WO2009068362A1 - Means for skin tanning - Google Patents

Abstract

The invention relates to a means for skin tanning, containing in a cosmetic carrier a combination of at least one CH acid compound according to formula (I) having constituents (B) at least of one compound of formula (II) and/or at least one compound of formula (III). These means are suitable for tanning the human skin without the skin having to be subjected to UV light.

Description

 "Tanning agent"

The invention relates to browning agents containing selected aldehyde derivatives in combination with specific 1,2-dihydro-2-oxopyrimidinium compounds, to the use of this combination for tanning human skin, and to a method of tanning human skin.

A tanned skin is perceived today by the consumer as a sign of health and an active, sporty lifestyle. A brown skin is considered attractive and the possession of a light tan as highly desirable. However, since the first ozone depletion in 1970, consumers have become increasingly aware that the tanning process caused by intense sunbathing is associated with a variety of skin damage, ranging from premature aging to increased skin cancer risk. With the use of tanning creams, the consumer can fulfill the desire for a tanned skin, without at the same time having to expose himself to the harmful UV-A and UV-B content of the sunlight.

The tanning creams on the market in most cases contain the active ingredient 1, 3-dihydroxyacetone. However, the use of dihydroxyacetone-containing creams can be associated with disadvantages for the consumer. Some consumers are allergic to dihydroxyacetone. The existing suspicion that dihydroxyacetone could split off formaldehyde over time also makes the use of dihydroxyacetone in cosmetics appear less advantageous. Furthermore, dihydroxyacetone has the disadvantage that it can lead to odor nuisance and uneven staining of the skin. Active ingredients which show a tanning effect of the skin without being burdened with the described disadvantages are hitherto unknown.

The object of the present invention is therefore to provide agents which are able to dye the skin in a beautiful, even shade of brown, without at the same time already show disadvantages described. Surprisingly, it has been found that the substance combinations according to the invention can be used to a great extent to achieve this object.

A first subject of the invention is a composition for tanning the human skin, comprising, in a cosmetic carrier, a combination of component (A) of at least one CH-acidic compound according to formula (I)

wherein

• R ¹ and R ² are independently a linear or cyclic Ci-C ₆ - alkyl group, a C ₂ -C ₆ alkenyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group, an aryl Ci-C ₆ - alkyl group, a C-ι-C ₆ hydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a Ci-C ₆ alkoxy-C ₆ alkyl group, a group R'R "N- (CH _{2) p} -, wherein R ¹ and R ¹¹ independently of one another represent a hydrogen atom, a C 1 -C ₄ -alkyl group, a C ¹ -C ₄ -hydroxyalkyl group or an aryl-C ¹ -C ₆ -alkyl group, where R ¹ and R ¹¹ together with the nitrogen atom can form a 5-, 6- or 7-membered ring and p stands for a number 2, 3, 4, 5 or 6,

• R ³ and R ⁵ are independently a hydrogen atom or a Ci-C ₆ - alkyl group, wherein at least one of the radicals R ³ or R ⁵ is a Ci-C ₆ alkyl group,

• R ⁴ represents a hydrogen atom, a C- | -C ₆ alkyl group, a Ci-C ₆ - hydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a Ci-C ₆ alkoxy group, a Ci-C ₆ -hydroxyalkoxy , a group R ^m R ^IV N- (CH ₂ ) _q -, in which R ^m and R ^IV independently of one another represent a hydrogen atom, a C ₁ -C ₆ -alkyl group, a C 1 -C ₆ -hydroxyalkyl group or an aryl-C 1 -C 4 -alkyl group. C ₆ alkyl group and q is a number 1, 2, 3, 4, 5 or 6, wherein the radical R ⁴ together with one of the radicals R ³ or R ^{5 can form} a 5- or 6-membered aromatic ring, the optionally substituted with a halogen atom, a Ci-C ₆ alkyl group, a -C ₆ hydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a Ci-C ₆ alkoxy group, a Ci-C ₆ - hydroxyalkoxy group, a nitro group, a hydroxy group, a group R ^V R ^VI N- (CH ₂ ) _S -, wherein R ^v and R ^vl independently represent a Hydrogen atom, a C- | -C ₆ alkyl group, a Ci-C ₆ alkyl hydroxyalkyl group, or an aryl-CrC ₆ and s is a number 0, 1, 2, 3, 4, 5 or 6 may be substituted,

• Y ¹ represents an oxygen atom, a sulfur atom or a group NR ^V ", wherein R ^v" stands for a hydrogen atom, an aryl group, a heteroaryl group, a Ci-C ₆ - alkyl group or an arylalkyl group dC _6,

• X ^' is a physiologically acceptable anion, with component

(B) at least one compound of the formula (II) and / or at least one compound of the formula (III)

wherein

R ¹ is a (dC ₆₎ alkyl, (C ₂ -C ₆₎ alkenyl, aryl, aryl (Ci-C ₆₎ - alkyl or heteroaryl (dC ₆₎ alkyl group,

R ² and R ³ each independently represent a hydrogen atom, a halogen atom, a

(C ₁ -C ₆ ) -alkyl group, a (C ₁ -C ₆ ) -alkoxy group, hydroxy (C ₁ -C ₆ ) -alkoxy group, hydroxyl group, nitro group, aryl group, trifluoromethyl group,

Amino group which may be substituted by (dC ₆ ) -alkyl groups, or (d-

C ₆ ) acyl group,

R ^{4 represents} a hydrogen atom, a nitro group, a hydroxy group or a (C ₁ to C ₃ ) -alkoxy group,

R ^{5 represents} a hydrogen atom, a hydroxy group or a (Ci to C ₃ ) -

Alkoxy group stands,

R ^{6 represents} a hydrogen atom or a (C ₁ to C ₃ ) alkyl group, R ^{7 represents} a hydrogen atom, a nitro group or a hydroxy group, R ^{8 represents} a hydrogen atom or a nitro group and A ^{~ represents} a physiologically acceptable anion.

Examples of C ₁ -C ₆ -alkyl radicals are the groups methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl and tert-butyl, n-pentyl and n-hexyl. Iso-propyl, propyl, ethyl and methyl are preferred (C ₁ to C ₃ ) -alkyl radicals, with methyl and ethyl being particularly preferred. Examples of corresponding cyclic alkyl groups are cyclopentyl and cyclohexyl. Examples of preferred C ₂ -C ₆ -alkenyl radicals are vinyl and allyl.

Furthermore, as preferred examples of a Ci-Cε-hydroxyalkyl group a

Hydroxymethyl, a 2-hydroxyethyl, a 2-hydroxypropyl, a 3-hydroxypropyl, a 4-

Hydroxybutyl group, a 5-hydroxypentyl and a 6-hydroxyethyl group.

A 2-hydroxyethyl group is particularly preferred.

Examples of a C ₂ -C ₆ -polyhydroxyalkyl group are the 2,3-dihydroxypropyl group, 3,4-

Dihydroxybutyl group and the 2,4-dihydroxybutyl group.

The methoxy, ethoxy, isopropoxy and propoxy are examples of C ₁ -C ₃ according to the invention

Alkoxy groups.

The methoxyethyl, ethoxyethyl, methoxypropyl, methoxybutyl, ethoxybutyl and the

Methoxyhexylgruppe are examples of CrC ₆ -AI koxy C ₂ -C ₆ alkyl groups according to the invention.

The other terms used are according to the invention of the given here

Definitions off.

The agents according to the invention contain the compounds of component (A) and the compounds of component (B) in a cosmetic carrier, for example aqueous cosmetic carriers or aqueous-alcoholic cosmetic carriers. For the purpose of skin tanning, such carriers are, for example, creams, emulsions, gels or surfactant-containing foaming solutions, such as, for example, shampoos, foam aerosols or other preparations which are suitable for use on the skin. However, it is also conceivable to integrate the said components in a powdery or tablet-like formulation.

An aqueous cosmetic carrier contains at least 40% by weight of water.

For the purposes of the present invention, aqueous-alcoholic carriers are to be understood as meaning aqueous compositions containing from 3 to 70% by weight of a C 1 -C ₄ -alcohol, in particular ethanol or isopropanol. The compositions according to the invention may additionally contain further organic solvents, for example methoxybutanol, benzyl alcohol, ethyl diglycol or 1,2-propylene glycol. Preference is given to all water-soluble organic solvents.

The compounds of formula I are in chemical equilibrium with their enamine forms. The latter are equivalent in terms of the invention.

The following substituent combinations according to compounds of the formula (I) are to be selected singly or in combination: In a preferred embodiment, Y ¹ according to formula (I) is an oxygen or a sulfur atom, particularly preferably an oxygen atom.

It is preferred according to the invention if at least one of the radicals R ³ or R ^{5 of} the formula (I) is a methyl group. Particularly preferably, both radicals are a methyl group. It is additionally preferred if R ^{1 of} the formula (I) is a C _r to C ₆ - alkyl group, in particular methyl.

Preferably, the compounds according to formula I are selected from one or more

Compounds of the group of salts with physiologically acceptable counterion X ^' , which is formed from salts of the

1, 2-dihydro-1, 3,4,6-tetramethyl-2-oxo-pyrimidinium,

1, 2-dihydro-1,3-diethyl-4,6-dimethyl-2-oxo-pyrimidinium,

1, 2-dihydro-1,3-dipropyl-4,6-dimethyl-2-oxo-pyrimidinium,

1, 2-dihydro-1,3-di (2-hydroxyethyl) -4,6-dimethyl-2-oxo-pyrimidinium,

1, 2-dihydro-1,3-diphenyl-4,6-dimethyl-2-oxo-pyrimidinium,

1, 2-dihydro-1, 3,4-trimethyl-2-oxo-pyrimidinium,

1, 2-dihydro-1,3-diethyl-4-methyl-2-oxo-pyrimidinium,

1, 2-dihydro-1,3-dipropyl-4-methyl-2-oxo-pyrimidinium,

1, 2-dihydro-1,3-di (2-hydroxyethyl) -4-methyl-2-oxo-pyrimidinium,

1, 2-dihydro-1,3-diphenyl-4-methyl-2-oxo-pyrimidinium,

1-allyl-1,2-dihydro-3,4,6-trimethyl-2-oxopyrimidinium,

1,2-dihydro-1- (2-hydroxyethyl) -3,4,6-trimethyl-2-oxo-pyrimidinium,

1, 2-dihydro-1, 3,4,6-tetramethyl-2-thioxo-pyrimidinium,

1, 2-dihydro-1,3-diethyl-4,6-dimethyl-2-thioxo-pyrimidinium,

1, 2-dihydro-1,3-dipropyl-4,6-dimethyl-2-thioxopyrimidiniums,

1, 2-dihydro-1,3-di (2-hydroxyethyl) -4,6-dimethyl-2-thioxo-pyrimidinium,

1, 2-dihydro-1,3-diphenyl-4,6-dimethyl-2-thioxo-pyrimidinium,

1, 2-dihydro-1, 3,4-trimethyl-2-thioxo-pyrimidinium,

1, 2-dihydro-1,3-diethyl-4-methyl-2-thioxo-pyrimidinium,

1, 2-dihydro-1,3-dipropyl-4-methyl-2-thioxo-pyrimidinium,

1, 2-dihydro-1,3-di (2-hydroxyethyl) -4-methyl-2-thioxo-pyrimidinium,

1, 2-dihydro-1, 3-diphenyl-4-methyl-2-thioxo-pyrimidinium,

1, 2-dihydro-3,4-dimethyl-2-oxo-quinazolinium and

1, 2-dihydro-3,4-dimethyl-2-thioxo-quinazolinium. Very particularly preferred compounds according to formula I are selected from one or more compounds of the group of salts with physiologically acceptable counterion X ^' , which is formed from salts of

1, 2-dihydro-1,3,6,6-tetramethyl-2-oxo-pyrimidinium,

1-allyl-1,2-dihydro-3,4,6-trimethyl-2-oxo-pyrimidinium and

1,2-dihydro-1- (2-hydroxyethyl) -3,4,6-trimethyl-2-oxopyrimidinium.

X ^" in formula (I) and in the above lists preferably represents halide, benzenesulfonate, p-toluenesulfonate, C 1 -C ₄ -alkanesulfonate, trifluoromethanesulfonate, perchlorate, 0.5 sulfate, hydrogensulfate, tetrafluoroborate, hexafluorophosphate or tetrachlorozincate , Bromide, iodide, hydrogen sulfate or p-toluenesulfonate used as X ^' .

The most preferred salts of the compounds according to formula (I) are disclosed below for clarity with their structural formulas:

The compounds of the formula (I) are preferably present in an amount of from 0.01% by weight to 5% by weight, in particular from 0.05% by weight to 1% by weight, based in each case on the weight of the ready-to-use agent , contain.

At least one compound of the formula (I) is present in the agent according to the invention combined with at least one compound of the formula (II) and / or of the formula (III).

The compounds of the formula (II) are present in aqueous carriers in chemical equilibrium with the hydrates of the formula (IIa). This is exemplified below:

(H) (IIa)

The hydrates can be isolated and are also suitable for use in the compositions of the invention.

Preferred compounds according to formula II are those in which the formyl group -CHO is bonded in the 2- or 4-position.

A ^~~ is according to formula II preferably halide, benzenesulfonate, p-toluenesulfonate, methanesulfonate, trifluoromethanesulfonate, perchlorate, sulfate, hydrogensulfate, tetrachlorozincate or N-oxide of quinoline, particularly preferably a p-toluenesulfonate, methanesulfonate, trifluoromethanesulfonate, Methylsulfate or benzenesulfonate ion. The preferred anion is the p-toluenesulfonate ion.

R ¹ is according to formula II preferably a (dC ₆ ) alkyl group.

The compounds according to formula II are particularly preferably selected from at least one compound of the group consisting of the benzenesulfonates, p-toluenesulfonates, methanesulfonates, trifluoromethanesulfonates, perchlorates, sulfates, chlorides, bromides, iodides and / or tetrachlorozincates of 4-formyl-i-methyl-quinolinium and 2-formyl-1-methylquinolinium. 4-Formyl-i-methyl-quinolinium p-toluenesulfonate and 2-formyl-1-methyl-quinolinium p-toluenesulfonate and the hydrates of the abovementioned compounds are very particularly preferred compounds of the formula II.

If the compounds of the formula (III) are nitroderivatized compounds, it is preferred according to the invention for these compounds if exactly one of the radicals R ⁴ , R ⁷ or R ^{8 is} a nitro group. In this case, it is again preferred if in addition at least one further of the radicals R ⁴ , R ⁵ , R ⁷ or R ⁸ is different from a hydrogen atom.

Particular preference is given to compounds of the formula (III) if they are selected from at least one compound from the following list 4-hydroxy-3-methoxy-6-nitrobenzaldehyde

3,4-dihydroxy-5-nitrobenzaldehyde

2-hydroxy-3-methoxy-5-nitro-benzaldehyde

4-hydroxy-3-methoxy-5-nitrobenzaldehyde (5-nitrovanillin)

3-hydroxy-4-methoxybenzaldehyde

3,4-dimethoxy-5-hydroxybenzaldehyde

In a particularly preferred embodiment of the invention, the agent in a cosmetic carrier contains a combination of (A) at least one CH-acidic compound of the formula (I)

wherein

• R ¹ and R ² independently of one another represent a linear or cyclic C ₁ -C ₆ - Alkyl group, a C ₂ -C ₆ alkenyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group, an aryl Ci-C ₆ - alkyl group, a Ci-C ₆ hydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a C -C ₆ alkoxy-Ci-C ₆ alkyl group, a group R'R "N- (CH ₂ ) _P -, wherein R ¹ and R ¹¹ are independently a hydrogen atom, a Ci-C ₄ alkyl group, a C ¹ -C ₄ -hydroxyalkyl group or an aryl-C ¹ -C ₆ -alkyl group, where R ¹ and R ¹¹ together with the nitrogen atom can form a 5-, 6- or 7-membered ring and p is a number 2, 3, 4, 5 or 6,

• R ³ and R ⁵ are independently a hydrogen atom or a C ₁ -C ₆ - alkyl group, wherein at least one of the radicals R ³ or R ⁵ is a Ci-C ₆ alkyl group,

• R ⁴ represents a hydrogen atom, a C- | -C ₆ alkyl group, a C ₁ -C ₆ - hydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a Ci-C ₆ alkoxy group, a C- | -C ₆ -Hydroxyalkoxygruppe, a group R ^m R ^lv N- (CH ₂ ) _q -, wherein R ^m and R ^IV independently represent a hydrogen atom, a Ci-C ₆ alkyl group, a C- | -C ₆ -Hydroxyalkylgruppe or an aryl-Ci-C ₆ -alkyl group and q is a number 1, 2, 3, 4, 5 or 6, wherein the radical R ⁴ together with one of the radicals R ³ or R ^{5 is} a 5- or 6-membered aromatic Ring can form, optionally with a halogen atom, a Ci-C ₆ alkyl group, a Ci-C ₆ -Hydroxyalkylgruppe, a C ₂ -C ₆ polyhydroxyalkyl, a C-ι-C ₆ alkoxy, a C ₁ -C ₆ - hydroxyalkoxy group, a nitro group, a hydroxy group, a group R ^V R ^VI N- (CH _{2) S} -, wherein R ^V and R ^VI are each independently a hydrogen atom, a dC ₆ alkyl group, a -C ₆ hydroxyalkyl group, or an arylCrC ₆ -alkyl group and s is a number 0, 1, 2, 3, 4, 5 or 6 may be substituted,

• Y ¹ represents an oxygen atom, a sulfur atom or a group NR ^V ", wherein R ^v" stands for a hydrogen atom, an aryl group, a heteroaryl group, a C ₁ -C ₆ - alkyl group or a -C ₆ -arylalkyl group,

• X ^" stands for a physiologically compatible anion, with

(B) at least one compound selected from

4-hydroxy-3-methoxy-6-nitrobenzaldehyde

3,4-dihydroxy-5-nitrobenzaldehyde

2-hydroxy-3-methoxy-5-nitro-benzaldehyde

4-hydroxy-3-methoxy-5-nitrobenzaldehyde (5-nitrovanillin)

3-hydroxy-4-methoxybenzaldehyde

3,4-dimethoxy-5-hydroxybenzaldehyde

4-formyl-1-nnethylchinoliniunn p-toluenesulfonate

O

2-formyl-1-methylquinolinium p-toluenesulfonate O = S = O

In a very particularly preferred embodiment of the invention, the agent in a cosmetic carrier contains a combination of

(A) at least one CH-acidic compound according to formula (I)

wherein

• R ¹ and R ² are independently a linear or cyclic -C ₆ - alkyl group, a C ₂ -C ₆ alkenyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group, an aryl-CrC ₆ - alkyl group, a Ci-C ₆ hydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a Ci-C ₆ alkoxy-C ₆ alkyl group, a group R'R "N- (CH _{2) p} -, wherein R ¹ and R" independently of one another represent a hydrogen atom, a C 1 -C ₄ -alkyl group, a C 1 -C ₄ -hydroxyalkyl group or an aryl-C ₁ -C ₆ -alkyl group, where R 'and R "together with the nitrogen atom are 5-, 6- or 7-membered ring and p is a number 2, 3, 4, 5 or 6,

• R ³ and R ⁵ are independently a hydrogen atom or a -C ₆ - alkyl group, wherein at least one of the radicals R ³ or R ⁵ is a C-ι-C ₆ alkyl group,

• R ⁴ represents a hydrogen atom, a CiC ₆ alkyl group, a -C ₆ - hydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a dC ₆ alkoxy group, a -C ₆ -hydroxyalkoxy group, a group R ^m R ^lv N- ( CH ₂ ) _q -, in which R ^m and R ^iv independently of one another represent a hydrogen atom, a C 1 -C ₆ -alkyl group, a C 1 -C ₆ -hydroxyalkyl group or an aryl-C 1 -C ₆ -alkyl group and q stands for a number 1, 2, 3, 4, 5 or 6, wherein the radical R ⁴ together with one of the radicals R ³ or R ^{5 can form} a 5- or 6-membered aromatic ring optionally with a halogen atom, a C 1 -C ₆ -alkyl group, a C 1 -C ₆ -hydroxyalkyl group , a C ₂ -C ₆ polyhydroxyalkyl group, a -C ₆ alkoxy group, a CrC ₆ - hydroxyalkoxy group, a nitro group, a hydroxy group, a group R ^V R ^VI N- (CH _{2) S} -, wherein, R ^v and R ^vl independently of one another represents a hydrogen atom, a C 1 -C ₆ -alkyl group, a C 1 -C ₆ -hydroxyalkyl group or an arylCrC ₆ alkyl group and s is a number 0, 1, 2, 3, 4, 5 or 6 may be substituted,

• Y ¹ represents an oxygen atom, a sulfur atom or a group NR ^V ", wherein R ^v" stands for a hydrogen atom, an aryl group, a heteroaryl group, a -C ₆ - alkyl group or a -C ₆ -arylalkyl group,

X ^" is a physiologically acceptable anion, With

(B) at least one compound selected from

4-formyl-i-methylquinolinium-p-toluenesulfonate

2-formyl-1-methylquinolinium-p-toluenesulfonate

In this case, it is again preferred if the agent according to the invention contains at least one of the following combinations of (A) and (B):

(a) 1, 2-dihydro-1, 3,4,6-tetramethyl-2-oxopyrimidinium hydrogensulfate and 4-formyl-1-methyl-quinolinium p-toluenesulfonate,

(b) 1, 2-dihydro-1, 3,4,6-tetramethyl-2-oxopyrimidinium hydrogensulfate and 2-formyl-1-methyl-quinolinium p-toluenesulfonate,

(c) 1-allyl-1,2-dihydro-3,4,6-trimethyl-2-oxopyrimidinium bromide and 4-formyl-1-methyl-quinolinium p-toluenesulfonate,

(d) 1-allyl-1,2-dihydro-3,4,6-trimethyl-2-oxopyrimidinium bromide and 2-formyl-1-methyl-quinolinium p-toluenesulfonate,

(e) 1, 2-Dihydro-1, 3,4,6-tetramethyl-2-oxo-pyrimidinium hydrogensulfate, 4-formyl-1-methyl-quinolinium p-toluenesulfonate and 2-formyl-1-methylquinolinium p-toluenesulfonate .

(f) 1-Allyl-1,2-dihydro-3,4,6-trimethyl-2-oxopyrimidinium bromide, 4-formyl-1-methylquinolinium p-toluenesulfonate and 2-formyl-1-methylquinolinium p-toluenesulfonate.

Most suitable are agents according to the invention which contain at least one of the combinations of (A) and (B):

(a) 1, 2-Dihydro-1, 3,4,6-tetramethyl-2-oxopyrimidinium hydrogensulfate and 4-formyl-1-methyl-quinolinium p-toluenesulfonate, (c) 1-allyl-1, 2- dihydro-3,4,6-trimethyl-2-oxopyrimidinium bromide and 4-formyl-1-methyl-quinolinium p-toluenesulfonate. The compounds of the formula (II) and / or formula (III) are preferably present in an amount of from 0.01% by weight to 5% by weight, in particular from 0.05% by weight to 1% by weight, each based on the weight of the ready-to-use agent included.

The agents according to the invention of all the aforementioned embodiments preferably have a pH of from pH 4 to pH 7.

As pH-adjusting agents, preference is given according to the invention to acids and / or alkalizing agents.

As acids according to the invention preferably mineral acids (such as hydrochloric acid, sulfuric acid or phosphoric acid) or edible acids (such as citric acid, tartaric acid or malic acid) are used.

Alkaliating agents useful in the invention are preferably selected from the group consisting of ammonia, basic amino acids, alkali hydroxides, alkanolamines, alkali metal metasilicates, urea, morpholine, N-methylglucamine, imidazole, alkali phosphates, and alkali hydrogen phosphates. The alkali metal ions used are preferably lithium, sodium, potassium, in particular sodium or potassium.

The basic amino acids which can be used as alkalizing agents according to the invention are preferably selected from the group formed from L-arginine, D-arginine, D, L-arginine, L-histidine, D-histidine, D, L-histidine, L-lysine, D-lysine, D, L-lysine, more preferably L-arginine, D-arginine, D, L-arginine used as an alkalizing agent according to the invention.

The alkali metal hydroxides which can be used as the alkalizing agent according to the invention are preferably selected from the group formed from sodium hydroxide and potassium hydroxide.

The alkanolamines which can be used as alkalizing agents according to the invention are preferably selected from primary amines having a C ₂ -C ₆ -alkyl basic body which carries at least one hydroxyl group. Particularly preferred alkanolamines are selected from the group formed from 2-aminoethan-1-ol (monoethanolamine), 3-aminopropan-1-ol, 4-aminobutan-1-ol, 5-aminopentan-1-ol, 1 -Aminopropan-2-ol, 1-aminobutan-2-ol, 1-aminopentan-2-ol, 1-aminopentan-3-ol, 1-aminopentan-4-ol, 3-amino-2-methylpropan-1-ol , 1-amino-2-methylpropan-2-ol, 3-aminopropane-1, 2-diol, 2-amino-2-methylpropane-1,3-diol. Very particularly preferred alkanolamines according to the invention are selected from the group consisting of 2-aminoethane-1-ol, 2-amino-2-methylpropan-1-ol and 2-amino-2-methyl-propane-1,3-diol. Particularly preferably, an alkalizing agent is selected from at least one compound from the group formed from ammonia, 2-aminoethanol, 2-amino-2-methylpropan-1-ol, 2-amino-2-methyl-propane-1, 3 diol, potassium hydroxide, L-arginine, D-arginine, DL-arginine, N-methylglucamine, morpholine, imidazole and urea.

The compounds of component (A) according to formula I and the compounds of component (B) of formulas (II) and (III) can be stored either in separate containers or together in a container, either in a liquid to pasty preparation (aqueous or anhydrous) or as a solid, for example as a dry powder. If the components (A) and (B) are stored together in a liquid preparation, it should be substantially anhydrous to reduce a reaction of the components and have an acidic pH. If the components are stored together, it is preferred to use them as a solid, in particular in the form of a preferably multilayer molding, e.g. as a tablet. In the case of the multilayer molded bodies, the component A is incorporated in one layer and the component B in another layer, wherein between these layers is preferably a further layer as a release layer. The separating layer is free of compounds of components A and B.

In the case of separate storage, a container contains a first composition comprising in a cosmetic carrier at least one compound of the above formula (I) and another container contains a second composition comprising in a cosmetic agent at least one compound of the above formula (II) and / or the above formula (IM).

The reactive components are intimately mixed with each other just prior to use. In dry storage, a defined amount of warm (3O ⁰ C to 8O ⁰ C) water is usually added prior to application and made a homogeneous mixture. The agents according to the invention result in each case from the resulting application mixtures.

It has been shown that the additional presence of further known skin tanning active ingredients in the composition according to the invention surprisingly does not have a negative effect on the achieved tanning result. Therefore, the agent according to the invention may additionally contain at least one tanning active, which enters into the so-called Maillard reaction with the protein of the skin and visibly tans the skin. As an additional tanning active, the compositions according to the invention may additionally comprise dihydroxyacetone. Dihydroxyacetone (abbreviation: DHA, 1,3-dihydroxypropan-2-one, ketotriose, INCI reference: dihydroxyacetone, EINECS 2024945) can be represented by the formula

HO-CH ₂ -C (O) -CH ₂ -OH

describe. In the cosmetics industry, dihydroxyacetone is used to make skin tanning agents, usually in combination with skin care and UV protection ingredients. The pigmentation mechanism is based on the reaction of an activated carbonyl group with the amino acids of the skin in the sense of a Maillrad reaction.

In addition to dihydroxyacetone or in its place, the compositions of the invention may also contain erythrulose as a tanning active. Erythrulose (1, 3,4-trihydroxybutan-2-one) is a chiral keto sugar derived from aldose erythrose. It is used in cosmetics because of its self-tanning properties. Erythrulose is biotechnologically produced from 1, 2,3,4-butanetetrol by the bacterium Gluconobacter oxydans and obtained for this purpose biotechnologically.

CH ₃ OH ChfeOH

HG ™ C-H

CH ₂ ON CH ₂ OH

Form D-Fotrni

Erythrulose reacts with free primary or secondary amino groups in the so-called Maillrad reaction. If this reaction takes place with the amino acids of keratin in the skin, this leads to the formation of brownish polymers, the melanoids. As a result, the skin appears browned. Compared to dihydroxyacetone, the Maillard reaction with erythrulose is slower. The tanning of the skin develops later, but at the same time becomes more uniform than with dihydroxyacetone, since erythrulose can be more evenly distributed in the stratum corneum.

If the agents according to the invention contain additional tanning agents as the trigger for the Maillard reaction with the skin protein, then in a preferred amount of 0.5 to 15.0% by weight, preferably 1.0 to 10.0% by weight. %, more preferably 1, 5 to 5.0 wt .-% and in particular 1, 75 to 3 wt .-%.

In addition to the compounds of component (A) and component (B), the agents according to the invention can additionally contain, as enhancers, special substances which are known from US Pat Stimulate melanin synthesis. By stimulating melanin synthesis, in combination with the self-tanning actives, a more natural skin tan and a color more in line with the consumer's desire.

As the first possible enhancer, the agents according to the invention may contain one or more

Contain compound (s) from the group of hexahydroxycyclohexanes.

Since it is common in the configuration designation of Hexahydroxycyclohexan isomers to name only the hydroxy groups, it can be - assuming that the isomers always in the

Depending on the position of these atoms (a = axial, e = equatorial) distinguish between:

Hexahydroxcyclohexane configuration conformation alpha- ααβαββαβεβα βαβαβαβε eeeeee gamma ααβααβα ααεεα delta αααβαβεεεεεεε αεεαεαα αααβββα αεαεε α αα α αα αααεα etea αα ααββααεαα αααεαα ααααα αααεα αααεα αααεα αααεαα αααεα αααεα αααεα αααεα αααεα αααε tetα αeaαeeα αeaαeeα αeaαeeα αeaαeeα αeaαeeα αeaαeeα αeeαeeα αeeeaα αeeαeeee αa-eeee αa-eeee αa-eeeea-a-a-a-a-a-a-a-

Particularly preferred is the compound quirinositol. D-Quiroinositol (EN-1)

) is a particularly suitable additional enhancer.

Instead of hexahydroxycyclohexanes or in addition thereto, the agents according to the invention may also contain, as enhancers, acetyl-methionyl-arginine-ethyl esters of the formula (EN-2)

contain.

When the agents according to the invention contain an additional enhancer, it is preferred, based on their weight, in an amount of from 0.02 to 10.0% by weight, preferably from 0.05 to 5.0% by weight, more preferably from 0.075 to 2.0 wt .-% and in particular from 0.1 to 1 wt .-%.

For application to human skin, the agents according to the invention are preferably incorporated into an aqueous cosmetic carrier. Suitable aqueous cosmetic carriers are as mentioned above, for. As creams, emulsions, gels or surfactant-containing foaming solutions such. As shampoos or other preparations that are suitable for use on the skin. If necessary, it is also possible to incorporate said drug combination into anhydrous carriers.

As a cosmetic carrier according to the invention, in particular an otherwise customary carrier of agents for tanning human skin is used. Apart from the components according to the invention, the agents according to the invention may be composed according to known skin treatment agents or contain these conventional ingredients. Examples of further suitable and inventively preferred ingredients are given below.

The agents according to the invention preferably additionally contain at least one silicone. The silicones, if they are present in the compositions according to the invention, preferably in amounts of from 0.05 to 5 wt .-%, preferably from 0.2 to 5 wt .-%, each based on the ready-to-use agent.

In particular, the silicones are preferably selected from at least one representative from the list which is formed from:

(i) polyalkylsiloxanes, polyarylsiloxanes, polyalkylarylsiloxanes which are volatile or non-volatile, straight chain, branched or cyclic, crosslinked or uncrosslinked;

(ii) polysiloxanes containing in their general structure one or more organofunctional groups selected from: a) substituted or unsubstituted aminated groups; b) (per) fluorinated groups; c) thiol groups; d) carboxylate groups; e) hydroxylated groups; f) alkoxylated groups; g) acyloxyalkyl groups; h) amphoteric groups; i) bisulfite groups; j) hydroxyacylamino groups; k) carboxy groups;

I) sulfonic acid groups; and m) sulfate or thiosulfate groups;

(iii) linear polysiloxane (A) - polyoxyalkylene (B) - block copolymers of the type (AB) _n with n>3;

(iv) grafted silicone polymers having a non-silicone-containing organic backbone consisting of an organic backbone formed from organic monomers containing no silicone to which at least one polysiloxane macromer has been grafted in the chain and optionally at least one chain end;

(v) grafted polysiloxane backbone silicone polymers having grafted thereto non-silicone organic monomers having a polysiloxane backbone onto which at least one organic macromer containing no silicone has been grafted in the chain, and optionally at least at one of its ends such as the commercial product Abil B 8832 from Degussa marketed under the INCI name BisPEG / PPG-20/20 dimethicone;

(vi) or mixtures thereof.

Particularly preferred cosmetic or dermatological preparations according to the invention are characterized in that they contain at least one silicone of the formula (Si-1)

(CH ₃ ) ₃ Si - [O-Si (CH ₃ ) 2] χ-O-Si (CH ₃ ) 3 (Si-1), in which x is a number from 0 to 100, preferably from 0 to 50, more preferably from 0 to 20 and in particular 0 to 10.

The inventively preferred cosmetic or dermatological preparations contain a silicone of the above formula (Si-1). These silicones are referred to as dimethicones according to the INCI nomenclature. It is in the context of the present invention as the silicone of the formula (Si-1), preferably the compounds:

(CH ₃ ) ₃ Si-O- (CH ₃ ) 2 Si-O-Si (CH ₃ ) 3

(CH ₃ ) ₃ Si - [O- (CH ₃ ) 2 Si] 2 O-Si (CH ₃ ) 3

(CH ₃ ) ₃ Si - [O - (CH ₃ ) 2 Si] 3 - O - Si (CH ₃ ) 3

(CH ₃ ) ₃ Si - [O- (CH ₃ ) 2 Si] 4 O-Si (CH ₃ ) 3

(CH ₃ ) ₃ Si - [O- (CH ₃ ) 2 Si] 5 O-Si (CH ₃ ) 3

(CH ₃ ) ₃ Si - [O - (CH ₃ ) 2 Si] ₆ --O - Si (CH ₃ ) 3

(CH ₃ ) ₃ Si - [O- (CH ₃ ) 2 Si] 7-O-Si (CH ₃ ) 3

(CH ₃ ) ₃ Si - [O - (CH ₃ ) 2 Si] 8 O-Si (CH ₃ ) 3

(CH ₃ ) ₃ Si - [O- (CH ₃ ) 2 Si] ₉ -O-Si (CH ₃ ) 3

(CH ₃ ) ₃ Si - [O- (CH ₃ ) 2 Si] ₁₀ -O-Si (CH ₃ ) ₃

(CH ₃ ) ₃ Si - [O- (CH ₃ ) 2 Si] ₁₁ -O-Si (CH ₃ ) 3

(CH ₃ ) ₃ Si - [O- (CH ₃ ) 2 Si] ₁ 2 -O-Si (CH ₃ ) 3

(CH3) 3Si- [O- (CH3) 2 Si] ₁₃ -O-Si (CH3) 3

(CH3) 3 Si - [O- (CH3) 2 Si] ₁₄ -O-Si (CH3) 3

(CH3) 3 Si - [O- (CH3) 2 Si] ₁₅ -O-Si (CH3) 3

(CH ₃ ) ₃ Si - [O- (CH ₃ ) 2 Si] ₁₆ -O-Si (CH ₃ ) 3

(CH ₃ ) ₃ Si [O- (CH ₃ ) ₂ Si] ₁₇ -O-Si (CH ₃ ) ₃

(CH ₃ ) ₃ Si [O- (CH ₃ ) ₂ Si] ₁₈ -O-Si (CH ₃ ) ₃

(CH ₃ ) ₃ Si [O- (CH ₃ ) ₂ Si] ₁₉ -O-Si (CH ₃ ) ₃

(CH ₃ ) ₃ Si [O- (CH ₃ ) ₂ Si] ₂₀ -O-Si (CH ₃ ) ₃

where (CH ₃ ) ₃ Si-O-Si (CH ₃ ) ₃ , (CH ₃ ) ₃ Si-O- (CH ₃ ) ₂ Si-O-Si (CH ₃ ) ₃ and / or (CH ₃ J ₃ Si [O- (CH ₃ ) ₂ Si] ₂ -O-Si (CH ₃ ) _{3 are} particularly preferred.

Of course, mixtures of the above-mentioned silicones may also be present in the preferred agents according to the invention. Preferred silicones according to invention have at 2O ⁰ C to viscosities of 0.2 to 2 mmV ^1, wherein silicones having viscosities of 0.5 to 1 mmV ¹ are particularly preferred.

Particularly preferred agents according to the invention contain one or more amino-functional silicones. Such silicones may e.g. by the formula (Si-2)

M (R _a Q _b Si0 ₍₄ - _a - _b ) / ₂ ) _x (R _c Si0 ₍₄ - _{c) / 2} ) _y M (Si-2)

Be described, taking in the above formula

R is a hydrocarbon or a hydrocarbon radical having 1 to about 6 carbon atoms, Q is a polar radical of the general formula -R ¹ HZ, wherein

R ^{1 is} a divalent linking group bonded to hydrogen and the radical Z composed of carbon and hydrogen atoms, carbon, hydrogen and oxygen atoms or carbon, hydrogen and nitrogen atoms, and

Z is an organic, amino-functional group containing at least one amino-functional group; a assumes values in the range of about 0 to about 2, b takes values in the range of about 1 to about 3, a + b is less than or equal to 3, and c is a number in the range of about 1 to about 3, and x a number ranging from 1 to about 2,000, preferably from about 3 to about 50, and most preferably from about 3 to about 25; and y is a number ranging from about 20 to about 10,000, preferably from about 125 to about

10,000 and most preferably from about 150 to about 1,000, and M is a suitable silicone end group as known in the art, preferably trimethylsiloxy.

Non-limiting examples of the groups represented by R in formula (Si-2) include alkyl groups such as methyl, ethyl, propyl, isopropyl, isopropyl, butyl, isobutyl, amyl, isoamyl, hexyl, isohexyl and the like; Alkenyl radicals such as vinyl, halovinyl, alkylvinyl, allyl, haloallyl, alkylallyl; Cycloalkyl radicals such as cyclobutyl, cyclopentyl, cyclohexyl and the like; Phenyl radicals, benzyl radicals, halohydrocarbon radicals such as 3-chloropropyl, 4-bromobutyl, 3,3,3-trifluoropropyl, chlorocyclohexyl, bromophenyl, chlorophenyl and the like, and sulfur-containing radicals such as mercaptoethyl, mercaptopropyl, mercaptohexyl, mercaptophenyl and the like; preferably R is an alkyl radical containing from 1 to about 6 carbon atoms, and most preferably R is methyl. Examples of R ¹ include methylene, ethylene, propylene, hexamethylene, decamethylene, - CH ₂ CH (CH ₃ ) CH ₂ -, phenylene, naphthylene, -CH ₂ CH ₂ SCH ₂ CH ₂ -, -CH ₂ CH ₂ OCH ₂ - , -OCH ₂ CH ₂ -, - OCH ₂ CH ₂ CH ₂ -, -CH ₂ CH (CH ₃ ) C (O) OCH ₂ -, - (CH ₂ J ₃ CC (O) OCH ₂ CH ₂ -, - C ₆ H ₄ C ₆ H ₄ -, -C ₆ H ₄ CH ₂ C ₆ H ₄ -; and - (CH ₂ ) ₃ C (O) SCH ₂ CH ₂ -.

Z is according to formula (Si-2) an organic, amino-functional radical containing at least one functional amino group. A possible formula for said Z is NH (CH ₂ ) _Z NH ₂ , where z is an integer greater than or equal to 1. Another possible formula for said Z is - NH (CH _{2) Z} (CH _{2) currently} NH wherein both z and zz are independently an integer of greater than or equal 1, wherein said structure comprises diamino-ring structures such as piperazinyl. Said Z is most preferably an -NHCH ₂ CH ₂ NH ₂ radical. Another possible formula for said Z is -N (CH ₂ ) _Z (CH ₂ ) _ZZ NX ₂ or -NX ₂ , wherein each X of X _{2 is} independently selected from the group consisting of hydrogen and alkyl groups of 1 to 12 carbon atoms, and zz is O

Q according to formula (Si-2) is most preferably a polar amino-functional radical of formula - CH ₂ CH ₂ CH ₂ NH ₂ CH ₂ CH ₂ NH ₂ .

In the formula (Si-2), α takes values in the range of 0 to 2, b takes values in the range of 2 to 3, a + b is less than or equal to 3, and c is a number in the range of 1 to 3. The molar ratio of the R _a Q _b SiO _{(4 a a b) / 2} units to the R ₀ SiO _{(4 C) 2} units in formula (Si-2) is in the range of about 1: From 2 to 1: 65, preferably from about 1: 5 to about 1:65, and most preferably from about 1:15 to about 1: 20. If one or more of the above formula (Si-2) silicones are used then the various variable substituents in the above formula may be different for the various silicone components present in the silicone blend.

Preferred cosmetic or dermatological preparations according to the invention contain an amino-functional silicone of the formula (Si-3)

R ' _a G ₃ . _a -Si (OSiG _{2) n} - (OSiG _b R _'2 _ _{b) m} -O-SiG. _{3 a} -R _'a (Si-3),

where:

G is -H, a phenyl group, -OH, -O-CH ₃ , -CH ₃ , -O-CH ₂ CH ₃ , -CH ₂ CH ₃ , -O-CH ₂ CH ₂ CH ₃ ,

-CH ₂ CH ₂ CH ₃ , -O-CH (CH ₃ ) ₂ , -CH (CH ₃ ) ₂ , -O-CH ₂ CH ₂ CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₂ CH ₃ , -O-CH ₂ CH (CH ₃ ) ₂ , -CH ₂ CH (CHs) ₂ , -O-CH (CH ₃ ) CH ₂ CH ₃ , -CH (CH ₃ ) CH ₂ CH ₃ , -O-C ( CH _{3) 3,} -C (CH _{3) 3;} a is a number between O and 3, in particular O; b is a number between O and 1, in particular 1, m and n are numbers whose sum (m + n) is between 1 and 2000, preferably between 50 and 150, where n is preferably values from 0 to 1999 and in particular from 49 to 149 and m preferably assumes values from 1 to 2000, in particular from 1 to 10,

R ^' is a monovalent radical selected from -QN (R ") - CH ₂ -CH ₂ -N (R") ₂ -QN (FT) ₂ -QN ⁺ (R ") ₃ A- -QN ⁺ H (R" ) ₂ A ^" -QN ⁺ H ₂ (R") A ^"

-QN (R ") - CH ₂ -CH ₂ -N ⁺ R" H ₂ A ^" , where each Q is a chemical bond, -CH ₂ -, -CH ₂ -CH ₂ -, -CH ₂ CH ₂ CH ₂ -, -C (CHa) ₂ -, -CH ₂ CH ₂ CH ₂ CH ₂ -, -CH ₂ C (CH ₃ ) ₂ -, -CH (CH ₃ ) CH ₂ CH ₂ -, R "is the same or various radicals from the group -H, -phenyl, -benzyl, -CH ₂ - CH (CH ₃ ) Ph, the d. ₂₀ -alkyl radicals, preferably -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ , -CH ₂ CH ₂ CH ₂ H ₃ , -CH ₂ CH (CH ₃ ) ₂ , -CH (CH ₃ ) CH ₂ CH ₃ , -C (CH ₃ ) ₃ , and A represents an anion, which is preferably selected from chloride, bromide, iodide or methosulfate.

Cationic silicone oils, such as the commercially available Dow Corning 929 emulsion (containing a hydroxylamino-modified silicone referred to as amodimethicone), DC 2-2078 (manufacturer Dow Corning, INCI name: Aminopropyl Phenyl Trimethicone), DC 5 are suitable according to the invention -7113 (manufacturer Dow Corning, INCI name: Silicone Quaternium 16), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil ^® quat 3270 and 3272 (manufacturer: Th Goldschmidt; diquatemäre. Polydimethylsiloxanes, quaternium-80).

Particularly preferred agents according to the invention are characterized in that they contain at least one amino-functional silicone of the formula (Si 3-a)

(CH ₃ ) ₃ Si [O-Si (CH ₃ ) ₂ ] _n [O-Si (CH ₃ )] _m -OSi (CH ₃ ) ₃ (Si-3a),

CH ₂ CH (CH ₃ ) CH ₂ NH (CH ₂ ) ₂ NH ₂ in which m and n are numbers whose sum (m + n) is between 1 and 2000, preferably between 50 and 150, where n preferably values of 0 to 1999 and in particular of 49 to 149 and m preferably values of 1 to 2000 , in particular from 1 to 10 assumes.

These silicones are referred to as trimethylsilylamodimethicones according to the INCI declaration and are available, for example, under the name Q2-7224 (manufacturer: Dow Corning, a stabilized trimethylsilylamodimethicone).

Particular preference is also given to compositions according to the invention which contain at least one amino-functional silicone of the formula (Si-3b)

R- [Si (CH _{3) 2} -O] _n1 [Si (R ') - O] _m - [Si (CH _{3) 2} -O] _n2 SiMe ₂ R (Si-3b),

(CH ₂ ) ₃ NH (CH ₂ ) ₂ NH ₂

contain, in which

R is -OH, a (optionally ethoxylated and / or propoxylated) (Ci to C ₂₀ ) -

Alkoxy group or a -CH ₃ group,

R 'is -OH, a (C ₁ to C ₂₀ ) alkoxy group or a -CH ₃ group and m, n1 and n2 are numbers whose sum (m + n1 + n2) is between 1 and 2,000, preferably between 50 and Is 150, wherein the sum (n1 + n2) is preferably 0 to 1999 and more preferably 49 to 149, and m is preferably values of

1 to 2000, in particular from 1 to 10 assumes.

These silicones are according to the INCI declaration as Amodimethicone, or as functionalized Amodimethicone, such as bis (C13-15 alkoxy) PG Amodimethicone (for example, as a commercial product: DC 8500 from Dow Corning available), trideceth-9 PG-amodimethicones (for example as a commercial product Silcare Silicone SEA available from Clariant).

Regardless of which amino-functional silicones are used, preference is given to cosmetic or dermatological preparations according to the invention which contain an amino-functional silicone whose amine number is above 0.25 meq / g, preferably above 0.3 meq / g and in particular above 0.4 meq / g is. The amine number stands for the milliequivalents of amine per gram of the amino-functional silicone. It can be determined by titration and also expressed in mg KOH / g.

Cosmetic or dermatological preparations preferred according to the invention are characterized characterized in that, based on their weight, 0.01 to 10 wt.%, Preferably 0.1 to 8 wt.%, Particularly preferably 0.25 to 7.5 wt.% And in particular 0.5 to 5 wt. % amino-functional silicone (s).

The cyclic dimethicones designated as cyclomethicones according to INCI can also be used with preference in accordance with the invention. Here, cosmetic or dermatological preparations according to the invention are preferred which contain at least one silicone of the formula (Si-4)

in which x is a number from 0 to 200, preferably from 0 to 10, more preferably from 0 to 7 and in particular 0, 1, 2, 3, 4, 5 or 6 stands.

The silicones described above have a backbone composed of -Si-O-Si units. Of course, these Si-O-Si units may also be interrupted by carbon chains. Appropriate molecules are accessible by chain extension reactions and are preferably used in the form of silicone-in-water emulsions.

The silicone-in-water emulsions which can be used according to the invention can be prepared by known processes, as disclosed, for example, in US Pat. No. 5,998,537 and EP 0 874 017 A1.

In summary, this method of preparation comprises the emulsifying mixture of components, one of which contains at least one polysiloxane, the other of which contains at least one organosilicone material which reacts with the polysiloxane in a chain extension reaction, with at least one metal ion-containing catalyst for the chain extension reaction, at least one surfactant and water present are.

Chain extension reactions with polysiloxanes are known and may include, for example, the hydrosilylation reaction in which an Si-H group having an aliphatically unsaturated group in the presence of a platinum / rhodium catalyst to form polysiloxanes having some Si (C) _P- Si bonds (p = 1-6), the polysiloxanes also being referred to as polysiloxane-polysilalkylene copolymers. The chain extension reaction may also include the reaction of an Si-OH group (e.g., a hydroxy-terminated polysiloxane) with an alkoxy group (e.g., alkoxysilanes, silicates, or alkoxysiloxanes) in the presence of a metal-containing catalyst to form polysiloxanes.

The polysiloxanes used in the chain extension reaction comprise a substantially linear polymer of the following structure:

R-Si (R ₂ HO-Si (R ₂ Hn-O-SiR ₃

In this structure, each R independently represents a hydrocarbon radical having up to 20 carbon atoms, preferably having 1 to 6 carbon atoms, such as an alkyl group (for example, methyl, ethyl, propyl or butyl), an aryl group (for example, phenyl), or group required for the chain extension reaction ("reactive group", for example Si-bonded H atoms, aliphatically unsaturated groups such as vinyl, allyl or hexenyl, hydroxy, alkoxy, such as methoxy, ethoxy or propoxy, alkoxy-alkoxy, acetoxy, amino, etc.), with the proviso that on average one to two reactive groups are present per polymer, n is a positive number> 1. Preferably, a plurality of the reactive groups, more preferably> 90%, and especially> 98% of the reactive groups, at the terminal Si -Atomen bound in siloxane. Preferably, n is numbers describing polysiloxanes having viscosities between 1 and 1,000,000 mm ² / s, more preferably viscosities between 1,000 and 100,000 mm ² / s.

The polysiloxanes may be branched to a low degree (for example, <2 mol% of the siloxane units), but the polymers are substantially linear, more preferably fully linear. In addition, the substituents R may in turn be substituted, for example with N-containing groups (for example amino groups), epoxy groups, S-containing groups, Si-containing groups, O-containing groups, etc. Preferably, at least 80% of the radicals R are alkyl radicals, especially preferably methyl groups.

The organosilicone material that reacts with the polysiloxane in the chain extension reaction may be either a second polysiloxane or a molecule that acts as a chain extender. When the organosilicone material is a polysiloxane, it has the above-mentioned general structure. In these cases, one polysiloxane in the reaction has (at least) one reactive group, and a second polysiloxane has (at least) a second reactive group that reacts with the first.

If the organosilicone material comprises a chain extension agent, this may be a material such as a silane, a siloxane (for example, disiloxanes or trisiloxane) or a silazane. For example, a composition comprising a polysiloxane according to the general structure described above having at least one Si-OH group can be chain extended by reacting with an alkoxysilane (for example, a dialkoxysilane or trialkoxysilane) in the presence of tin or titanium-containing catalysts is reacted.

The metal-containing catalysts in the chain extension reaction are usually specific for a particular reaction. Such catalysts are known in the art and include, for example, metals such as platinum, rhodium, tin, titanium, copper, lead, etc. In a preferred chain extension reaction, a polysiloxane having at least one aliphatically unsaturated group, preferably an end group, is reacted with an organosilicone material Presence of a hydrosilylation catalyst which is a siloxane or polysiloxane having at least one (preferably terminal) Si-H group. The polysiloxane has at least one aliphatically unsaturated group and satisfies the general formula given above in which R and n are as defined above, with an average of between 1 and 2 groups R having one aliphatically unsaturated group per polymer. Representative aliphatic unsaturated groups are, for example, vinyl, allyl, hexenyl and cyclohexenyl or a group R ² CH = CHR ³ in which R ^{2 is} a divalent aliphatic silicon-bonded chain and R ^{3 is} a hydrogen atom or an alkyl group. The organosilicone material having at least one Si-H group preferably has the above-mentioned structure, wherein R and n are as defined above and wherein, on average, between 1 and 2 groups R is hydrogen and n is 0 or a positive integer.

This material may be a polymer or a low molecular weight material such as a siloxane (for example, a disiloxane or a trisiloxane).

The polysiloxane having at least one aliphatic unsaturated group and the organosilicone material having at least one Si-H group react in the presence of a hydrosilylation catalyst. Such catalysts are known in the art and include, for example, platinum and rhodium-containing materials. The catalysts may take any known form, for example platinum or rhodium coated on support materials (such as silica gel or activated carbon) or other suitable compounds such as platinum chloride, salts of platinum or chloroplatinic acids. Chloroplatinic acid either as a commercially available hexahydrate or in anhydrous form is a preferred catalyst because of good dispersibility in organosilicone systems and low color change.

In another preferred chain extension reaction, a polysiloxane having at least a Si-OH group, preferably an end group, reacted with an organosilicone material having at least one alkoxy group, preferably a siloxane having at least one Si-OR group or an alkoxysilane having at least two alkoxy groups. In this case, the catalyst used is again a metal-containing catalyst.

For the reaction of an Si-OH group with an Si-OR group, there are many catalysts known from the literature, for example organometallic compounds such as organotin salts, tolates or titanium chelates or complexes. Examples include stannous octoate, dibutyltin dilaurate, dibutyltin diacetate, dimethyltin dineodecanoate, dibutyltin dimethoxide, isobutyltin triceroate, dimethyltin dibutyrate, dimethyltin dineodecanoate, triethyltin tartrate, tin oleate, tin naphthenate, tin butyrate, tin acetate, tin benzoate, tin sebacate, Tin succinate, tetrabutyl titanate, tetraisopropyl titanate, tetraphenyl titanate, tetraoctadecyl titanate, titanium naphthanate, ethyl triethanolamine titanate, titanium diisopropyl diethyl acetoacetate, titanium diisopropoxy diacetyl acetonate and titanium tetra alkoxides in which the alkoxide is butoxy or propoxy.

Agents which are likewise preferred according to the invention are characterized in that they contain at least one silicone of the formula (Si-5)

R ₃ Si [O-SiR ₂ ] χ- (CH ₂ ) _n - [O-SiR ₂ ] _y -O-SiR 3 (Si-5),

in which R is identical or different radicals from the group -H, -phenyl, -benzyl, -CH ₂ -CH (CH ₃ ) Ph, the Ci _-20- alkyl radicals, preferably -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ , -CH ₂ CH ₂ CH ₂ H ₃ , -CH ₂ CH (CH ₃ ) ₂ , -CH (CH ₃ ) CH ₂ CH ₃ , -C (CH ₃ J ₃₎ , x or y is a number from 0 to 200, preferably from 0 to 10, more preferably from 0 to 7 and in particular 0, 1, 2, 3, 4, 5 or 6, and n is a number from 0 to 10, preferably from 1 to 8 and in particular from 2, 3, 4, 5, 6.

The silicones are preferably water-soluble. According to preferred means of the embodiment with a silicone are characterized in that the silicone is water-soluble.

Corresponding hydrophilic silicones are selected, for example, from the compounds of the formulas (Si-6) and / or (Si-7). Particularly preferred water-soluble silicone-based surfactants are selected from the group of dimethicone copolyols which are preferably alkoxylated, in particular polyethoxylated or polypropoxylated. Dimethicone copolyols are understood according to the invention as meaning preferably polyoxyalkylene-modified dimethylpolysiloxanes of the general formulas (Si-6) or (Si-7):

O) _b -R (Si-6)

R'- Si ^■ [OSi (CH _{3) 2] x} - (OC ₂ H _{4) a} - (OC ₃ H _{6) b} -OR "

(Si-7) where the radical R is a hydrogen atom, an alkyl group having 1 to 12 C atoms, a

Alkoxy group having 1 to 12 carbon atoms or a hydroxyl group, the radicals R 'and R "are alkyl groups having 1 to 12 carbon atoms, x is an integer from 1 to 100, preferably from 20 to 30, y is a integer from 1 to 20, preferably from 2 to 10 and a and b are integers from 0 to 50, preferably from 10 to 30.

Particularly preferred dimethicone copolyols according to the invention are, for example, the products sold commercially under the trade name SILWET (Union Carbide Corporation) and DOW CORNING (Dow).

Dimethicone copolyols particularly preferred according to the invention are Dow Corning 190 and Dow Corning 193 (Dow).

The use of surfactants in the compositions according to the invention has proved to be particularly advantageous. In a further preferred embodiment, the agents according to the invention therefore additionally contain at least one surfactant. The term "surfactants" is understood as meaning surface-active substances which form adsorption layers on the upper and boundary surfaces or which can aggregate in volume phases to give micelle colloids or lyotropic mesophases. A distinction is made anionic surfactants consisting of a hydrophobic group and a negatively charged hydrophilic head group, amphoteric surfactants which carry both a negative and a compensating positive charge, cationic surfactants, which in addition to a hydrophobic group having a positively charged hydrophilic group, and nonionic surfactants which have no charges but strong dipole moments and are highly hydrated in aqueous solution.

Suitable anionic surfactants (E1) in preparations according to the invention are all anionic surfactants suitable for use on the human body. These are characterized by a water-solubilizing, anionic group such as. As a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group having about 8 to 30 carbon atoms. In addition, glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups may be present in the molecule. Examples of suitable anionic surfactants are, in each case in the form of the sodium, potassium and ammonium as well as the mono-, di- and trialkanolammonium salts having 2 to 4 C atoms in the alkanol group, linear and branched fatty acids having 8 to 30 C atoms (Soap),

Ethercarbonsäuren the formula RO- (CH2-CH2θ) _χ -CH2-COOH, in which R is a linear

Alkyl group having 8 to 30 C atoms and x = 0 or 1 to 16,

Acylsarcosides having 8 to 24 carbon atoms in the acyl group,

Acyltaurides having 8 to 24 carbon atoms in the acyl group,

Acyl isethionates having 8 to 24 carbon atoms in the acyl group,

Sulfobernsteinsäuremono- and -dialkylester having 8 to 24 carbon atoms in the alkyl group and

Sulfosuccinic acid mono-alkyl polyoxyethyl esters having 8 to 24 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups, linear alkanesulfonates having 8 to 24 carbon atoms, linear alpha-olefin sulfonates having 8 to 24 carbon atoms,

Alpha-sulfofatty acid methyl esters of fatty acids having 8 to 30 carbon atoms, - alkyl sulfates and Alkylpolyglykolethersulfate of the formula RO (CH ₂ -CH ₂ O) _X -OSO ₃ H, in which R is a preferably linear alkyl group having 8 to 30 carbon atoms and x = 0 or 1 to 12, sulfated hydroxyalkylpolyethylene and / or hydroxyalkylene-propylene glycol ethers

Sulfonates of unsaturated fatty acids having 8 to 24 carbon atoms and 1 to 6 double bonds

Esters of tartaric acid and citric acid with alcohols containing adducts of about 2-

15 molecules of ethylene oxide and / or propylene oxide to fatty alcohols having 8 to 22 carbon atoms,

Alkyl and / or alkenyl ether phosphates of the formula (E1-I),

R ¹ (OCH ₂ CH ₂ ) _n -OP (O) (OX) -OR ² (E 1 -I)

in the R ^{1 is} preferably an aliphatic hydrocarbon radical having 8 to 30 carbon atoms atoms, R ^{2 is} hydrogen, a radical (CH ₂ CH ₂ O) _n R ² or X, n is from 1 to 10 and X is hydrogen, an alkali or alkaline earth metal or NR ³ R ⁴ R ⁵ R ⁶ , with R ³ to R ⁶ independently of one another represent hydrogen or a C ₁ to C ₄ hydrocarbon radical, sulfated fatty acid alkylene glycol esters of the formula (E≡ 1-11) R ⁷ CO (Al k O) _n SO ₃ M (E1-II) in the R ⁷ CO- is a linear or branched, aliphatic, saturated and / or unsaturated acyl radical having 6 to 22 C atoms, Alk is CH ₂ CH ₂ , CHCH ₃ CH ₂ and / or CH ₂ CHCH ₃ , n is 0 , 5 to 5 and M is a cation, monoglyceride sulfates and monoglyceride ether sulfates of the formula (E1-III)

CH ₂ O (CH ₂ CH ₂ O) _x -COR ⁸ CHO (CH ₂ CH ₂ O) _y H (E1-III)

CH ₂ O (CH ₂ CH ₂ O) _Z SO ₃ X in the R ⁸ CO for a linear or branched acyl radical having 6 to 22 carbon atoms, x, y and z in total for 0 or for numbers from 1 to 30, preferably 2 to 10, and X is an alkali or alkaline earth metal. Typical examples of monoglyceride (ether) sulfates suitable for the purposes of the invention are the reaction products of lauric acid monoglyceride, coconut fatty acid monoglyceride, palmitic acid monoglyceride, stearic acid monoglyceride, oleic acid monoglyceride and tallow fatty acid monoglyceride and their ethylene oxide adducts with sulfur trioxide or chlorosulfonic acid in the form of their sodium salts. Preferably, monoglyceride sulfates of the formula (E1-III) are used in which R ⁸ CO is a linear acyl radical having 8 to 18 carbon atoms, amide-ether carboxylic acids,

Condensation products of C ₈ - C ₃ o - fatty alcohols with protein hydrolysates and / or amino acids and derivatives thereof, .which the skilled person are known as protein fatty acid condensates, such as Lamepon ^® - types Gluadin ^® - types Hostapon ^® KCG or Amisoft ^® - types.

Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids having 10 to 18 C atoms in the alkyl group and up to 12 glycol ether groups in the molecule, sulfosuccinic acid mono- and dialkyl esters having 8 to 18 C atoms in the alkyl group and sulfosuccinic acid monoalkylpolyoxyethylester with 8 to 18 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups, Monoglycerdisulfate, alkyl and Alkenyletherphosphate and Eiweissfettsäurekondensate. Zwitterionic surfactants (E2) are those surface-active compounds which carry at least one quaternary ammonium group and at least one -COO ⁽⁾ or -SO ₃ '^"' group in the molecule. Alkyl-N, N-dimethylammonium glycinates, for example, the cocoalkyl-di-methylammoniumglycinat, N-acyl-aminopropyl-N, N-dimethylammoniumglycinate, for example Kokosacylaminopropyl-dimethylammoniumglycinat, and 2-alkyl-3-carboxymethyl-3-hydroxyethyl-imidazoline The preferred zwitterionic surfactant is the fatty acid amide derivative known by the INCI name cocamidopropyl betaine.

Ampholytic surfactants (E3) are understood as meaning those surface-active compounds which contain, in addition to a C ₈ -C ₂₄ -alkyl or -acyl group, at least one free amino group and at least one -COOH or -SO ₃ H group in the molecule and for forming internal Salts are capable. Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each having about 8 to 24 C Atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and the C ₂ - C ₈ - sarcosine.

Nonionic surfactants (E4) contain as hydrophilic group e.g. a polyol group, a polyalkylene glycol ether group, or a combination of polyol and polyglycol ether groups. Such compounds are, for example

Addition products of 2 to 50 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide to linear and branched fatty alcohols having 8 to 30 carbon atoms, to fatty acids having 8 to 30 carbon atoms and alkylphenols having 8 to 15 carbon atoms in the alkyl group , end-capped adducts of 2 to 50 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide with linear or branched fatty alcohols containing 8 to 30 carbon atoms, with fatty acids containing 8 to 30 carbon atoms, with a methyl or C ₂ -C ₆ -alkyl radical. Atoms and alkylphenols having 8 to 15 carbon atoms in the alkyl group, such as the available under the sales names Dehydol ^® LS, Dehydol ^® LT (Cognis) types, C ₂ -C ₃₀ fatty acid mono- and diesters of addition products of 1 to 30 moles of ethylene oxide with glycerol,

Addition products of 5 to 60 mol ethylene oxide onto castor oil and hydrogenated castor oil, polyol fatty acid esters, such as the commercially available product ^® Hydagen HSP (Cognis) or Sovermol - types (Cognis), alkoxylated triglycerides, alkoxylated fatty acid alkyl esters of the formula (E4-I)

R ¹ CO- (OCH ₂ CHR ² ) _W OR ³ (E4-I)

in the R ¹ CO is a linear or branched, saturated and / or unsaturated acyl radical having 6 to 22 carbon atoms, R ^{2 is} hydrogen or methyl, R ^{3 is a} linear or branched alkyl radical having 1 to 4 carbon atoms and w is a number from 1 to 20 stands,

Amine oxides,

hydroxy mixed,

Sorbitan fatty acid esters and adducts of ethylene oxide with sorbitan fatty acid esters such as the polysorbates,

Sugar fatty acid esters and addition products of ethylene oxide with sugar fatty acid esters,

Addition products of ethylene oxide to fatty acid alkanolamides and fatty amines,

Sugar surfactants of the alkyl and alkenyl oligoglycoside type of formula (E4-II),

in which R ^{4 is} an alkyl or alkenyl radical having 4 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and p is a number from 1 to 10. They can be obtained by the relevant methods of preparative organic chemistry. The alkyl and alkenyl oligoglycosides can be derived from aldoses or ketoses with 5 or 6 carbon atoms, preferably glucose. The preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucosides. The index number p in the general formula (E4-II) indicates the degree of oligomerization (DP), ie the distribution of mono- and oligoglycosides and stands for a number between 1 and 10. While p in the individual molecule must always be integer and here before For all given values p = 1 to 6, the value p for a given alkyloligoglycoside is an analytically determined arithmetic quantity, which usually represents a fractional number. Preference is given to using alkyl and / or alkenyl oligoglycosides having an average degree of oligomerization p of from 1.1 to 3.0. From an application point of view, those alkyl and / or alkenyl oligoglycosides whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.4 are preferred. The alkyl or alkenyl radical R ⁴ can be derived from primary alcohols having 4 to 11, preferably 8 to 10 carbon atoms. Typical examples are butanol, caproic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and their technical mixtures, as used, for example, in the hydrogenation of technical niche fatty acid methyl esters or in the course of the hydrogenation of aldehydes from the Roelen oxo synthesis can be obtained. Preference is given to alkyl oligoglucosides of chain length Cs-C ₁₀ (DP = 1 to 3), which are obtained as a feedstock in the distillative separation of technical Cs-C ₁₈ coconut fatty alcohol and with a content of less than 6 wt .-% C-i2 alcohol may be contaminated and alkyl oligoglucosides based on technical Cg _/ n-oxo alcohols (DP = 1 to 3). The alkyl or alkenyl radical R ¹⁵ can also be derived from primary alcohols having 12 to 22, preferably 12 to 14 carbon atoms. Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol, and technical mixtures thereof which can be obtained as described above. Alkyl oligoglucosides based on hydrogenated _{C12 /} i ₄ coconut alcohol with a DP of 1 to 3

Sugar surfactants of the fatty acid N-alkylpolyhydroxyalkylamide type, a nonionic surfactant of the formula (E4-III),

R ⁵ CO-NR ⁶ - [Z] (E4-III)

R ^{5 is} CO for an aliphatic acyl radical having 6 to 22 carbon atoms, R ^{6 is} hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 12 carbon atoms and 3 to 10 hydroxyl groups stands. The fatty acid N-alkyl polyhydroxyalkylamides are known substances which are usually obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride. Preferably, the fatty acid N-alkylpolyhydroxyalkylamides are derived from reducing sugars having 5 or 6 carbon atoms, especially glucose. The preferred fatty acid N-alkylpolyhydroxyalkylamides are therefore fatty acid N-alkylglucamides, as represented by the formula (E4-IV):

R ⁷ CO-NR ⁸ -CH ₂ - (CHOH) ₄ -CH ₂ OH (E4-IV)

The fatty acid N-alkylpolyhydroxyalkylamides used are preferably glucamides of the formula (E4-IV) in which R ^{8 is} hydrogen or an alkyl group and R ^{7 is} CO for the acyl radical of caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmitic acid, Stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, arachidic acid, gadoleic acid, behenic acid or Erucic acid or derer technical mixtures. Particular preference is given to fatty acid N-alkylglucamides of the formula (E4-IV) which are obtained by reductive amination of glucose with methylamine and subsequent acylation with lauric acid or C12 / 14 coconut fatty acid or a corresponding derivative. Furthermore, the polyhydroxyalkylamides can also be derived from maltose and palatinose.

The preferred nonionic surfactants are the alkylene oxide addition products of saturated linear fatty alcohols and fatty acids having in each case 2 to 30 moles of ethylene oxide per mole of fatty alcohol or fatty acid. Preparations having excellent properties are also obtained if they contain fatty acid esters of ethoxylated glycerol as nonionic surfactants.

These connections are identified by the following parameters. The alkyl radical R contains 6 to 22 carbon atoms and may be both linear and branched. Preference is given to primary linear and methyl-branched in the 2-position aliphatic radicals. Such alkyl radicals are, for example, 1-octyl, 1-decyl, 1-lauryl, 1-myristyl, 1-cetyl and 1-stearyl. Particularly preferred are 1-octyl, 1-decyl, 1-lauryl, 1-myristyl. When so-called "oxo-alcohols" are used as starting materials, compounds with an odd number of carbon atoms in the alkyl chain predominate.

Furthermore, very particularly preferred nonionic surfactants are the sugar surfactants. These may preferably be contained in the agents used according to the invention in amounts of from 0.1 to 20% by weight, based on the total agent. Amounts of 0.5 to 15 wt .-% are preferred, and very particularly preferred amounts of 0.5 to 7.5 wt.%.

The compounds used as surfactant with alkyl groups may each be uniform substances. However, it is usually preferred to start from the production of these substances from native plant or animal raw materials, so as to obtain substance mixtures with different, depending on the particular raw material alkyl chain lengths.

In the case of the surfactants which are adducts of ethylene oxide and / or propylene oxide with fatty alcohols or derivatives of these addition products, both products with a "normal" homolog distribution and those with a narrow homolog distribution can be used. By "normal" homolog distribution are meant mixtures of homologues which are used in the reaction of fatty alcohol and alkylene oxide using alkali metals, alkali metal hydroxides or alkali metal alcoholates Catalysts receives. Narrowed homolog distributions are obtained when, for example, hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or alcoholates are used as catalysts. The use of products with narrow homolog distribution may be preferred.

Cationic surfactants of the type of the quaternary ammonium compounds, the esterquats and the amidoamines can be used according to the invention. Preferred quaternary ammonium compounds are ammonium halides, in particular chlorides and bromides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkyl methylammonium chlorides, eg. For example, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride, as well as the imidazolium compounds known under the INCI names Quaternium-27 and Quaternium-83. The long alkyl chains of the above-mentioned surfactants preferably have 10 to 18 carbon atoms.

According to the invention, preference is given to using QAV with behenyl radicals, in particular those known as behentrimonium chloride or bromide (docosanyltrimethylammonium chloride or bromide). Other preferred QAV's have at least two behenyl residues, with QAV being particularly preferred, which are two behenyl residues on an imidazolinium backbone. Commercially available, these substances, for example, under the names Genamin ^® KDMP (Clariant) and Crodazosoft ^® DBQ (Crodauza) are.

Esterquats are known substances which contain both at least one ester function and at least one quaternary ammonium group as a structural element. Preferred esterquats are quaternized ester salts of fatty acids with triethanolamine, quaternized ester salts of fatty acids with diethanolalkylamines and quaternized ester salts of fatty acids with 1,2-dihydroxypropyldialkylamines. Such products are marketed under the trade names Stepantex® ^{®, ®} and Dehyquart® Armocare® ^®. The products Armocare ^® VGH-70, a N, N-bis (2-palmitoyloxyethyl) dimethylammonium chloride, as well as Dehyquart ^® F-75, Dehyquart ^® C-4046, Dehyquart ^® L80 and Dehyquart ^® AU-35 are examples of such esterquats.

The alkylamidoamines are usually prepared by amidation of natural or synthetic fatty acids and fatty acid cuts with dialkylaminoamines. An inventively particularly suitable compound from this group of substances under the name Tegoamid ^® S 18 commercial stearamidopropyl dimethylamine is. For the cationic surfactants, the compositions according to the invention contain preferred amounts of from 0.05 to 10% by weight, based on the composition. Amounts of 0.1 to 5 wt .-% are particularly preferred.

Anionic, nonionic, zwitterionic and / or amphoteric surfactants and mixtures thereof may be preferred according to the invention.

In summary, agents according to the invention are preferred which, based on their weight, contain 0.5 to 50% by weight, preferably 1 to 40% by weight and in particular 5 to 25% by weight of anionic (s) and / or nonionic (s ) and / or cationic and / or amphoteric surfactant (s).

Another preferred group of additional ingredients of the compositions of the invention are vitamins, provitamins or vitamin precursors. These are described below:

The group of substances called vitamin A includes retinol (vitamin A ₁ ) and 3,4-didehydroretinol (vitamin A ₂ ). The ß-carotene is the provitamin of retinol. As vitamin A component according to the invention, for example, vitamin A acid and its esters, vitamin A aldehyde and vitamin A alcohol and its esters such as the palmitate and the acetate into consideration. The agents according to the invention preferably contain the vitamin A component in amounts of 0.05-1% by weight, based on the total preparation.

The vitamin B group or the vitamin B complex include vitamin B ₁ (thiamine) vitamin B ₂ (riboflavin)

Vitamin B ₃ . Under this name, the compounds nicotinic acid and nicotinamide (niacinamide) are often performed. Preferred according to the invention is the nicotinic acid amide which is contained in the agents used according to the invention preferably in amounts of from 0.05 to 1% by weight, based on the total agent.

Vitamin B ₅ (pantothenic acid, panthenol and pantolactone). Panthenol and / or pantolactone are preferably used in the context of this group. Derivatives of panthenol which can be used according to the invention are, in particular, the esters and ethers of panthenol and also cationically derivatized panthenols. Individual representatives are, for example, the panthenol triacetate, the panthenol monoethyl ether and its monoacetate and also the cationic panthenol derivatives disclosed in WO 92/13829. The said compounds of the vitamin B ₅ type are preferably contained in the agents according to the invention in amounts of 0.05-10% by weight, based on the total agent. Amounts of 0.1-5 wt .-% are particularly preferred. Vitamin B ₆ (pyridoxine and pyridoxamine and pyridoxal).

Vitamin C (ascorbic acid). Vitamin C is used in the agents according to the invention preferably in amounts of 0.1 to 3 wt .-%, based on the total agent. Use in the form of palmitic acid ester, glucosides or phosphates may be preferred. The use in combination with tocopherols may also be preferred.

Vitamin E (tocopherols, especially α-tocopherol). Tocopherol and its derivatives, which include in particular the esters such as the acetate, the nicotinate, the phosphate and the succinate, are preferably present in the agents according to the invention in amounts of 0.05-1% by weight, based on the total agent.

Vitamin F. The term "vitamin F" is usually understood as meaning essential fatty acids, in particular linoleic acid, linolenic acid and arachidonic acid.

Vitamin H. Vitamin H is the compound (3aS, 4S, 6aR) -2-oxohexahydrothienol [3,4-c /] -imidazole-4-valeric acid, for which, however, the trivial name biotin has meanwhile prevailed. Biotin is preferred in the inventive compositions in amounts of

In summary, agents according to the invention containing vitamins, pro-vitamins and vitamin precursors, which are assigned to groups A, B, C, E, F and H, are preferred, preferred compositions containing said compounds in amounts of from 0.1 to 5% by weight. %, preferably from 0.25 to 4 wt .-% and in particular from 0.5 to 2.5 wt .-%, each based on the total agent.

In a further preferred embodiment, the agents according to the invention may additionally contain emulsifiers. Emulsifiers effect at the phase interface the formation of water- or oil-stable adsorption layers, which protect the dispersed droplets against coalescence and thus stabilize the emulsion. Emulsifiers are therefore constructed like surfactants from a hydrophobic and a hydrophilic part of the molecule. Hydrophilic emulsifiers preferably form O / W emulsions and hydrophobic emulsifiers preferably form W / O emulsions. An emulsion is to be understood as meaning a droplet-like distribution (dispersion) of a liquid in another liquid under the expense of energy in order to create stabilizing phase interfaces by means of surfactants. The selection of these emulsifying surfactants or emulsifiers depends on the substances to be dispersed and the respective outer phase and the fineness of the emulsion. Emulsifiers which can be used according to the invention are, for example Addition products of 4 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide to linear fatty alcohols having 8 to 22 carbon atoms, to fatty acids having 12 to 22 carbon atoms and to alkylphenols having 8 to 15 carbon atoms in the alkyl group,

C ₂ -C ₂₂ -fatty acid mono- and diesters of addition products of from 1 to 30 mol of ethylene oxide onto polyols having from 3 to 6 carbon atoms, in particular to glycerol, ethylene oxide and polyglycerol addition products of methylglucoside fatty acid esters, fatty acid alkanolamides and fatty acid glucamides,

C ₈ -C ₂₂ -alkylmono- and -oligoglycosides and their ethoxylated analogues, where C ¹ degrees of gyration of from 1.1 to 5, in particular 1.2 to 2.0, and glucose as sugar component are preferred,

Glucosides mixtures of alkyl (oligo) and fatty alcohols, for example, the commercially available product ^® Montanov 68,

Addition products of 5 to 60 moles of ethylene oxide with castor oil and hydrogenated castor oil, partial esters of polyols having 3-6 carbon atoms with saturated fatty acids having 8 to 22 carbon atoms,

Sterols. Sterols are understood to mean a group of steroids which have a hydroxyl group on C-atom 3 of the steroid skeleton and are isolated both from animal tissue (zoosterols) and from vegetable fats (phytosterols). Examples of zoosterols are cholesterol and lanosterol. Examples of suitable phytosterols are ergosterol, stigmasterol and sitosterol. Mushrooms and yeasts are also used to isolate sterols, the so-called mycosterols.

Phospholipids. Of these, especially the glucose phospholipids, e.g. as lecithins or phosphatidylcholines from e.g. Egg yolk or plant seeds (e.g., soybeans) are understood.

Fatty acid esters of sugars and sugar alcohols, such as sorbitol,

Polyglycerols and polyglycerol derivatives such as polyglycerol poly-12-hy- droxystearat (Dehymuls ^® PGPH commercial product)

Linear and branched fatty acids with 8 to 30 C atoms and their Na, K, ammonium, Ca, Mg and Zn salts.

The agents according to the invention preferably contain the additional emulsifiers in amounts of from 0.1 to 25% by weight, in particular from 0.5 to 15% by weight, based on the total agent.

The compositions according to the invention may preferably contain at least one nonionogenic emulsifier having an HLB value of 8 to 18. Nonionic emulsifiers with an HLB value of 10 to 15 may be particularly preferred according to the invention. As further advantageous, it has been shown that polymers are included in the inventive compositions. In a preferred embodiment, therefore, polymers are added to the compositions used according to the invention, both cationic, anionic, amphoteric and nonionic polymers having proven effective.

Cationic or amphoteric polymers are preferably usable according to the invention. Cationic or amphoteric polymers are to be understood as meaning polymers which have a group in the main and / or side chain which may be "temporary" or "permanent" cationic. According to the invention, "permanently cationic" refers to those polymers which have a cationic group, irrespective of the pH of the agent. These are usually polymers containing a quaternary nitrogen atom, for example in the form of an ammonium group. Preferred cationic groups are quaternary ammonium groups. In particular, those polymers in which the quaternary ammonium group is bonded via a C 1-4 hydrocarbon group to a polymer main chain constructed from acrylic acid, methacrylic acid or derivatives thereof have proven to be particularly suitable.

Homopolymers of the general formula (G1-I),

R ¹

I - [CH ₂ -CI _n X ^" (G 1-1)

CO-O- (CH ₂ ) _m -N ⁺ R ² R ³ R ⁴

in which R ¹ = -H or -CH ₃ , R ² , R ³ and R ^{4 are} independently selected from C 1-4 -alkyl, -alkenyl or -hydroxyalkyl groups, m = 1, 2, 3 or 4, n is a natural number and X ^"is a physiologically acceptable organic or inorganic anion, and copolymers consisting essentially of the monomer units listed in formula (G1-I) and nonionic monomer units are particularly preferred cationic polymers preferably, for which at least one of the following conditions applies:

R ¹ is a methyl group

R ² , R ³ and R ⁴ are methyl groups m has the value 2. Suitable physiologically tolerated counterions X ^" are, for example, halide ions, sulfate ions, phosphate ions, methosulfate ions and organic ions such as lactate, citrate, tartrate and acetate ions, preference being given to halide ions, in particular chloride.

A particularly suitable homopolymer is the, if desired crosslinked, poly (methacryloyloxyethyltrimethylammonium chloride) with the INCI name

Polyquaternium-37. Such products are available, for example under the names Rheocare ^® CTH (Cosmetic Rheologies) and Synthalen® ^® CR (Ethnichem) in trade. If desired, the crosslinking can be carried out with the aid of poly olefinically unsaturated compounds, for example divinylbenzene, tetraallyloxyethane, methylenebisacrylamide, diallyl ether, polyallylpolyglyceryl ethers, or allyl ethers of sugars or sugar derivatives such as erythritol, pentaerythritol, arabitol, mannitol, sorbitol, sucrose or glucose. Methylenebisacrylamide is a preferred crosslinking agent.

The homopolymer is preferably used in the form of a nonaqueous polymer dispersion which should not have a polymer content of less than 30% by weight. Such polymer dispersions are (under the names Salcare ^® SC 95 about 50% polymer content, additional components: mineral oil (INCI name: Mineral Oil) and tridecyl-polyoxypropylene-polyoxyethylene-ether (INCI name: PPG-1 trideceth-6) ) and Salcare ^® SC 96 (about 50% polymer content, additional components: mixture of diesters of propylene glycol with a mixture of caprylic and capric acid (INCI name: propylene glycol Dicaprylate / Dicaprate) and tridecyl polyoxypropylene-polyoxyethylene-ether (INCI Designation: PPG-1-trideceth-6)) are commercially available.

Copolymers with monomer units of the formula (G1-I) as the non-ionic monomer, preferably acrylamide, methacrylamide, acrylic acid and methacrylic acid alkyl esters Ci- _{4-C-ι- 4} -alkyl. Among these nonionic monomers, the acrylamide is particularly preferred. These copolymers can also be crosslinked, as described above in the case of the homopolymers. A copolymer preferred according to the invention is the crosslinked acrylamide-methacryloyloxyethyltrimethylammonium chloride copolymer. Such copolymers in which the monomers are present in a weight ratio of about 20:80, are commercially available as approximately 50% non-aqueous polymer dispersion 92 under the name Salcare ^® SC.

Further preferred cationic polymers are, for example quaternized CeIIu lose-derivatives, such as are available under the names Celquat ^® and Polymer JR ^® commercially. The compounds Celquat ^® H 100, Celquat ^® L 200 and Polymer JR ^® 400 are preferred quaternized cellulose derivatives, cationic alkyl polyglycosides according to DE-PS 44 13 686, cationized honey, for example the commercial product Honeyquat ^® 50, cationic guar derivatives, such as in particular the products sold under the trade name Cosmedia guar ^® and Jaguar ^® products, polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid. Under the names Merquat ^® 100 (Poly (dimethyldiallylammonium chloride)) and Merquat ^® 550 (dimethyldiallylammonium chloride-acrylamide copolymer) are examples of such cationic polymers,

Copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoalkyl acrylate and methacrylate, such as diethyl sulfate quaternized vinylpyrrolidone-dimethylaminoethyl methacrylate copolymers. Such compounds are sold under the names Gafquat ^® 734 and Gafquat ^® 755 commercially,

Vinylpyrrolidone-vinyl imidazolium copolymers, such as those offered under the names Luviquat ^® FC 370, FC 550, FC 905 and HM 552, quaternized polyvinyl alcohol, as well as by the names of Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27, having quaternary Nitrogen atoms in the polymer backbone.

Can be used as cationic polymers are sold under the names Polyquaternium-24 (commercial product z. B. Quatrisoft ^® LM 200), known polymers. , Gaffix ^® VC 713 (manufactured by ISP): Also according to the invention can be used the copolymers of vinylpyrrolidone, such as the commercial products Copolymer 845 (ISP manufacturer) are Gafquat ^® ASCP 1011, Gafquat ^® HS 110, Luviquat ^® 8155 and Luviquat ^® MS 370 available are.

Other cationic polymers which can be used in the agents according to the invention are the so-called "temporary cationic" polymers. These polymers usually contain an amino group which, at certain pH values, is present as quaternary ammonium group and thus cationic. For example, chitosan and its derivatives are preferred as Hydagen CMF ^®, Hydagen HCMF ^®, Kytamer ^® PC and Chitolam ^® NB / 101 are freely available commercially, for example under the trade names. According to the invention preferred cationic polymers are cationic cellulose derivatives and chitosan and its derivatives, in particular the commercial products Polymer ^® JR 400, Hydagen ^® HCMF and Kytamer ^® PC, cationic guar derivatives, cationic honey derivatives, in particular the commercial product Honeyquat ^® 50, cationic Alkylpolyglycodside according to DE-PS 44 13 686 and polymers of the type Polyquaternium-37.

Furthermore, cationized protein hydrolysates are to be counted among the cationic polymers, wherein the underlying protein hydrolyzate from the animal, for example from collagen, milk or keratin, from the plant, for example from wheat, corn, rice, potatoes, soy or almonds, marine life forms, for example from fish collagen or algae, or biotechnologically derived protein hydrolysates. The protein hydrolyzates on which the cationic derivatives according to the invention are based can be obtained from the corresponding proteins by chemical, in particular alkaline or acid hydrolysis, by enzymatic hydrolysis and / or a combination of both types of hydrolysis. The hydrolysis of proteins usually results in a protein hydrolyzate having a molecular weight distribution of about 100 daltons up to several thousand daltons. Preference is given to those cationic protein hydrolyzates whose underlying protein content has a molecular weight of 100 to 25,000 daltons, preferably 250 to 5000 daltons. Furthermore, cationic protein hydrolyzates are to be understood as meaning quaternized amino acids and mixtures thereof. The quaternization of the protein hydrolyzates or amino acids is often carried out using quaternary ammonium salts such as N, N-dimethyl-N- (n-alkyl) -N- (2-hydroxy-3-chloro-n-propyl) ammonium halides. Furthermore, the cationic protein hydrolysates may also be further derivatized. As typical examples of the cationic protein hydrolysates and derivatives according to the invention, those mentioned under the INCI names in the "International Cosmetic Ingredient Dictionary and Handbook", (seventh edition 1997, The Cosmetic, Toiletry, and Fragrance Association 1101 17 ^th Street, NW, Suite 300 Cocodimium Hydroxypropyl Hydrolyzed Collagen, Cocodimopnium Hydroxypropyl Hydrolyzed Casein, Cocodimonium Hydroxypropyl Hydrolyzed Collagen, Cocodimonium Hydroxypropyl Hydrolyzed Hair Keratin, Cocodimonium Hydroxypropyl Hydrolyzed Keratin, Cocodimonium Hydroxypropyl Hydrolyzed Rice Protein, Cocodimonium Hydroxypropyl Hydrolyzed Soy Protein, Cocodimonium Hydroxypropyl Hydrolyzed Wheat Protein, Hydroxypropyl Arginine Lauryl / Myristyl Ether HCl, Hydroxypropyltrimonium Gelatin, Hydroxypropyltrimonium Hydrolyzed Casein, Hydroxypropyltrimonium Hydrolyzed Collagen, Hydroxypropyltrimonium Hydrolyzed Conchio Protein, Hydroxypropyltrimonium Hydrolyzed Keratin, Hydroxypropyltrimonium Hydrolyzed Rice Bran Protein, Hydroxypropyltrimonium Hydrolyzed Soy Protein, Hydroxypropyl Hydrolyzed Vegetable Protein, Hydroxypropyltrimonium Hydrolyzed Wheat Protein, Hydroxypropyltrimonium Hydrolyzed Wheat Protein / Siloxysilicate, Lauridimonium Hydroxypropyl Hydrolyzed Wheat Protein, Lauridimonium Hydroxypropyl Hydrolyzed Wheat Protein, Laurydimium Hydroxypropyl Hydrolyzed Wheat Protein / Siloxysilicate, Lauryldimonium Hydroxypropyl Hydrolyzed Casein, Lauryldimonium Hydroxypropyl Hydrolyzed Collagen, Lauryldimonium Hydroxypropyl Hydrolyzed Keratin, Lauryldimonium Hydroxypropyl Hydrolyzed Soy Protein, Steardimonium Hydroxypropyl Hydrolyzed Casein, Steardimonium Hydroxypropyl Hydrolyzed Collagen, Steardimonium Hydroxypropyl Hydrolyzed Keratin, Steardimonium Hydroxypropyl Hydrolyzed Rice Protein, Steardimonium Hydroxypropyl Hydrolyzed Soy Protein, Steardimonium Hydroxypropyl Hydrolyzed Vegetable Protein, Steardimonium Hydroxypropyl Hydrolyzed Wheat Protein, Steartrimonium Hydroxyethyl Hydrolyzed Collagen, Quaternium-76 Hydrolyzed Collagen, Quaternium-79 Hydrolyzed Collagen, Quaternium-79 Hydrolyzed Keratin, Quaternium-79 Hydrolyzed Milk Protein, Quaternium-79 Hydrolyzed Soy Prote in, Quaternium-79 Hydrolyzed Wheat Protein.

Very particular preference is given to the cationic protein hydrolysates and derivatives based on plants.

In addition to cationic polymers or in their place, the agents according to the invention can also contain amphoteric polymers. These additionally have at least one negatively charged group in the molecule and are also referred to as zwitterionic polymers. In the context of the present invention, preferably usable zwitterionic polymers are composed essentially together

A) monomers with quaternary ammonium groups of the general formula (Z-I),

R ¹ -CH = CR ² -CO-Z- (C _n H _2n ) -N ( ⁺ ) R ³ R ⁴ R ⁵ A ^ ( ^{Z ~} ')

In the R ¹ and R ² independently of one another represent hydrogen or a methyl group and R °, R and R independently represent alkyl groups having 1 to 4 carbon atoms, Z is an NH group or an oxygen atom, n is an integer from 2 to 5 and A "is the anion of an organic or inorganic acid

and B) monomeric carboxylic acids of the general formula (Z-II),

R ⁶ -CH = CR ⁷ -COOH (ZI

R 7 in which R and R independently of one another are hydrogen or methyl groups.

Suitable starting monomers are, for. Dimethylaminoethylacrylamide, dimethylaminoethylmethacrylamide, dimethylaminopropylacrylamide, dimethylamino-propylmethacrylamide and diethylaminoethylacrylamide when Z is an NH group or dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate and diethylaminoethyl acrylate when Z is an oxygen atom.

The monomers containing a tertiary amino group are then quaternized in a known manner, with methyl chloride, dimethyl sulfate or diethyl sulfate being particularly suitable as alkylating reagents. The quaternization reaction can be carried out in aqueous solution or in the solvent.

Advantageously, those monomers of the formula (Z-I) are used, which are derivatives of acrylamide or methacrylamide. Preference is furthermore given to those monomers which contain halide, methoxysulfate or ethoxysulfate ions as counterions. Also preferred are those monomers of formula (Z-I) wherein R, R and R are methyl groups.

The acrylamidopropyltrimethylammonium chloride is a most preferred monomer of formula (Z-I).

Suitable monomeric carboxylic acids of the formula (Z-II) are acrylic acid, methacrylic acid, crotonic acid and 2-methylcrotonic acid. Preference is given to using acrylic or methacrylic acid, in particular acrylic acid.

The zwitterionic polymers which can be used according to the invention are prepared from monomers of the formulas (ZI) and (Z-II) by polymerization processes known per se. The Polymerization can be carried out either in aqueous or aqueous-alcoholic solution. The alcohols used are alcohols having 1 to 4 carbon atoms, preferably isopropanol, which simultaneously serve as polymerization regulators. However, other components than regulators may also be added to the monomer solution, eg. For example, formic acid or mercaptans, such as thioethanol and thioglycolic acid. The initiation of the polymerization takes place with the aid of free-radical-forming substances. For this purpose, redox systems and / or thermally decomposing radical formers of the azo compound type, such. As azoisobutyronitrile, azo-bis (cyanopentanoic acid) or azo-bis (amidinopropane) dihydrochloride can be used. As redox systems are z. B. combinations of hydrogen peroxide, potassium or ammonium oxodisulfate and tertiary butyl hydroperoxide with sodium sulfite, sodium dithionite or hydroxylamine hydrochloride as a reduction component.

The polymerization can be carried out isothermally or under adiabatic conditions, depending on the concentration ratios by the heat of polymerization released, the temperature range for the course of the reaction between 20 and 200 ⁰ C may vary, and the reaction may optionally be carried out under autogenous pressure. Preferably, the reaction temperature is between 20 and 100 ⁰ C.

The pH during the copolymerization may vary within a wide range. Advantageously, polymerization is carried out at low pH values; however, pH values above the neutral point are also possible. After the polymerization is treated with an aqueous base, for. As sodium hydroxide, potassium hydroxide or ammonia, to a pH between 5 and 10, preferably 6 to 8 set. Further details of the polymerization process can be found in the examples.

As particularly effective, such polymers have been found in which the monomers of the formula (ZI) were present in excess over the monomers of the formula (Z-II). It is therefore preferred according to the invention to use those polymers which consist of monomers of the formula (ZI) and the monomers of the formula (Z-II) in a molar ratio of 60:40 to 95: 5, in particular from 75:25 to 95: 5 , consist. The cationic or amphoteric polymers are preferably contained in the agents according to the invention in amounts of from 0.05 to 10% by weight, based on the total agent. Amounts of 0.1 to 5 wt .-% are particularly preferred.

The anionic polymers (G2) are anionic polymers which have carboxylate and / or sulfonate groups. Examples of anionic monomers from which such polymers may consist are acrylic acid, methacrylic acid, crotonic acid, maleic anhydride and 2-acrylamido-2-methylpropanesulfonic acid. The acidic groups may be wholly or partly present as sodium, potassium, ammonium, mono- or triethanolammonium salt. Preferred monomers are 2-acrylamido-2-methylpropanesulfonic acid and acrylic acid.

Anionic polymers which contain 2-acrylamido-2-methylpropanesulfonic acid as the sole or co-monomer can be found to be particularly effective, it being possible for the sulfonic acid group to be wholly or partly present as sodium, potassium, ammonium, mono- or triethanolammonium salt ,

More preferably, the homopolymer of 2-acrylamido-2-methyl propane sulfonic acid, which is available for example under the name Rheothik ^® 11-80 is commercially.

Within this embodiment, it may be preferable to use copolymers of at least one anionic monomer and at least one nonionic monomer. With regard to the anionic monomers, reference is made to the substances listed above. Preferred nonionic monomers are acrylamide, methacrylamide, acrylic esters, methacrylic esters, vinylpyrrolidone, vinyl ethers and vinyl esters.

Preferred anionic copolymers are acrylic acid-acrylamide copolymers and in particular polyacrylamide copolymers with sulfonic acid-containing monomers. A particularly preferred anionic copolymer consists of 70 to 55 mol% of acrylamide and 30 to 45 mol% of 2-acrylamido-2-methylpropanesulfonic acid, wherein the sulfonic acid group is wholly or partly in the form of sodium, potassium, ammonium, mono- or triethanolammonium Salt is present. This copolymer may also be crosslinked, with crosslinking agents preferably polyolefinically unsaturated compounds such as tetraallyloxyethane, allylsucrose, allylpentaerythritol and methylene-bisacrylamide are used. Such a polymer is contained in the commercial product Sepigel ^® 305 from SEPPIC. The use of this compound, which in addition to the polymer component contains a hydrocarbon mixture (Ci ₃ -Ci ₄ -lsoparaffin) and a nonionic emulsifier (laureth-7), has proved to be particularly advantageous in the context of the teaching of the invention. Also sold under the name Simulgel 600 as a compound with isohexadecane and polysorbate 80 Natriumacryloyldimethyltaurat copolymers have proven to be particularly effective according to the invention.

Likewise preferred anionic homopolymers are uncrosslinked and crosslinked polyacrylic acids. Allyl ethers of pentaerythritol, sucrose and propylene may be preferred crosslinking agents. Such compounds are for example available under the trademark Carbopol ^® commercially.

Copolymers of maleic anhydride and methyl vinyl ether, especially those with crosslinks, are also color-retaining polymers. A 1, 9-decadiene crosslinked maleic acid-methyl vinyl ether copolymer is available under the name ^® Stabileze QM.

Furthermore, amphoteric polymers (G3) can be used as polymers for increasing the activity of the active ingredient complex (A) according to the invention. The term amphoteric polymers includes both those polymers which contain in the molecule both free amino groups and free -COOH or SO ₃ H groups and are capable of forming internal salts, as well as zwitterionic polymers which in the molecule have quaternary ammonium groups and -COO - or - contain SO ₃ ^~ groups and those polymers comprising -COOH or SO ₃ H groups and quaternary ammonium groups.

An example of the present invention amphopolymer suitable is the acrylic resin commercially available as Amphomer ^®, which is a copolymer of tert-butylaminoethyl methacrylate, N- (1, 1, 3,3-tetramethylbutyl) -acrylamide and two or more monomers from the group of acrylic acid, Represents methacrylic acid and its simple esters.

Preferably used amphoteric polymers are those polymers which are composed essentially

(a) monomers having quaternary ammonium groups of the general formula (G3-I),

R ¹ -CH = CR ² -CO-Z- (C _n H _2n ) -N ⁽⁺⁾ R ³ R ⁴ R ⁵ A ⁽⁾ (G ³ -I)

in which R ¹ and R ² independently of one another are hydrogen or a methyl group and R ³ , R ⁴ and R ⁵ independently of one another are alkyl groups having 1 to 4 carbon atoms, Z is an NH group or an oxygen atom, n is an integer from 2 to 5 and A is the anion of an organic or inorganic acid, and (b) monomeric carboxylic acids of the general formula (G3-II),

R ⁶ -CH = CR ⁷ -COOH (G3-II)

in which R ⁶ and R ^{7 are} independently hydrogen or methyl groups.

These compounds can be used both directly and in salt form, which is obtained by neutralization of the polymers, for example with an alkali metal hydroxide, according to the invention. Very particular preference is given to those polymers in which monomers of the type (a) are used in which R ³ , R ⁴ and R ^{5 are} methyl groups, Z is an NH group and A ^{() is} a halide, methoxysulfate or ethoxysulfate ion is; Acrylamidopropyltrimethylammonium chloride is a particularly preferred monomer (a). Acrylic acid is preferably used as monomer (b) for the stated polymers.

In another embodiment, the agents according to the invention may contain nonionic polymers (G4).

Suitable nonionic polymers are, for example:

Vinylpyrrolidone / vinyl ester copolymers, as sold, for example, under the trademark Luviskol ^® (BASF). Luviskol ^® VA 64 and Luviskol ^® VA 73, each vinylpyrrolidone / vinyl acetate copolymers, are also preferred nonionic polymers. Cellulose ethers such as hydroxypropyl cellulose, hydroxyethyl cellulose and hydroxypropylcellulose Methylhy-, as sold for example under the trademark Culminal® ^® and Benecel ^® (AQUALON) and Natrosol ^® grades (Hercules). Starch and its derivatives, in particular starch, such as Structure XL ^® (National Starch), a multifunctional, salt-tolerant starch; shellac

Polyvinylpyrrolidones, as sold for example under the name Luviskol ^® (BASF).

Siloxanes. These siloxanes can be both water-soluble and water-insoluble. Both volatile and nonvolatile siloxanes are suitable, nonvolatile siloxanes being understood as meaning those compounds whose boiling point is above 200 ^° C. under normal pressure. Preferred siloxanes are polydialkylsiloxanes, such as, for example, polydimethylsiloxane, polyalkylarylsiloxanes, such as, for example, polyphenylmethylsiloxane, ethoxylated polydialkylsiloxanes and polydialkylsiloxanes which contain amine and / or hydroxyl groups. Glycosidically substituted silicones.

It is also possible according to the invention that the preparations used contain a plurality of, in particular two different polymers of the same charge and / or in each case an ionic and an amphoteric and / or nonionic polymer.

The polymers are contained in the agents according to the invention preferably in amounts of 0.05 to 10 wt .-%, based on the total agent. Amounts of 0.1 to 5, in particular from 0.1 to 3 wt .-%, are particularly preferred.

In addition to the substances mentioned, the compositions according to the invention may contain further care substances. Another group of care agents which may be included in the compositions of the invention are the protein hydrolysates and their derivatives. Protein hydrolysates are product mixtures obtained by acid, alkaline or enzymatically catalyzed degradation of proteins (proteins). According to the invention, the term protein hydrolyzates also means total hydrolyzates as well as individual amino acids and their derivatives as well as mixtures of different amino acids. Furthermore, according to the invention, polymers made up of amino acids and amino acid derivatives are understood by the term protein hydrolyzates. The latter include, for example, polyalanine, polyasparagine, polyserine, etc. Further examples of compounds which can be used according to the invention are L-alanyl-L-proline, polyglycine, glycyl-L-glutamine or D / L-methionine-S-methylsulfonium chloride. Of course, according to the invention, β-amino acids and their derivatives such as β-alanine, anthranilic acid or hippuric acid can also be used. The molecular weight of the protein hydrolysates which can be used according to the invention is between 75, the molecular weight for glycine, and 200,000, preferably the molecular weight is 75 to 50,000 and very particularly preferably 75 to 20,000 daltons.

According to the invention, protein hydrolysates of both vegetable and animal or marine or synthetic origin can be used.

Animal protein hydrolysates are, for example, elastin, collagen, keratin and milk protein protein hydrolysates, which may also be present in the form of salts. Such products are, for example, under the trademarks Dehylan ^® (Cognis), Promois® ^® (Interorgana) Collapuron ^® (Cognis), Nutrilan® ^® (Cognis), Gelita-Sol ^® (German Gelatinefabriken Stoess & Co), Lexein ^® (Inolex) and kerasol tm ^® (Croda) sold.

Preferred according to the invention is the use of protein hydrolysates of plant origin, z. Soybean, almond, pea, potato and wheat protein hydrolysates. Such products are, for example, under the trademarks Gluadin ^® (Cognis), diamine ^® (Diamalt) ^® (Inolex), Hydrosoy ^® (Croda), hydro Lupine ^® (Croda), hydro Sesame ^® (Croda), Hydro tritium ^® (Croda) and Crotein ^® (Croda) available.

Although the use of the protein hydrolysates is preferred as such, amino acid mixtures otherwise obtained may be used in their place, if appropriate. Also possible is the use of derivatives of protein hydrolysates, for example in the form of their fatty acid condensation products. Such products are sold, for example, under the names Lamepon® ^® (Cognis), Lexein ^® (Inolex), Crolastin ^® (Croda) or crotein ^® (Croda).

Of course, the teaching of the invention includes all isomeric forms, such as eis - trans - isomers, diastereomers and chiral isomers.

According to the invention it is also possible to use a mixture of several protein hydrolysates.

The protein hydrolysates are preferably present in the compositions in concentrations of from 0.01% by weight to 20% by weight, preferably from 0.05% by weight to 15% by weight and most preferably in amounts of 0.05% by weight. up to 5% by weight.

Furthermore, in a preferred embodiment of the invention, an agent according to the invention may also contain UV filters. The UV filters to be used according to the invention are not subject to any general restrictions with regard to their structure and their physical properties. On the contrary, all UV filters which can be used in the cosmetics sector and whose absorption maximum is in the UVA (315-400 nm), in the UVB (280-315 nm) or in the UVC (<280 nm) range are suitable. UV filters with an absorption maximum in the UVB range, in particular in the range from about 280 to about 300 nm, are particularly preferred.

The UV filters used according to the invention can be selected, for example, from substituted benzophenones, p-aminobenzoic acid esters, diphenylacrylic esters, cinnamic acid esters, salicylic acid esters, benzimidazoles and o-aminobenzoic acid esters.

Examples of UV filters which can be used according to the invention are 4-aminobenzoic acid, N, N, N-trimethyl-4- (2-oxoborn-3-ylidenemethyl) aniline methylsulfate, 3,3,5-trimethylcyclohexyl salicylate (homosalates), 2-hydroxy-4-methoxy-benzophenone (benzophenone-3; Uvinul ^® M 40, Uvasorb MET ^{®, ®} Neo Heliopan BB, Eusolex ^® 4360), 2-phenylbenzimidazole-5-sulfonic acid and its potassium, sodium and triethanolamine (Phenylbenzimidazole Sulfonic Acid; Parsol ^® HS; Neo Heliopan Hydro ^®), 3,3 '- (1, 4-phenylenedimethylene) bis (7,7-dimethyl-2-oxo-bicyclo- [2.2.1] hept-1-yl-methanesulfonic acid) and its salts, 1- (4-tert-butylphenyl) -3- (4-methoxyphenyl) -propane-1,3-dione (butylmethoxydibenzoylmethane; Parsol ^® 1789 Eusolex ^® 9020), α- (2-oxoborn-3-ylidene) toluene-4-sulfonic acid and salts thereof, ethoxylated 4-aminobenzoic acid ethyl ester (PEG-25 PABA; Uvinul ^® P 25), 4-dimethylaminobenzoic acid -2-ethylhexyl (octyl dimethyl PABA; Uvasorb ^® DMO, Escalol ^® 507, Eusolex ^® 6007), salicylic acid 2-ethylhexyl (octyl salicylate; Escalol ^® 587, Neo Heliopan OS ^®, Uvinul ^® 018), 4-methoxy-isopen - tylester (isoamyl p-Methoxycinnamate; Neo Heliopan e 1000 ^®), 4-methoxycinnamic acid 2-ethylhexyl ester (octyl Methoxycinnamate; Parsol ^® MCX, Escalol ^® 557, Neo Heliopan AV ^®), 2-hydroxy-4-methoxybenzophenone 5-sulfonic acid and its sodium alz (Benzophenone-4; Uvinul ^® MS 40; Uvasorb S 5 ^®), 3- (4'-methylbenzylidene) -D, L-camphor (4-methylbenzylidene camphor; Parsol ^® 5000, Eusolex ^® 6300), 3-benzylidene camphor (3-Benzylidene camphor), 4-lsopro pylbenzyl salicylate, 2,4,6-trianilino (p-carbo-2'-ethylhexyl-1'-oxy) -1,3,5-triazine, 3-imidazol-4-yl-acrylic acid and its ethyl ester, polymers of the N - {(2 and 4) - [2-oxoborn-3-ylidenemethyl] benzyl} - acrylamide, 2,4-dihydroxy (benzophenone-1; Uvasorb ^® 20 H, Uvinul ^® 400) 1, 1 '- Diphenylacrylonitrilsäure- 2-ethylhexyl ester (Octocrylene; Eusolex ^® OCR, Neo Heliopan ^® Type 303, Uvinul ^® N 539 SG), o-aminobenzoic acid menthyl ester (menthyl Anthranilate; Neo Heliopan MA ^®), 2,2 ', 4,4'- tetrahydroxy benzophenone (benzophenone-2; Uvinul ^® D-50), 2,2'-dihydroxy-4,4'-dimethoxybenzophenone (Benzophenone-6), 2,2'-dihydroxy-4,4'-dimethoxybenzophenone-5 sodium sulfonate and 2-cyano-3,3-diphenylacrylic acid 2'-ethylhexyl ester. Preference is given to 4-aminobenzoic acid, N, N, N-trimethyl-4- (2-oxoborn-3-ylidenemethyl) aniline methylsulfate, 3,3,5-trimethylcyclohexylsalicylate, 2-hydroxy-4-methoxybenzophenone , 2-phenylbenzimidazole-5-sulfonic acid and its potassium, sodium and triethanolamine salts, 3,3 '- (1, 4-phenylenedimethylene) -bis (7,7-dimethyl-2-oxo-bicyclo- [2.2.1] hept-1-yl-methanesulphonic acid) and its salts, 1- (4-tert-butylphenyl) -3- (4-methoxyphenyl) -propane-1,3-dione, α- (2-oxoborn-3-) yliden) -toluene-4-sulfonic acid and its salts, ethoxylated 4-aminobenzoic acid ethyl ester, 2-ethylhexyl A-dimethylaminobenzoate, 2-ethylhexyl salicylate, A-

Methoxycinnamic acid isopentyl ester, 4-methoxycinnamic acid 2-ethylhexyl ester, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its sodium salt, 3- (4'-methylbenzylidene) -D, L-camphor, 3-benzylidene-camphor, 4-Isopropylbenzyl salicylate, 2,4,6-trianilino (p-carbo-2'-ethylhexyl-1'-oxy) -1, 3,5-triazine, 3-imidazol-4-yl-acrylic acid and its ethyl ester, polymers of the N- {(2 and 4) - [2-oxoborn-3-ylidenemethyl] benzyl} -acrylamide. Very particularly preferred according to the invention are 2-hydroxy-4-methoxybenzophenone, 2-phenylbenzimidazole-5-sulfonic acid and its potassium, sodium and triethanolamine salts, 1- (4-tert-butylphenyl) -3- (4-methoxyphenyl) Propan-1, 3-dione, 4-methoxycinnamic acid 2-ethylhexyl ester and 3- (4'-methylbenzylidene) -D, L-camphor. Preference is given to those UV filters whose molar extinction coefficient at the absorption maximum is above 15,000, in particular above 20,000.

Furthermore, it has been found that structurally similar UV filters in many cases, the water-insoluble compound in the teaching of the invention has the higher effect compared to such water-soluble compounds that differ from it by one or more additional ionic groups. For the purposes of the invention, water-insoluble UV filters are those which dissolve in water at not more than 1% by weight, in particular not more than 0.1% by weight, at 20 ^° C. Furthermore, these compounds should be soluble in the usual cosmetic oil components at room temperature to at least 0.1, in particular at least 1 wt .-%). The use of water-insoluble UV filters may therefore be preferred according to the invention.

According to a further embodiment of the invention, preference is given to those UV filters which have a cationic group, in particular a quaternary ammonium group.

These UV filters have the general structure U - Q.

The power section U stands for a UV-absorbing group. This group can in principle be derived from the known UV filters which can be used in the cosmetics sector, in which a group, generally a hydrogen atom, of the UV filter is replaced by a cationic group Q, in particular having a quaternary amino function , Compounds from which the structural part U can be derived are, for example, substituted benzophenones, p-aminobenzoic acid esters,

diphenylacrylic,

cinnamic,

salicylic acid,

Benzimidazoles and o-aminobenzoic acid ester.

Structural parts U which are derived from cinnamic acid amide or from N, N-dimethylaminobenzoic acid amide are preferred according to the invention.

The structural parts U can in principle be chosen so that the absorption maximum of the UV Filter can be in both the UVA (315-400 nm) -, as well as in the UVB (280-315nm) - or in the UVC (<280 nm) - range. UV filters with an absorption maximum in the UVB range, in particular in the range from about 280 to about 300 nm, are particularly preferred.

Furthermore, the structural part U, also as a function of structural part Q, is preferably selected so that the molar extinction coefficient of the UV filter at the absorption maximum is above 15,000, in particular above 20,000.

The structural part Q preferably contains, as a cationic group, a quaternary ammonium group. This quaternary ammonium group may in principle be connected directly to the structural part U, so that the structural part U represents one of the four substituents of the positively charged nitrogen atom it. Preferably, however, one of the four substituents on the positively charged nitrogen atom is a group, especially an alkylene group of 2 to 6 carbon atoms, which functions as a compound between the structural portion U and the positively charged nitrogen atom.

Advantageously, the group Q has the general structure - (CH ₂ ) χ-N ⁺ R ¹ R ² R ³ X ^' , in which x is an integer from 1 to 4, R ¹ and R ² independently of one another represent |. ₄ alkyl groups, R ³ is a C |. ₂₂ alkyl group or a benzyl group and X ^"is a physiologically acceptable anion. Within this general structure, x is preferably the number 3, R ¹ and R ² are each a methyl group and R ³ is either a methyl group or a saturated or unsaturated , linear or branched hydrocarbon chain having 8 to 22, in particular 10 to 18, carbon atoms.

Physiologically acceptable anions are, for example, inorganic anions such as halides, in particular chloride, bromide and fluoride, sulfate ions and phosphate ions and organic anions such as lactate, citrate, acetate, tartrate, methosulfate and tosylate.

Two preferred UV filters with cationic groups are the commercially available compounds cinnamic acid-trimethylammonium chloride (lncroquat ^® UV-283) and dodecyl tosylate (Escalol ^® HP 610).

Of course, the teaching of the invention also includes the use of a combination of several UV filters. In the context of this embodiment, the combination of at least one water-insoluble UV filter with at least one UV filter with a cationic group is preferred.

The UV filters are in the inventively used in amounts usually from 0.1 to 5 wt .-%, based on the total agent included. Amounts of 0.4 to 2.5 wt .-% are preferred.

The compositions of the invention may further contain a 2-pyrrolidinone-5-carboxylic acid and derivatives thereof. Preference is given to the sodium, potassium, calcium, magnesium or ammonium salts in which the ammonium ion carries, in addition to hydrogen, one to three C 1 to C ₄ alkyl groups. The sodium salt is most preferred. The amounts used in the compositions according to the invention are preferably from 0.05 to 10% by weight, based on the total composition, particularly preferably from 0.1 to 5, and in particular from 0.1 to 3,% by weight.

Finally, the compositions of the invention may also contain plant extracts.

Usually these extracts are produced by extraction of the whole plant. However, in individual cases it may also be preferred to prepare the extracts exclusively from flowers and / or leaves of the plant.

With regard to the plant extracts which can be used according to the invention, particular reference is made to the extracts listed in the table beginning on page 44 of the 3rd edition of the guideline for the ingredient declaration of cosmetic products, published by the Industrial Association for Personal Care and Detergent e.V. (IKW), Frankfurt.

The extracts of green tea, oak bark, stinging nettle, witch hazel, hops, henna, chamomile, burdock root, horsetail, hawthorn, linden, almond, aloe vera, spruce needle, horse chestnut, sandalwood, juniper, coconut, mango, apricot, lime , Wheat, kiwi, melon, orange, grapefruit, sage, rosemary, birch, mallow, meadowfoam, quenelle, yarrow, thyme, lemon balm, toadstool, coltsfoot, marshmallow, meristem, ginseng and ginger root.

Particularly preferred are the extracts of green tea, oak bark, stinging nettle, witch hazel, hops, chamomile, burdock root, horsetail, lime blossom, almond, aloe vera, coconut, mango, apricot, lime, wheat, kiwi, melon, orange, grapefruit, sage, Rosemary, birch, meadowfoam, quenelle, yarrow, toadstool, meristem, ginseng and ginger root.

Especially suitable for the use according to the invention are the extracts of green tea, almond, aloe vera, coconut, mango, apricot, lime, wheat, kiwi and melon.

As extraction agent for the preparation of said plant extracts may be water, alcohols and mixtures thereof are used. Among the alcohols are lower alcohols such as ethanol and isopropanol, but especially polyhydric alcohols such as ethylene glycol and propylene glycol, both as sole extractant and in admixture with water, are preferred. Plant extracts based on water / propylene glycol in a ratio of 1:10 to 10: 1 have proven to be particularly suitable.

The plant extracts can be used according to the invention both in pure and in diluted form. If they are used in diluted form, they usually contain about 2 to 80 wt .-% of active substance and as a solvent used in their extraction agent or extractant mixture.

Furthermore, it may be preferred to use in the compositions according to the invention mixtures of several, especially two, different plant extracts.

In addition, it may prove to be advantageous if the compositions according to the invention contain penetration aids and / or swelling agents. These include, for example, urea and urea derivatives, guanidine and its derivatives, arginine and its derivatives, water glass, imidazole and its derivatives, histidine and its derivatives, benzyl alcohol, glycerol, glycol and glycol ethers, propylene glycol and propylene glycol ethers, for example propylene glycol monoethyl ether, carbonates, bicarbonates, Diols and triols, and in particular 1, 2-diols and 1, 3-diols such as 1, 2-propanediol, 1, 2-pentanediol, 1, 2-hexanediol, 1, 2-dodecanediol, 1, 3-propanediol, 1 , 6-hexanediol, 1, 5-pentanediol, 1, 4-butanediol.

Furthermore, it may be preferred according to the invention to use hydroxycarboxylic acids and here again in particular the dihydroxy, trihydroxy and polyhydroxycarboxylic acids as well as the dihydroxy, trihydroxy and polyhydroxy di-, tri- and polycarboxylic acids in the compositions according to the invention. It has been found that in addition to the hydroxycarboxylic acids, the hydroxycarboxylic acid esters and the mixtures of hydroxycarboxylic acids and their esters as well as polymeric hydroxycarboxylic acids and their esters can be very particularly preferred. Preferred hydroxycarboxylic acid esters are, for example, full esters of glycolic acid, lactic acid, malic acid, tartaric acid or citric acid. Further basically suitable hydroxycarboxylic acid esters are esters of β-hydroxypropionic acid, tartronic acid, D-gluconic acid, sugar acid, mucic acid or glucuronic acid. Suitable alcohol components of these esters are primary, linear or branched aliphatic alcohols having 8 to 22 carbon atoms, ie, for example, fatty alcohols or synthetic fatty alcohols. The esters of C12 to C15 fatty alcohols are particularly preferred. Esters of this type are commercially available, eg under the trademark Cosmacol® ^® EniChem, Augusta Industriale. Particularly preferred polyhydroxypolycarboxylic acids are polylactic acid and polyuric acid and their esters.

Compositions of the invention may be in solid, semi-solid, liquid, disperse, emulsified, suspended or gel form. Furthermore, the agents according to the invention can be formulated as an aerosol, that is, they are packaged in a pressure vessel, from which they can be sprayed with the aid of a propellant. Furthermore, the agents according to the invention can be sprayed as a propellant-free pump spray.

In a particularly preferred embodiment, the agents according to the invention are in the form of a hydrogel. Hydrogels are water-containing gels based on hydrophilic but water-insoluble polymers, which exist as three-dimensional networks. In water, these networks swell up to an equilibrium volume, with largely retaining their shape. The network formation occurs predominantly via chemical linking of the individual polymer chains, but is also physically possible by electrostatic, hydrophobic or dipole / dipole interactions between individual segments of the polymer chains. The choice of the monomers used for the polymer synthesis, the type of crosslinking and the crosslinking density can be used to tailor desired properties of the hydrogels. The necessary hydrophilicity of the polymers is mediated, inter alia, by hydroxyl, carboxylate, sulfonate and / or amide groups. Synthetic hydrogels are based inter alia on poly (meth) acrylic acids, poly (meth) acrylates, polyvinylpyrrolidone or polyvinyl alcohol. Preferred anionic polymeric hydrogel formers which can promote the action of the active ingredient used according to the invention contain carboxylate and / or sulfonate groups and as monomers, for example, acrylic acid, methacrylic acid, crotonic acid, maleic anhydride and 2-acrylamido-2-methylpropanesulfonic acid. The acidic groups may be wholly or partly present as sodium, potassium, ammonium, mono- or triethanolammonium salt. Preferred monomers are 2-acrylamido-2-methylpropanesulfonic acid and acrylic acid. Very particularly preferred anionic polymers contain 2-acrylamido-2-methylpropanesulfonic acid as the sole monomer or as comonomer, it being possible for the sulfonic acid group to be wholly or partly in salt form. Within this embodiment, it is preferred to use copolymers of at least one anionic monomer and at least one nonionic monomer. With regard to the anionic monomers, reference is made to the substances listed above. Preferred nonionic monomers are acrylamide, methacrylamide, acrylic esters, methacrylic acid esters, vinylpyrrolidone, vinyl ethers and vinyl esters. Preferred anionic copolymers are acrylic acid-acrylamide copolymers and in particular polyacrylamide copolymers with monomers containing sulfonic acid groups. A particularly preferred anionic copolymer consists of 70 to 55 mol% of acrylamide and 30 to 45 mol% of 2-acrylonitrile amido-2-methylpropanesulfonic acid, wherein the sulfonic acid groups are completely or partially present as sodium, potassium, ammonium, mono- or triethanolammonium salt. This copolymer may also be crosslinked, with crosslinking agents preferably polyolefinically unsaturated compounds such as tetraallyloxyethane, allylsucrose, allylpentaerythritol and methylene-bisacrylamide are used. Such a polymer is contained in the commercial product Sepigel ^® 305 from SEPPIC. The use of this compound has proven to be particularly advantageous in the context of the teaching of the invention. Also, the NS under the designations Simulgel ^® 600, Simulgel ^®, Simulgel ^® EG, Simulgel ^® EPG and Sepiplus ^® 400 as a compound with an oil such as isohexadecane, squalane or hydrogenated polyisobutene, and an emulsifier, such as polysorbate, Laureth-7 or Caprylyl / Capryl glucosides, sold sodium acryloyldimethyltaurate copolymers (with monomers selected from acrylamide, sodium acrylate, hydroxyethyl acrylate and / or acrylic acid) have proved to be particularly effective according to the invention. Further preferred are hydrogel Ammoniumacryloyl- dimethyltaurat-vinyl pyrrolidone copolymers, especially the commercial product Aristoflex ^® AVC from Clariant.

Further particularly preferred anionic homopolymer hydrogel formers are uncrosslinked and crosslinked polyacrylic acids. Allyl ethers of pentaerythritol, sucrose and propylene may be preferred crosslinking agents. Such compounds are for example the commercial products Carbopol ^®. A particularly preferred anionic copolymer contains 80 to 98% of an unsaturated C ₃ monomer. _6- carboxylic acid or its anhydride and to 2 - 20% of acrylic acid esters of saturated C ₁₀ - ₃ o-carboxylic acids, wherein the copolymer can be crosslinked with the aforementioned crosslinking agents. Corresponding commercial products are Pemulen ^®, and Carbopol ^® grades 954, 980, 1342 and ETD 2020 (ex Noveon or BF Goodrich).

Preferred nonionic polymeric hydrogel formers are, for example, polyvinyl alcohols which may be partially saponified, e.g. B. the commercial products Mowiol ^® and vinylpyrrolidone / vinyl ester copolymers and polyvinylpyrrolidones, the z. B. under the trademark Luviskol ^® (BASF) are sold.

Natural hydrogel-forming agents which are preferred according to the invention are in particular selected from, if desired, physically (thermally) and / or chemically modified cellulose derivatives, preferably hydroxyalkylcelluloses such as hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, methylcellulose, hydroxymethylcellulose, carboxymethylcellulose, in particular starches and starch degradation products such as amylose and amylopectin, chemically and / or or thermally modified starches, e.g. B. hydroxypropyl starch phosphate, Dihydroxypropyldistärkephosphat, in particular the anionic starch derivatives aluminum starch octenyl succinate (for example the commercial products Dry Flo ^®), Natriumstärkeoctenylsuccinat, Calciumstärkeoctenylsuccinat further chitosan and its derivatives, further polysaccharides gum or gums form, such as guar gum, xanthan gum, alginates, in particular Sodium alginate, gum arabic, karaya gum, carrageenans, locust bean gum, linseed gums, shellac and agar agar.

In a further particularly preferred embodiment, the agents according to the invention are in the form of an oil-in-water emulsion. Such oil-in-water emulsions may, also preferably, be stabilized by at least one of the abovementioned hydrogel formers.

In a further particularly preferred embodiment, the agents according to the invention are in liquid form. The application can be carried out preferably with spray devices. These spraying devices contain in a container a filling of the inventive (liquid, mushy or powdery) skin treatment agent. The filling may be under the pressure of a propellant (compressed gas cans, compressed gas packages, aerosol dispensers), or it may be a mechanically operated pump sprayer. The containers have a removal device, preferably in the form of valves, which allow the removal of the contents as fog, smoke, foam, powder, paste or liquid jet. As a container for the sprayers are mainly cylindrical vessels made of metal (aluminum, tinplate, volume preferably <1000 ml), protected or non-splintering glass or plastic (volume preferably <220 ml) or splintering glass or plastic (volume preferably <150 ml ) in question.

Creamy, gelatinous, pastose and liquid agents may e.g. be packaged in pump or squeeze dispensers, especially in multi-chamber pump or squeeze dispensers.

For the purposes of the invention, the term liquid also includes any solid dispersions in liquids. Compositions according to the invention may also be present as pastes, ointments, lotions or creams. Solid funds can be present as a loose powder, pressed powder or as a pen.

The application may, for example, in the case of liquid agents preferably also be carried out with a roller applicator, as it is known for example from the field of deodorant scooters. Such scooters have a ball mounted in a ball bed which moves by movement over a surface can be. The ball absorbs some of the agent to be distributed and conveys this to the surface to be treated. With such applicators can be specifically and sparingly treated only the actually affected by acne and / or impurities skin areas.

The application may e.g. also be carried out with substrates which are acted upon by a preparation according to the invention. Especially preferred are wet wipes, i. prefabricated for the user, preferably individually packaged, wet wipes, such as. B. from the field of glass cleaning (eyeglass cleaning cloths) or from the field of wet toilet paper are well known. Such wet wipes, which may advantageously also contain preservatives, are then advantageously impregnated or applied with an agent according to the invention, advantageously they are individually packaged. You can z. B. as a cleaning cloth or facial tissue (make-up removal) are used, which is particularly interesting for use on the go.

Preferred substrate materials are preferably selected from porous sheet-like cloths. They can be made of a fibrous or cellular flexible material which has sufficient mechanical stability and softness for application to the skin. These wipes include cloths of woven and non-woven synthetic and natural fibers, felt, paper or foam, such as hydrophilic polyurethane foam.

Preferably, conventional cloths of nonwoven material (nonwovens) are used here. Nonwovens are generally defined as adhesively bonded fibrous products having a mat or layered fibrous structure, or those comprising fibrous mats in which the fibers are randomly or randomly distributed. The fibers may be natural such as wool, silk, jute, hemp, cotton, flax, sisal or ramie; or synthetically, such as rayon, cellulose esters, polyvinyl derivatives, polyolefins, polyamides or polyesters. In general, any fiber diameter or titer is suitable for the present invention. The nonwoven fabrics employed herein tend not to rupture or disintegrate due to the random or random arrangement of fibers in the nonwoven material which impart excellent strength in all directions. Examples of nonwoven fabrics suitable as substrates in the present invention are known, for example, from WO 98/18441. Preferred porous and flat cleaning cloths consist of one or different fiber materials, in particular of cotton, refined cotton, polyamide, polyester or mixtures of these. The substrates in fabric form preferably have an area of from 10 to 5000 cm ² , preferably from 50 to 2000 cm ² , in particular from 100 to 1500 cm ² and particularly preferably from 200 to 1000 cm ² . The grammage of the material is usually between 20 and 1000 g / m ² , preferably from 30 to 500 g / m ² and in particular from 50 to 150 g / m ² . Skin treatment substrates which are preferred according to the invention can be obtained by impregnation or impregnation or else by melting the agents according to the invention onto a substrate.

The agents according to the invention, preferably liquid agents, may also be multiphase, the phases may e.g. horizontally, so one above the other, or vertically, so next to each other, be arranged. It may also be a disperse system in which e.g. the solid constituents are distributed inhomogeneously in the liquid matrix, so that such a dispersed system should be shaken before use.

A further subject of the present invention is a method for the cosmetic tanning of human skin without the action of UV radiation, in which an inventive agent of the first subject of the invention is applied to the skin. In this case, it is preferred according to the invention if the agent according to the invention of the first subject of the invention immediately prior to application to the skin from a first composition comprising in a cosmetic carrier at least one compound of the above formula (I) and a second composition comprising in a cosmetic carrier at least one compound of the above formula (II) and / or the above formula (III) is mixed. This mixing process can also be done by sequential application of said first and second compositions without any intermediate rinsing step on the skin. After application, the agent according to the invention of the first subject of the invention can preferably be rinsed off the skin after a contact time (of preferably 5 to 45 minutes). Furthermore, it is preferable to increase the effect of the composition according to the invention after application to the skin in the sense of a leave-on application on the skin.

With regard to preferred methods according to the invention, what is said in the context of the first subject of the invention to preferred agents according to the invention applies mutatis mutandis.

Further objects of the present invention are the use of agents according to the invention for protecting the skin from UV radiation, the use of agents according to the invention for protecting the skin from and / or for treating polymorphic light dermatosis and the use of agents according to the invention of the first subject of the invention for skin tanning.

Also with regard to preferred uses according to the invention, mutatis mutandis, the statements made in the context of the first subject of the invention to preferred means according to the invention. Examples

The following example formulations of Tables 1 to 6 are suitable as skin tanning agents according to the invention. Unless otherwise indicated, the amounts given are all% by weight, based on the weight of the particular agent. The following raw materials were used to provide the compositions:

Abir EM 90 INCI name: Cetyl PEG / PPG-10/1 Dimeticone (Evonik Degussa Goldschmidt) Aristoflex ^® AVC INCI name: Ammonium Acryloyldimethyltaurate / VP copolymer, t-Butyl Alcohol (Clariant)

Baysilone ^® M 350 INCI name: Dimethiocone (GE Bayer Silicones) Cetiol ^® B INCI name: Dibutyladipate (Cognis) Cetiol ^® 868 ethylhexyl stearate (INCI name: Ethyl hexyl Stearate) (Cognis) Controx KS ^® at least 56% of tocopherol; INCI name: Tocopherol, Hydrogenated Palm Glycerides Citrate (Cognis)

Culminal ^® MPHC 100 INCI name: Hydroxypropyl Methylcellulose (Hercules) Cutina ^® MD Glycerol mono / distearate (INCI name: Glyceryl Stearate) (Cognis)

Dow Corning ^® 200 fluid polydimethylsiloxane (INCI designation: Dimethicone) (Dow Corning) Dow Corning ^® 245 fluid decamethylcyclopentasiloxane; INCI name: Cyclomethicone (Dow Corning) Dow Corning ^® 9040 INCI name: Cyclomethicone Dimethicone Crosspolymer (Dow Corning) Dry Flo Plus ^® INCI name: Aluminum Starch Octenylsuccinate (National Starch) DSH-C N dimethylsilanol; aqueous solution, preserved (1kg DSH-C contains 3.0g dimethylsilanediol, 15g mucopolysaccharides, 1.5g sodium hyaluronate, preservative: 0.128% methylparaben sodium salt, 0.032% propylparaben, 0.200% imidazolidinylurea; INCI name: dimethylsilanol hyaluronate) (exsymol)

Fucogef 1000 INCI name: Biosaccharide Gum-1 (Solabia) Glucamate SSE 20 ^® INCI name: PEG 20 methyl glucose Sesquistearate (Noveon)

Keltrol ^® SF INCI name: Xanthan Gum (Kelco) Lanette ^® 22 INCI. Title: behenyl Alcohol (Cognis) Lipoid ^® S 75-3 INCI name: Aqua, lecithins (Lipoid GmbH) Montanov® ^® 202 INCI name: arachidyl alcohol, behenyl alcohol, arachidyl glucosides (Seppic) Myritol ^® 318 INCI name: Caprylic / Capric Triglyceride (Cognis) Novata ^® AB INCI name: Cocoglycerides (Cognis) Phenonip ^® hydroxybenzoate-hydroxybenzoic säureethylester--hydroxybenzoate-phenoxyethanol Hydroxybenzoesäurebutylester- mixture (ca. 28% active substance; INCI name : Phenoxyethanol, methylparaben, ethylparaben, propylparaben, butylparaben) (Nipa)

Simulgel ^® NS INCI name: Hydroxyethyl Acrylate / Sodium Acryloyldimethyl Taurate Copolymer / Squalane / Polysorbate 60 (Seppic)

Sisterna SP ^® 30 C INCI name: Sucrose Distearate (Sisterna BV) Sisterna SP ^® 70 C INCI name: Sucrose Stearate (Sisterna BV) Stenol 1618 ^® C _{16-i 8} fatty alcohol (INCI name: Cetearyl Alcohol) (Cognis ) Symdiol ^® 68 INCI name: 1, 2-octanediol, 1, 2-hexanediol (Symrise) Sympatens ^® BS / 080 INCI name: PEG-8 Stearate (Dr. W. Kolb) Tego Carbomer ^® 140 carboxyvinyl polymer (INCI Name: Carbomer) (Goldschmidt) Wacker Belsil ^® 100 INCI name: Dimethicone (Wacker)

Table 1 :

Table 2:

Table 3:

Table 4:

Table 5:

Table 6:

Claims

Patent claims

1. A composition for tanning the human skin, comprising in a cosmetic carrier a combination of component (A) of at least one CH-acidic compound according to formula (I)

wherein

• R ¹ and R ² are independently a linear or cyclic Ci-C ₆ - alkyl group, a C ₂ -C ₆ alkenyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group, an aryl-dC ₆ - alkyl group, a C -C ₆ hydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a -C ₆ alkoxy-C ₆ alkyl group, a group R'R "N- (CH ₂₎ p-, wherein R ¹ and R" independently represent a hydrogen atom, a C ₁ -C ₄ - alkyl group, a C- | -C ₄ -hydroxyalkyl group or an aryl Ci-C ₆ alkyl group, wherein R ¹ and R ¹¹ together with the nitrogen atom form a 5-, 6 or p-membered ring and p is a number 2, 3, 4, 5 or 6,

• R ³ and R ⁵ are independently a hydrogen atom or a d-C ₆ -alkyl group, where at least one of the radicals R ³ or R ⁵ is a -C ₆ - alkyl group,

• R ⁴ represents a hydrogen atom, a Ci-C ₆ alkyl group, a -C ₆ - hydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a -C ₆ - alkoxy group, a -C ₆ -hydroxyalkoxy group, a group R "'R ^lv N- (CH _{2) q} - in which R ^m and R ^IV are independently a hydrogen atom, a CrC ₆ alkyl group, a C _r C ₆ hydroxyalkyl group, or an aryl-dC ₆ - alkyl group, and q is a number 1 , 2, 3, 4, 5 or 6, wherein the radical R ⁴ together with one of the radicals R ³ or R ^{5 can form} a 5- or 6-membered aromatic ring which is optionally substituted by a halogen atom, a C 1 -C ₆ -alkyl group, a -C ₆ hydroxyalkyl group, a C ₂ -C ₆ - polyhydroxyalkyl group, a dC ₆ alkoxy group, a CrC ₆ - hydroxyalkoxy group, a nitro group, a hydroxy group, a group R ^V R ^VI N- (CH _{2) S} -, wherein R ^v and R ^vι independently of one another represent a hydrogen atom, a C 1 -C ₆ -alkyl group, a C 1 -C ₆ -hydroxyalkyl group or an aryl-Ci-C ₆ alkyl group and s is a number O, 1, 2, 3, 4, 5 or 6 may be substituted,

Y ¹ represents an oxygen atom, a sulfur atom or a group NR ^V ", in which R ^v " represents a hydrogen atom, an aryl group, a heteroaryl group, a C ₁ -C ₆ -alkyl group or a C ₁ -C ₆ -arylalkyl group,

• X ^' is a physiologically acceptable anion, with component

(B) at least one compound of the formula (II) and / or at least one compound of the formula (III)

wherein

R ¹ is a (Ci-C ₆₎ alkyl, (C ₂ -C ₆₎ alkenyl group, aryl group, aryl- (C- | _-C6) alkyl or heteroaryl (C- | _-C6) alkyl stands,

R ² and R ^{3 are} each independently a hydrogen atom, a halogen atom, a (C ₁ -C ₆ ) alkyl group, a (C ₁ -C ₆ ) alkoxy group, hydroxy (C ₁ -C ₆ ) alkoxy group, hydroxy group, nitro group, aryl group, trifluoromethyl group , amino group, by (C ₁ -C ₆₎ - denote alkyl groups may be substituted, or (Ci-C ₆₎ acyl group,

R ^{4 is} a hydrogen atom, a nitro group, a hydroxy group or a (C ₁ to C ₃ ) -alkoxy group, R ^{5 is} a hydrogen atom, a hydroxy group or a (C ₁ to C ₃ ) -alkoxy group,

R ^{6 is} a hydrogen atom or a (C ₁ to C ₃ ) -alkyl group, R ^{7 is} a hydrogen atom, a nitro group or a hydroxy group,

R ^{8 represents} a hydrogen atom or a nitro group and A ^{~ represents} a physiologically acceptable anion.

2. Composition according to claim 1, characterized in that Y ¹ according to formula (I) represents an oxygen or a sulfur atom, in particular an oxygen atom.

3. Composition according to one of claims 1 or 2, characterized in that at least one of the radicals R ³ or R ^{5 of} the formula (I) is a methyl group.

4. Composition according to one of claims 1 to 3, characterized in that the compounds of formula (I) are selected from one or more compounds of the group of salts with physiologically acceptable counterion X ^' , which is formed from salts of

1, 2-dihydro-1, 3,4,6-tetramethyl-2-oxo-pyrimidinium,

1, 2-dihydro-1,3-diethyl-4,6-dimethyl-2-oxo-pyrimidinium,

1, 2-dihydro-1,3-dipropyl-4,6-dimethyl-2-oxo-pyrimidinium,

1, 2-dihydro-1,3-di (2-hydroxyethyl) -4,6-dimethyl-2-oxo-pyrimidinium,

1, 2-dihydro-1,3-diphenyl-4,6-dimethyl-2-oxo-pyrimidinium,

1, 2-dihydro-1, 3,4-trimethyl-2-oxo-pyrimidinium,

1, 2-dihydro-1,3-diethyl-4-methyl-2-oxo-pyrimidinium,

1, 2-dihydro-1,3-dipropyl-4-methyl-2-oxo-pyrimidinium,

1, 2-dihydro-1,3-di (2-hydroxyethyl) -4-methyl-2-oxo-pyrimidinium,

1, 2-dihydro-1,3-diphenyl-4-methyl-2-oxo-pyrimidinium,

1-allyl-1,2-dihydro-3,4,6-trimethyl-2-oxopyrimidinium,

1,2-dihydro-1- (2-hydroxyethyl) -3,4,6-trimethyl-2-oxo-pyrimidinium,

1, 2-dihydro-1, 3,4,6-tetramethyl-2-thioxo-pyrimidinium,

1, 2-dihydro-1,3-diethyl-4,6-dimethyl-2-thioxo-pyrimidinium,

1, 2-dihydro-1,3-dipropyl-4,6-dimethyl-2-thioxopyrimidiniums,

1, 2-dihydro-1,3-di (2-hydroxyethyl) -4,6-dimethyl-2-thioxo-pyrimidinium,

1, 2-dihydro-1,3-diphenyl-4,6-dimethyl-2-thioxo-pyrimidinium,

1, 2-dihydro-1, 3,4-trimethyl-2-thioxo-pyrimidinium,

1, 2-dihydro-1,3-diethyl-4-methyl-2-thioxo-pyrimidinium,

1, 2-dihydro-1,3-dipropyl-4-methyl-2-thioxo-pyrimidinium,

1, 2-dihydro-1,3-di (2-hydroxyethyl) -4-methyl-2-thioxo-pyrimidinium,

1, 2-dihydro-1, 3-diphenyl-4-methyl-2-thioxo-pyrimidinium,

1, 2-dihydro-3,4-dimethyl-2-oxo-quinazolinium and

1, 2-dihydro-3,4-dimethyl-2-thioxo-quinazolinium.

5. Composition according to one of claims 1 to 4, characterized in that the compounds of formula (I) in an amount of 0.01 wt .-% to 5 wt .-%, in particular 0.05 wt .-% to 1 % By weight, based in each case on the weight of the ready-to-use agent.

6. Composition according to one of claims 1 to 5, characterized in that according to formula II, the formyl group -CHO is bonded in 2- or 4-position.

7. Composition according to one of claims 1 to 6, characterized in that the compounds of formula II are selected from at least one compound of the group consisting of the benzenesulfonates, p-toluenesulfonates, methanesulfonates, trifluoromethanesulfonates, perchlorates, sulfates, chlorides, bromides, iodides and / or tetrachlorozincates of 4-formyl-1-methylquinolinium and 2-formyl-1-methylquinolinium

8. Composition according to one of claims 1 to 7, characterized in that the compounds of formula (III) is selected from at least one compound, from

4-hydroxy-3-methoxy-6-nitrobenzaldehyde

3,4-dihydroxy-5-nitrobenzaldehyde

2-hydroxy-3-methoxy-5-nitro-benzaldehyde

4-hydroxy-3-methoxy-5-nitrobenzaldehyde (5-nitrovanillin)

3-hydroxy-4-methoxybenzaldehyde

3,4-dimethoxy-5-hydroxybenzaldehyde

9. Composition according to one of claims 1 to 8, characterized in that at least one of the following combinations of (A) and (B) is contained:

(a) 1,2-dihydro-1, 3,4,6-tetramethyl-2-oxopyrimidinium hydrogen sulfate and 4-formyl-1-methyl-quinolinium p-toluenesulfonate,

(b) 1, 2-dihydro-1, 3,4,6-tetramethyl-2-oxopyrimidinium hydrogensulfate and 2-formyl-1-methyl-quinolinium p-toluenesulfonate,

(c) 1-allyl-1,2-dihydro-3,4,6-trimethyl-2-oxopyrimidinium bromide and 4-formyl-1-methyl-quinolinium p-toluenesulfonate,

(d) 1-allyl-1,2-dihydro-3,4,6-trimethyl-2-oxopyrimidinium bromide and 2-formyl-1-methyl-quinolinium p-toluenesulfonate,

(e) 1, 2-Dihydro-1, 3,4,6-tetramethyl-2-oxo-pyrimidinium hydrogensulfate, 4-formyl-1-methyl-quinolinium p-toluenesulfonate and 2-formyl-1-methylquinolinium p-toluenesulfonate .

(f) 1-Allyl-i, 2-dihydro-3,4,6-trimethyl-2-oxopyrimidinium bromide, 4-formyl-1-methylquinolinium p-toluenesulfonate and 2-formyl-1-methylquinolinium p-toluenesulfonate.

10. Composition according to one of claims 1 to 9, characterized in that the compounds of formula (II) and / or formula (III) in an amount of 0.01 wt .-% to 5 wt .-%, in particular of 0 , 05 wt .-% to 1 wt .-%, each based on the weight of the ready-to-use agent, are included.

11. Composition according to one of claims 1 to 10, characterized in that it has a pH of pH 4 to pH 7.

12. A process for the cosmetic tanning of human skin without the action of UV radiation, in which an agent according to any one of claims 1 to 11 is applied to the skin.

13. Use of an agent according to any one of claims 1 to 11 for the protection of the skin from UV radiation.

14. Use of an agent according to one of claims 1 to 11 for the protection of the skin from and / or for the treatment of polymorphic photodermatosis

15. Use of an agent according to any one of claims 1 to 11 for tanning the skin.