 A12 A13 A14 A15 A16 A17

Texapon ^® NSO 35,00 40,00 30,00 45,00 27,00

Plantacare ^® 2000 5,00 5,50 4,90 3,50 7,00

Tego Betain L7 10,00 5,00 12,50 7,50 15,00

Fragrance 0.10 0.10 0.10 0.10 0.10 0.10 0.10

Mixture 1 3.00 12.00 4.00 20.00

Mixture 2 3,50 10,00 35,00

D-panthenol USP 0.50 1.00 0.80 1.50 0.50

Preservative 0,10 0,10 0,10 0,10 0,10 0,10 0,10

Citric Acid 0.10 0.10 0.10 0.10 0.10

Rewopal ^® LA 3 0,50 2,00 0,50 0,50 2,00

Sodium Chloride 1, 50 1.50 1, 50 1, 50 1.50

Water the. ad 100 ad 100 ad 100 ad 100 ad 100 ad 100 ad 100 A18 - A20 Conditioner shampoos with pearlescent

pH adjusted to 6.0

A21 - A23 Clear Conditioner Shampoos

pH adjusted to 6.0 A24 - A26 clear light shampoos with volume effect

pH adjusted to 5.5

Claims

claims

1. The use of a) copolymers obtainable by copolymerization of (A) at least one ethylenically unsaturated dicarboxylic acid anhydride derived from at least one dicarboxylic acid having 4 to 8 C atoms,

(B) at least one oligomer of branched or unbranched C ₃ -C ₁₀ alkanes, wherein at least one oligomer has an average molecular weight

M _{n is} in the range from 300 to 5000 g / mol, preferably up to 1200 g / mol, or is obtainable by oligomerization of at least 3 equivalents of C ₃ -C ₁₀ -alkene,

(D) optionally at least one further ethylenically unsaturated comonomer other than (A), (B) and (C),

if appropriate, reaction with (E) at least one compound of the general formula Ia, Ib, Ic or Id

Ia Ib

Id

where A ^{1 is} C ₂ -C ₂ o-alkylene, identical or different,

R ^{1 is} Ci-C _3tr alkyl, linear or branched, phenyl or hydrogen, n is an integer from 1 to 200, optionally subsequent contact with water,

optionally mixed with b) at least one branched or unbranched oligomer, wherein at least one oligomer is a medium molecular weight

weight M _n in the range from 300 to 5000 g / mol, preferably up to 1200 g / mol, or by oligomerization of at least 3 equivalents

lente ken is available,

in shampoos and hair products.

2. Use according to claim 1, wherein oligomer (B) is an oligomer of branched

OIeRn is.

3. Use according to one of claims 1 or 2, wherein oligomer (B) is polyisobutene.

4. Use according to any one of claims 1 to 3, wherein the at least one ethylenically unsaturated dicarboxylic acid anhydride (A) is maleic anhydride.

5. Use according to any one of claims 1 to 4, wherein the at least one α-olefin (C) is selected from isobutene, diisobutene and 1-dodecene.

6. Use according to any one of claims 1 to 5, wherein the at least one further ethylenically unsaturated comonomer (D) is selected from ethylenically unsaturated C ₃ -C ₈ carboxylic acids and carboxylic acid derivatives of the general formula II

Carboxylic acid amides of the formula

non-cyclic amides of the general formula IV a or cyclic amides of the general formula IV b

C1-C20-alkyl vinyl ethers,

N-vinyl derivatives of nitrogen-containing aromatic compounds, α, β-unsaturated nitriles, alkoxylated unsaturated ethers of the general formula V

Esters or amides of the general formula I VI

unsaturated esters of the general formula VII

vinyl aromatic compounds of the formula VIII

Phosphorus, phosphonate, sulfate and sulfonate group-containing comonomers, α-olefins having 18 to 40 carbon atoms, wherein in the general formulas the variables are defined as follows:

R ² , R ^{3 are} identical or different and selected from hydrogen, unbranched or branched C 1 -C 5 -alkyl and COOR ⁴ ,

R ^{4 is} identical or different and selected from hydrogen or C 1 -C ₂₂ -alkyl, branched or unbranched, R ^{5 is} hydrogen or methyl, x is an integer in the range from 2 to 6, y is an integer selected from 0 or 1, a is an integer in the range from 0 to 6, R ⁶ , R ^{7 are} identical or different and selected from Hydrogen, unbranched or branched C 1 -C ₁₀ -alkyl,

X oxygen or NR ⁴

R ⁸ [A ³ -O] _n -R ⁴ ,

R ^{9 is} identical or different and selected from hydrogen, unbranched or branched C ₁ -C 10 -alkyl,

R ¹⁰ , R ¹¹ independently of one another are hydrogen, methyl or ethyl,

R ^{12 is} selected from methyl and ethyl, k is an integer in the range from 0 to 2,

A ² , A ³ C ₂ -C ₂₀ -alkylene A ⁴ CrCao-alkylene or a single bond and the other variables are as defined above.

7. Use according to any one of claims 1 to 6, wherein the copolymer (a) is obtainable by copolymerization of (A) in the range of 5 to 60 mol% (A),

(B) in the range of 1 to 95 mol% (B),

(C) in the range of 0 to 60, preferably 10 to 55 mol% (C),

(D) in the range of 0 to 70 mol%, in each case based on copolymer, wherein the sum of (A), (B), (C) and (D) gives 100 mol%, and reaction with

(E) in the range of 0 to 50 mol%, based on all carboxyl groups of the copolymer.

8. Use according to one of claims 1 to 7, wherein the weight ratio of oligomer b) to copolymer a) in the range of 0.1: 1 to 100: 1, preferably from 0.5: 1 to 10: 1.

9. Use according to any one of claims 1 to 8, wherein oligomer (b) is polyisobutene.

10. shampoos and hair care compositions containing a copolymer a), optionally mixed with an oligomer b) as in any one of claims 1 to 9 Are defined.

11. shampoos and hair care composition according to claim 10, further comprising at least one oil and / or fat component.

12. shampoos and hair care composition according to any one of claims 10 or 11, further comprising at least one surfactant.

13. Shampoos and hair care composition according to any one of claims 10 to 12, further comprising at least one conditioning agent.

14. hair care product according to any one of claims 10 to 13, wherein the hair care agent is selected from the group consisting of pre-treatment agents, hair conditioners, hair conditioners, hair balms, leave-on hair treatments, rinse-off hair treatments, hair lotions, pomades, hairdressing creams, hairdressing lotions, Hairdressing gels, top fluids, hot oil treatments and foam cures.