WO2010060513A2

WO2010060513A2 - Method for the photo stabilisation of ascorbic acid derivatives

Info

Publication number: WO2010060513A2
Application number: PCT/EP2009/007685
Authority: WO
Inventors: Thomas Rudolph
Original assignee: Merck Patent Gmbh
Priority date: 2008-11-26
Filing date: 2009-10-28
Publication date: 2010-06-03
Also published as: WO2010060513A3

Abstract

The invention relates to the use of a compound selected from the group containing diphenyl acrylate UV filters, phenolic antioxidants or mixtures of the same, for improving the UV stability of a preparation containing at least one ascorbic acid derivative as a UV filter.

Description

Process for photostabilization of ascorbic acid derivatives

The invention relates to the use of a compound selected from the group consisting of diphenylacrylate UV filters, dibenzoylmethane UV filters, phenolic antioxidants or mixtures thereof, for improving UV radiation.

Stability of a preparation containing at least one ascorbic acid derivative as a UV filter.

WO 2008/017346 describes a use of ascorbic acid derivatives for the functionalization of matrices. In particular, the suitability of ascorbic acid derivatives as skin-binding UV filters is described when the ascorbic acid derivatives of the given formula I contain UV chromophores, as listed in detail. The purpose of these compounds is to bind the substances to the skin as a result of oxidation of the ascorbic acid portion and hence to absorb UV light as constantly as possible via the UV chromophore. In order to achieve pronounced absorption constancy, it is desirable for the UV chromophore used in the ascorbic acid derivative to be as light-stable as possible. In addition, it is advantageous if the skin binding is accelerated by photooxidation of the ascorbic acid portion.

It is known from the literature that UV filters can not only be structurally photoinstable, but their photostability can be considerably influenced by the composition of the surrounding medium. The most prominent example is the UV filter t-butylmethoxydibenzoylmethane, which is generally considered to be photoinstable, but can be almost completely stailised in polar protic media.

The object of the invention is therefore to provide a process which is suitable when photostability of the UV chromophore contained in ascorbic acid derivatives occurs during UV irradiation To achieve the highest possible integral UV absorption of Ascorbinsäurederivates.

Surprisingly, it has now been found that the absorption stability of the preparation containing an ascorbic acid derivative, as described below, is improved by the following substance classes:

Diphenyl cyanoacrylate UV filter, for example 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate, also known as octocrylene, and derivatives thereof derived partly from polymeric compounds, for example as Polycrylene® [INCI polyester].

8th; CAS 862993-96-2]) or Solasil® PSF [INCI: Undecylcrylene dimethicone];

- Dibenzoylmethane UV filter, for example - (4-tert-butylphenyl) -3- (4-methoxyphenyl) propane-1, 3-dione, also known under the name Avobenzone;

Phenolic antioxidants, for example bis-ethylhexylhydroxydimethoxybenzyl malonate, also known under the trade name RonaCare® AP or bis-ethylhexylhydroxydimethoxybenzylidenemalonate (Oxynex® ST) and mixtures of the three classes of substances.

A first aspect of the invention is therefore the use of a compound selected from the group of diphenylacrylate UV filters, dibenzoylmethane UV filters, phenolic antioxidants or mixtures thereof, for improving the UV stability of a preparation comprising at least one ascorbic acid derivative of the formula I,

in which R ¹ or R ^{2 are} each independently hydroxy, -O-alkyl, -OC (O) -

Alkyl, -OPO ₃ M or O-glycosyl,

Alkyl C 1 -C 6 -alkyl,

M alkali or alkaline earth metal cation or H,

R ³ or R ^{4 are} each independently hydroxy or a radical B and

B is a substituent of the formula II, III, IV, V, VI, VII ₁ VIII, IX, X, Xl and / or XII means

-A-

R ⁷

30

in which

R ⁵ to R ^{16 are} each independently H, -OH ₁ -OA ₁ -A ₁ -NH ₂ , -NHA ₁ -

NA ₂ , -NH- (CH ₂ -CH ₂ -O) _n -H, -N [(CH ₂ -CH ₂ -O) _n -H] _{2 l} - [NHA ₂ ] X ₁ - [NA ₃ ] X, -SO ₃ H ₁

- [SO ₃ ] X or 2H-benzotriazol-2-yl mean and

A is alkyl having 1 to 20 C atoms, n is an integer from 1 to 25,

X is the counterion to the cations [NHA ₂ ] ⁺ and [NA ₃ ] ⁺ or the anion [SO ₃ ] ^" and

Y and Z are each independently -ascorbyl, hydroxy, -O-2-ethylhexyl, -O-hexyl, -OA or -NH-C (CH ₃ ) ₃ , with the proviso that at least one of R ³ or R ³ ⁴ for one

Rest B stands.

For the purposes of the present invention, the term preparation or formulation is used synonymously.

The preparations are usually either topically applicable preparations, for example cosmetic, pharmaceutical or dermatological formulations. The preparations in this case contain a cosmetically, pharmaceutically or dermatologically suitable carrier and, if desired Property profile optional further suitable ingredients. The topical preparations are preferably used as a cosmetic or dermatological preparation, particularly preferably as a cosmetic preparation.

The compounds of formula I according to the invention are typically present in amounts of from 0.01 to 20% by weight, preferably in amounts of from 0.05% by weight to 10% by weight, more preferably in amounts of 0.5% by weight. % to 3.0 wt .-% used .. It does not give the expert any difficulty to select the amounts depending on the intended effect of the preparation accordingly.

Compounds called diphenyl acrylate UV filters are, for example, compounds of the formula A,

in which,

X = C ₁ -C ₃₀ -alkyl, branched or unbranched or

Aryl.

R =

or

Yi and Y2 in formula A are each independently H, a branched or unbranched alkyl group having 1 to 4 C atoms or a branched or unbranched alkoxy group having 1 to 8 C atoms, Y ₃ in formula A is H or CN.

Particularly preferred compounds from the group of diphenylacrylate UV filters of the formula A are compounds in which Y _{3 is} CN. Most particularly preferred for this group is octocrylene or, in other words, the compound 2-ethylhexyl-2-cyano-3,3-diphenylacrylate, and its derivatives in polymeric form such as, for example, Polycrylene® [INCI Polyester-8; CAS 862993-96-2]); Solasil® PSF [INCI: Undecylcrylene dimethicone] from Hallstar. Such polymeric structures are described, for example, in US Pat. No. 6,890,521 or 6,899,866.

An organically modified silicone polymer is, for example, Solasil® PSF [INCI: Undecylcrylene Dimethicone] or Polysilicone 15.

Dibenzoylmethane derivatives are in themselves already well-known products which are described in particular in the above-mentioned publications FR-A-2 326 405, FR-A-2 440 933 and EP-A-0 114 607. Preferred dibenzoylmethane derivatives correspond to the formula B

wherein R ^1, R ^2, R ³ and R ^4, which are identical or different, represent hydrogen, a linear or branched Cis-alkyl group or a straight or branched Ci _-8 alkoxy group, in particular

2-methyldibenzoylmethane, 4-methyldibenzoylmethane,

4-isopropyldigenoylmethane,

4-tert-butyldibenzoylmethane,

2,4-dimethyldibenzoylmethane,

4,4'-diisopropyldibenzoylmethane, 4 ₎ 4'-methoxy-tert-butyldibenzoylmethane, 2,5-dimethyldibenzoylmethane,

2-methyl-5-isopropyl-4'-methoxydibenzoylmethane,

2-methyl-5-tert-butyl-4'-methoxydibenzoylmethane,

2,4-dimethyl-4'-methoxydibenzoylmethane and

2,6-dimethyl-4-tert-butyl-4'-methoxydibenzoylmethane, but this list is not limitative.

Of the abovementioned dibenzoylmethane derivatives, in particular the 4,4'-methoxy-tert-butyldibenzoylmethane and in particular particular the left under the trade name Eusolex ^® 9020 from Merck commercially 4,4'-methoxy-t-butyldibenzoylmethane, wherein this filter corresponds to the following structural formula:

Another preferred dibenzoylmethane derivative is 4-isopropyldibenzoylmethane.

Since dibenzoylmethane derivatives can be photoinstable, they can in turn be stabilized by the ascorbic acid derivatives according to the invention.

Compounds called phenolic antioxidants are, for example, compounds of the formula C,

wherein

A-B denotes a single bond or a double bond,

R ^{1 can be selected} from the group -C (O) CH ₃ , -CO ₂ R ³ , -C (O) NH ₂ and -C (O) N (R ⁴ ) ₂ ,

X is O or NH,

R ^{2 is} linear or branched alkyl having 1 to 30 C atoms,

R ^{3 is} linear or branched alkyl having 1 to 20 C atoms,

R ^{4 are} each independently of one another H or linear or branched alkyl having 1 to 8 C atoms, R ^{5 is} linear or branched alkyl having 1 to 8 C atoms or linear or branched alkoxy having 1 to 8 C atoms and R ^{6 is} linear or branched alkyl having 1 to 8 C atoms, preferably 2- (4-hydroxy-3 , 5-dimethoxybenzy) malonic acid-bis (2-ethylhexyl) ester (known as RonaCare ^® AP) or bis (2-ethylhexyl) -2- (4-hydroxy-3,5-dimethoxybenzyl) malonate (known as Oxynex® ST).

C 1 -C ₆ -alkyl denotes an alkyl group having 1, 2, 3, 4, 5 or 6 C atoms, for example methyl, ethyl, isopropyl, n-propyl, isobutyl, n-butyl, tert-butyl, n Pentyl or n-hexyl. An alkyl group having 1 to 20 C atoms is analogous to the empirical formula C _n H _2n + i with n = 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20 and includes both the unbranched and the isomeric branched forms. An alkyl group having 1 to 30 C atoms is analogous to the empirical formula C _n H _2n + i with n = 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30 and includes both the unbranched and the isomeric branched forms.

Aryl in formula A is phenyl which is unsubstituted or substituted by alkyl groups having 1 to 6 C atoms or alkoxy groups having 1 to 6 C atoms or alkylamino groups having 1 to 6 C atoms or dialkylamino groups having 1 to 6 C atoms.

In the formula I for the ascorbic acid derivatives, suitable alkoxy radicals for R ¹ or R ² are those alkyl groups which contain 1 to 6 C atoms, preferably 1 to 4 C atoms. Examples of alkoxy groups are methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy or tert-butoxy.

The group -OPO ₃ M is preferably the -OPO 3 H group, but it is also possible to use salts of the formula I where M in formula I corresponds to an alkali metal cation, for example of Na or K, or of an alkaline earth metal cation, for example of Mg or Ca.

The attachment of a carbohydrate in position 2 or 3 of ascorbic acid, referred to as O-glycosyl in formula I, can be used, for example, for monosaccharides such as ribose, arabinose xylose, lyxose, allose, altrose, glucose, mannose, gulose, idose, galactose, talose, ribulose , Xylulose, psicose, fructose, sorbose or tagatose. In this list both isomers, i. each contain the D or L forms. Preferably, glucose, galactose or fructose, most preferably glucose, are used.

In principle, however, disaccharides are also suitable, such as sucrose (or else called sucrose), lactose, trehalose, maltose, cellobiose, gentiobiose or melibiose. This list includes both the α and β forms.

From the group of disaccharides are preferably sucrose or lactose, particularly preferably sucrose used.

Preferably, the radical R ¹ in formula I is hydroxy and R ² is -O-alkyl, -OC (O) -alkyl, -OPO ₃ M or O-glycosyl, as described above.

Preferably, the radical R ² in formula I is hydroxy and R ¹ is

-O-alkyl, -OC (O) -alkyl, -OPO ₃ M or O-glycosyl, as previously described.

Particularly preferably, both radicals R ² and R ^{1 are} hydroxy.

R ³ or R ⁴ are each independently hydroxy or a radical B and the radical B corresponds to a partial structure of the formula II, III, IV, V, VI, VII, VIII, IX, X ₁ XI or XII, as described above. In a preferred embodiment, the radical R ^{3 is} hydroxy and R ⁴ corresponds to a radical B, as described above and preferred below.

However, according to the invention it is also possible to stabilize mixtures of ascorbic acid derivatives of the formula I in which the radical

B is both R ³ and R ⁴ , as well as R ³ or R ⁴ .

In the formulas II to XII described above, A denotes alkyl having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20 C atoms each independently represent a linear or branched alkyl group. for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or tert-butyl, and also pentyl, 1-, 2- or 3-methylbutyl, 1, 1, 1, 2 or 2 , 2-Dimethylpropyl, 1-ethylpropyl, hexyl, 1-, 2-, 3- or 4-methylpentyl, 1, 1, 1, 2, 1, 3, 2,2, 2,3 or 3 , 3-Dimethylbutyl, 1- or 2-ethylbutyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl, 1, 1, 2- or 1, 2,2-trimethylpropyl or alkyl groups and their isomers of the empirical formulas C ₇ H ₁₅ to

n is an integer from 1 to 25, preferably an integer from 1, 2, 3, 4 or 5.

X describes the counterion for the cations [NHA ₂ ] ⁺ and [NA ₃ J ⁺ , where A has one of the meanings given above, preferably Cl ^" , Br ^" , I ^" or [SO ₄ ] ^{2 '} or the counterion of the anion [ SO ₃ ] ^" , preferably an ammonium ion or an alkali metal or alkaline earth metal cation such as Na ⁺ , K ⁺ , Mg ²⁺ or Ca ²⁺ .

However, it is also possible that partial charges in the molecule itself is compensated for, ie that compounds of the formula I can exist as a zwitterionic structure. Compounds of the formula I can also be present as salts in the preparation, ie at least one hydroxy group of the ascorbic acid skeleton is present deprotonated and the charge becomes by a counter cation, for example an alkali or alkaline earth metal cation, balanced.

For the substituents of the formula II, the radicals R ⁵ to R ⁹ , R ¹¹ and R ^{12 are} preferably H and

R ^{10 is} -OH ₁ -OA, -A, -NH ₂ , -NHA, -NA ₂ , -NH- (CH ₂ -CH ₂ -O) _n -H, -Nf (CH ₂ -CH ₂ -O) _n -H] ₂ , - [NHA ₂ ] X, - [NA ₃ ] X, -SO ₃ H, - [SO ₃ ] X or 2H-benzotriazol-2-yl.

R ¹⁰ in formula II is preferably -OA, -NH ₂ , -NHA or -NA ₂ , most preferably -OA or -NA ₂ . where A has one of the meanings given above. A in R ^{10 of} the formula II is very particularly preferably methyl, ethyl, n-butyl, n-hexyl.

For the substituents of the formula III, the radicals R ⁵ , R ⁶ , R ⁸ and R ^{9 are} preferably H and

R ^{7 is} -OH, -OA, -A, -NH ₂ , -NHA ₁ -NA ₂ , -NH- (CH ₂ -CH ₂ -O) _n -H, -N [(CH ₂ -CH ₂ -O) _n -H] ₂ , - [NHA ₂ ] X, - [NA ₃ ] X ₁ -SO ₃ H ₁ - [SO ₃ ] X or 2H-benzotriazol-2-yl.

R ⁷ in formula III is preferably -OA, -NH ₂ , -NHA or -NA ₂ , most preferably -OA or -NA ₂ , wherein A has one of the meanings given above. A in R ^{7 of} the formula III is very particularly preferably methyl, ethyl, n-butyl, n-hexyl.

For the substituents of the formula IV, the radicals R ⁵ , R ⁶ , R ⁸ and R ^{9 are} preferably H and

R ^{7 is} -OH, -OA, -A, -NH ₂ , -NHA, -NA ₂ , -NH- (CH ₂ -CH ₂ -O) _n -H ₁ -N [(CH ₂ -CH ₂ -O) _n -H] ₂ , - [NHA ₂ ] X, - [NA ₃ ] X, -SO ₃ H, - [SO ₃ ] X or 2H-benzotriazol-2-yl.

R ⁷ in formula IV is preferably -OA, -NH ₂ , -NHA or -NA ₂ , most preferably -OA or -NA ₂ , wherein A has one of the meanings given above. A in R ^{7 of} the formula IV is very particularly preferably methyl, ethyl, n-butyl, n-hexyl. Alternatively, for the substituents of formula IV, the radicals R ⁵ , R ⁸ and R ^{9 are} preferably H, R ⁶ is 2H-benzotriazol-2-yl and R ⁷ is -OH, -OA, -A, -NH ₂ , -NHA , -NA ₂ , -NH- (CH ₂ -CH ₂ -O) _n -H, -N [(CH ₂ -CH ₂ -O) _n -H] ₂ , - [NHA ₂ ] X, - [NA ₃ ] X, -SO ₃ H or - [SO ₃ ] X. In this substituent arrangement, R ^{7 is more} preferably OH.

For the substituents of the formula V, the radicals R ⁶ , R ⁸ , R ¹¹ and R ^{13 are} preferably H and the substituents R ⁵ , R ⁷ , R ⁹ , R ¹⁰ , R ¹² and R ^{14 are} each independently H, -OH, -OA, -A, -NH ₂ , -NHA, -NA ₂ , -NH- (CH ₂ - CH ₂ -O) _n -H. -Nf (CH ₂ -CH ₂ -O) _n -H] ₂ . - [NHA ₂ ] X. - [NA ₃ ] X. -SO ₃ H, - [SO ₃ ] X or 2H-benzotriazol-2-yl.

R ⁵ , R ⁷ , R ⁹ , R ¹⁰ , R ¹² and R ¹⁴ in formula V are each independently preferably H, -OA, -NH ₂ , -NHA or -NA ₂ , most preferably H, wherein A is one of has previously given meanings.

For the substituents of the formula VI, the radicals R ⁶ , R ⁸ , R ⁹ , R ¹² , R ¹³ and R ^{16 are} preferably H and the substituents R ⁵ , R ⁷ , R ¹⁰ , R ¹¹ , R ¹⁴ and R ^{15 are} each independently each other is H, -OH, -OA, -A, -NH ₂ , -NHA, -NA ₂ , -NH- (CH ₂ -CH ₂ -O) _n -H, -NI (CH ₂ -CH ₂ -O) _n -H] ₂ , - [NHA ₂ ] X, - [NA ₃ ] X, -SO ₃ H, - [SO ₃ ] X or 2H-benzotriazol-2-yl.

R ⁵ , R ⁷ , R ¹⁰ , R ¹¹ , R ¹⁴ and R ¹⁵ in formula VI are each, independently of one another, preferably H, -OA, -NH ₂ , -NHA or -NA ₂ , very particularly preferably H, where A is one of has previously given meanings.

For the substituents of the formula VII, the radicals R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ^{10 are} preferably H and Z is -ascorbyl, hydroxy, -O-2-ethylhexyl, -O-hexyl, -OA or -NH-C (CH ₃ ) ₃ .

Z in formula VII is particularly preferably OH. For the substituents of the formula VIII, the radicals R ⁵ , R ⁶ , R ⁷ and R ^{8 are} preferably H and the substituent R ⁹ is preferably -OH, -OA, -A, - NH ₂ , -NHA, -NA ₂ , - NH- (CH ₂ -CH ₂ -O) _n -H, -N [(CH ₂ -CH ₂ -O) _n -H] ₂ , - [NHA ₂ ] X, - [NA ₃ ] X, -SO ₃ H, - [SO ₃ ] X or 2H-benzotriazol-2-yl.

R ⁹ in formula VIII particularly preferably means -OA.

For the substituents of the formula IX, the radicals R ⁵ , R ⁶ , R ⁷ and R ^{8 are} preferably H and the substituent R ⁹ is preferably -OH, -OA, -A, - NH ₂ , -NHA, -NA ₂ , - NH- (CH ₂ -CH ₂ -O) _n -H, -Nf (CH ₂ -CH ₂ -O) _n -H] ₂ , - [NHA ₂ ] X, - [NA ₃ ] X, -SO ₃ H , - [SO ₃ ] X or 2H-benzotriazol-2-yl.

R ⁹ in formula IX particularly preferably means -OA.

For the substituents of the formula X, the radicals R ⁵ , R ⁷ and R ^{8 are} preferably H and the substituent R ⁶ is preferably -OH, -OA, -A, - NH ₂ , -NHA, -NA ₂ , -NH- ( CH ₂ -CH ₂ -O) _n -H, -N [(CH ₂ -CH ₂ -O) _n -H] ₂ , - [NHA ₂ ] X, - [NA ₃ ] X, -SO ₃ H, - [SO ₃ ] X or 2H-benzotriazol-2-yl.

R ⁶ in formula X is particularly preferably -OH.

For the substituents of the formula XI, the radicals R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹¹ and R ^{12 are} preferably H and the substituent R ¹⁰ is preferably H, -OH, -OA, -A, - NH _2, -NHA, -NA _2, -NH- (CH ₂ -CH ₂ -O) _n -H, -N [(CH ₂ -CH ₂ -O) _n - H] _2, - [NHA _2] X , - [NA ₃ ] X, -SO ₃ H, - [SO ₃ ] X or 2H-benzotriazol-2-yl.

R ¹⁰ in formula XI particularly preferably denotes H.

For the substituents of the formula XII, the radicals R ⁵ , R ⁶ , R ⁸ and R ^{9 are} preferably H and the substituent R ⁷ is preferably -OH, -OA, -A, - NH ₂ , -NHA, -NA ₂ , - NH- (CH ₂ -CH ₂ -O) _n -H, -N [(CH ₂ -CH ₂ -O) _n -H] ₂ , - [NHA ₂ ] X, - [NA ₃ ] X, -SO ₃ H, - [SO ₃ ] X or 2H-benzotriazol-2-yl. R ⁷ in formula XII particularly preferably denotes A. In a particular variant, compounds of the formula XII which are suitable as substituent R ^{7 are also} the partial structure

exhibit.

Further preferred combinations are disclosed in the claims.

Particularly preferred embodiments of the radical B can be seen in the following substructures:

25

30

10

villa

VIIIb

25

30

In formula I, the substructure IVe and IIIa or the substructure IVe or IIIa for the substituent B is very particularly preferred.

The preparation to be stabilized containing at least one

Ascorbic acid derivative of the formula I or preferred compounds of the formula I contains from 0.1 to 10% by weight of the stabilizing compound selected from the group consisting of diphenylacylate UV filters, dibenzoylmethane UV filters, phenolic antioxidants or mixtures thereof, based on the total weight of the preparation. Preferably, the stabilizing compound, as previously selected, is added in 0.5 to 3% by weight, based on the total preparation. The ratio of the at least one ascorbic acid derivative to the stabilizing compound of the selected group is 5: 1 to 1: 5, preferably 2: 1 to 1: 2. The stabilized preparation according to the invention containing at least one ascorbic acid derivative of the formula I or a preferred compound of the formula I and at least one stabilizing compound of the selected group, as described above, may optionally contain further active ingredients or adjuvants.

Preferred further active ingredients which may be present in the preparation are, for example, further UV filters, vitamins, antioxidants, anti-aging active ingredients, anti-cellulite active substances, depigmentation active ingredients or customary skin-sparing or skin-care active ingredients.

The preparations may comprise or contain, consist essentially of or consist of said necessary or optional ingredients. Any compounds or components which may be used in the compositions are either known and commercially available or may be synthesized by known methods.

Furthermore, combinations with particulate UV filters, both as a powder and as a dispersion or paste, of the following types are possible.

Here, both those from the group of titanium dioxides, such as coated titanium dioxide (for example Eusolex ^® T-2000, Eusolex ^® T-AQUA, Eusolex ^® T-AVO, Eusolex ^® T-OLEO), zinc oxides (eg Sachtotec® ^®), iron oxides and also Cerium oxides and / or zirconium oxides are preferred.

Furthermore, combinations with pigmentary titanium oxide or

Zinc oxide possible, wherein the particle size of these pigments are greater than or equal to 200 nm, for example Hombitec® COS.

Furthermore, it can be preferred according to the invention if the preparations contain inorganic UV filters which are prepared by customary methods, for example in Cosmetics & Toiletries, February 1990, Vol. 105, pp. 53-64, were post-treated. This can be an or may be selected from among the following aftertreatment components: amino acids, beeswax, fatty acids, fatty acid alcohols, anionic surfactants, lecithin, phospholipids, sodium, potassium, zinc, iron or aluminum salts of fatty acids, polyethylenes, silicones, proteins (especially collagen or elastin) , Alkanolamines, silica,

Alumina, other metal oxides, phosphates, such as sodium hexametaphosphate or glycerol.

Preferably used further particulate UV filters are:

untreated titanium dioxides, e.g. the products Microtitanium

Dioxide MT 500 B from Tayca; Titanium Dioxide P25 from Degussa,

Post-treated micronized titanium dioxides with alumina and silica. the product "Microtitanium Dioxide MT 100 SA of Tayca; or the product "Tioveil Fin" the Fa.

Uniqema,

Aftertreated micronised titanium dioxides with alumina and / or aluminum stearates / laurate aftertreatment, e.g. Microtitanium Dioxide MT 100 T from Tayca, Eusolex T-2000 from Merck,

Post-treated micronized titanium dioxides with iron oxide and / or

Iron stearates aftertreatment such as e.g. the product "Microtitanium

Dioxide MT 100 F "from Tayca,

Aftertreated micronised titanium dioxides with silicas, alumina and silicone aftertreatment, e.g. the product "Microtitanium Dioxide MT 100 SAS", the company Tayca,

Aftertreated micronised titanium dioxides with sodium hexametaphosphates, e.g. the product "Microtitanium Dioxide MT 150 W" from Tayca.

The treated micronized titanium dioxides used for combination may also be post-treated with: Octyltrimethoxysilane; such as the product Tego Sun T 805 from Degussa,

silica; such as. the product Parsol T-X from DSM,

Alumina and stearic acid; such as. the product UV titanium M160 from Kemira,

Aluminum and glycerin; such as. the product UV-Titan of the company Kemira,

Aluminum and silicone oils, e.g. the product UV-Titan M262 the

Fa. Kemira, 0

Sodium hexamethaphosphate and polyvinylpyrrolidone,

Polydimethylsiloxanes, e.g. the product 70250 Cardre UF TiO2SI3 "from the company Cardre,

Polydimethylhydrogensiloxanes, e.g. Microtitanium Dioxide USP Grade Hydrophobie "from Color Techniques .O

Furthermore, the combination with the following products may also be advantageous:

Untreated zinc oxides such. B. the product Z-Cote Fa. BASF (Sunsmart), Nanox Fa. Elementis 0. Post-treated zinc oxides such as the following products: o "Zinc Oxide CS-5" from Toshibi (ZnO aftertreated with polymethylhydrogenosiloxanes) Nanogard Zinc Oxide FN from Nanophase Technologies o "SPD-Z1" from Shin-Etsu (ZnO aftertreated with a5

Silicone grafted acrylic polymer dispersed in

Cyclodimethylsiloxanes o "Escalol Z100" of the company ISP (aluminum oxide aftertreated ZnO dispersed in an ethylhexyl methoxycinnamate / PVP-hexadecenes / methicone copolymer mixture) 0 o "Fuji ZNO-SMS-10" from Fuji Pigment (ZnO aftertreated with silica and polymethylsilsquioxane) ; o Untreated cerium oxide micropigment, for example with the name "Colloidal Cerium Oxide" from Rhone Poulenc o Untreated and / or post-treated iron oxides with the name Nanogar from Arnaud.

By way of example, mixtures of various metal oxides, e.g. Titanium dioxide and cerium oxide with and without Nachbenhandlung be used, such. the product Sunveil A of the company Ikeda. In addition, mixtures of alumina, silica, and silicon aftertreated titanium dioxide may also be used. Zinc oxide mixtures such. the product UV titanium M261 from Kernira can be used in combination with the UV protection agent according to the invention.

These inorganic UV filters are typically used in an amount of from 0.1% to 25% by weight, preferably 2% by weight to 10%

Wt .-%, incorporated into the preparations.

The preparations may of course also contain one or more additional hydrophilic or lipophilic sunscreen filters which are in the UV-A range and / or UV-B range and (/ or IR and / or VIS range ( These additional filters may in particular be derived from cinnamic acid derivatives, salicylic acid derivatives, camphor derivatives, triazine derivatives, β-diphenylacrylate derivatives, p-aminobenzoic acid derivatives and polymeric filters and silicone filters described in the application WO-93/04665. Further examples of organic filters are given in the patent application EP-A 0 487 404. In the following, the named UV filters are usually named according to the INCI nomenclature.

In particular, here are:

para-aminobenzoic acid and its derivatives: PABA, ethyl PABA, ethyl dihydroxypropyl PABA, ethylhexyl dimethyl PABA, e.g. B. under the name "Escalol 507" from the company ISP, glyceryl

PABA, PEG-25 PABA, e.g. B. under the name "Uvinul P25" from BASF. Salicylates: Homosalates are sold under the name "Eusolex HMS" by Merck; Ethyl hexyl salicylates, e.g. B. under the name "Neo Heliopan OS" from the company. Haarmann and Reimer, Dipropylene glycol salicylate, z. B. sold under the name "Dipsal" by the company Scher,

TEA salicylates, e.g. B. under the name "Neo Heliopan TS" from the company Haarmann and Reimer.

ß.ß-diphenyl acrylates derivatives: Octocrylene, z. B. under the name "Uvinul N539" from BASF, Etocrylene, z. B. under the name "Uvinul N35" from BASF.

Benzophenone Derivatives: Benzophenone-1, e.g. B. operated under the name "Uvinul 400"; Benzophenone-2, e.g. B. operated under the name "Uvinul D50"; Benzophenone-3 or oxybenzone, e.g. B. sold under the name "Uvinul M40" Benzophenone-4, z. B. operated under the name "Uvinul MS40"; Benzophenone-9, e.g. B. operated under the

Name "Uvinul DS-49" from BASF, Benzophenone-5, Benzophenone-6, z. B. under the name "Helisorb 11" from the company. Norquay, Benzophenone-8, z. Sold under the name "SpectraSorb UV-24" from American Cyanamid, Benzophenone-12 n-hexyl 2- (4-diethylamino-2-hydroxybenzoyl) benzoate or 2-hydroxy-4-methoxybenzophenone, marketed by from Merck, Darmstadt under the name Eusolex® 4360.

Benzylidene camphor derivatives: 3-benzylidenecamphor, e.g. B. under the name "Mexoryl SD" from the company. Chimex, 4-Methylbenzylidene- camphor, z. B. under the name "Eusolex 6300" from the Fa.

Merck, Benzylidenecamphorsulfonsäure, z. B. under the name "Mexoryl SL" from the company Chimex, Camphor benzalkonium methosulfate, z. B. under the name "Mexoryl SO" from the company. Chimex, Terephthalylidenedicamphorsulfonsäure, z. B. under the name "Mexoryl SX" from the Fa Chimex, Polyacrylamidomethylbenzylidene- camphor operated under the name "Mexoryl SW" from the company Chimex. Phenylbenzimidazole derivatives: phenylbenzimidazolesulfonic acid, e.g. B. under the name "Eusolex 232" from the company Merck, disodium phenyl dibenzimidazole tetrasulfonate, z. B. under the name "Neo Heliopan AP" from the company Haarmann and Reimer.

Phenylbenzotriazole derivatives: Drometrizole trisiloxanes, e.g. B. under the name "Silatrizole" from the Fa. Rhodia Chimie, Methylenebis (benzotriazolyl) tetramethylbutylphenol in solid form, eg. B. under the name "MIXXIM BB / 100" from the company. Fairmount Chemical, or in micronized form as an aqueous dispersion, eg. B. under the name "Tinosorb M" from the company. Ciba Specialty Chemicals.

Triazines derivatives: ethylhexyltriazone, e.g. B. under the name "Uvinul T150" from the Fa. BASF, Diethylhexylbutamidotriazone, z. B. under the name "Uvasorb HEB" from the company. Sigma 3V, 2,4,6-tris (diisobutyl 4'-aminobenzalmalonate) -s-triazines.

Anthraniline derivatives: menthyl anthranilate, e.g. B. under the name "Neo Heliopan MA" from the company Haarmann and Reimer.

Imidazole derivatives: Ethylhexyldimethoxybenzylidenedioxoimidazoline propionate.

Benzalmalonate Derivatives: Polyorganosiloxanes containing functional benzalmalonate groups, e.g. Polysilicone-15, e.g. B. sold under the name "Parsol SLX" by Hoffmann LaRoche.

4,4-Diarylbutadiene derivatives: 1,1-dicarboxy (2,2'-dimethylpropyl) -4,4-diphenylbutadiene.

Benzoxazole derivatives: 2,4-bis [5- (1-dimethylpropyl) benzoxazol-2-yl (4-phenyl) imino] -6- (2-ethylhexyl) imino-1,3,5-triazines, e.g. B. sold under the name Uvasorb K2A from the company. Sigma 3V and mixtures thereof containing.

Piperazine derivatives such as the compound

The compounds listed in the list are only to be considered as examples. Of course, other UV filters can be used.

The organic UV-protective substances suitable for combination with the ascorbic acid derivatives of the formula I are preferably to be selected from the following list: ethylhexyl salicylate, phenylbenzimidazolesulfonic acid, benzophenone-3, benzophenone-4, benzophenone-5, n-hexyl 2- (4-diethylamino 2-hydroxybenzoyl) benzoates, 4-methylbenzylidenecamphor, terephthalylidenedicamphorsulfonic acid, disodium phenyldibenzimidazoletetrasulfonate,

Methylenebis (benzotriazolyl) tetramethylbutylphenol, ethylhexyl triazone, diethylhexyl butamido triazone, drometrizole trisiloxane, polysilicone-15,1,1-dicarboxy (2,2'-dimethylpropyl) -4,4-diphenylbutadiene _I 2,4-bis [5-1 ( dimethylpropyl) benzoxazol-2-yl (4-phenyl) imino] -6- (2-ethylhexyl) imino-1,3,5-triazines and mixtures thereof.

These organic UV filters are usually incorporated in formulations in an amount of from 0.01% to 20% by weight, preferably 1% to 10% by weight.

As a rule, organic UV filters are incorporated in formulations in an amount of from 0.01% by weight to 20% by weight, preferably from 0.5% by weight to 20% by weight. There are many known and proven substances known from the literature which can be used as antioxidants, eg amino acids (eg glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazoles, (eg urocaninic acid) and their derivatives, peptides such as D, L- Carnosine, D-carnosine, L-carnosine and their derivatives (eg anserine), carotenoids, carotenes (eg α-carotene, β-carotene, lycopene) and their derivatives, chlorogenic acid and its derivatives, lipoic acid and derivatives thereof (eg dihydrolipoic acid), Aurothioglucose, propylthiouracil and other thiols (eg thioredoxin, glutathione, cysteine, cystine, cystamine and their glycosyl, N-acetyl, methyl, ethyl, propylamyl, butyl and lauryl, palmitoyl, oleyl, γ Linoleyl, cholesteryl and glyceryl esters) and their salts, dilauryl thiodipropionate, distearyl thiodipropionate, thiodipropionic acid and derivatives thereof (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) and sulfoximine compounds (eg buthionine sulfoximines, homocysteine ulfoximine, buthione sulfones, penta, hexa, heptathionine sulfoximine) in very low tolerated dosages (eg pmol to μmol / kg), furthermore (metal) chelators (eg α-hydroxyfatty acids, palmitic acid, phytic acid, lactoferrin), α-hydroxy acids (eg citric acid,

Lactic acid, malic acid), humic acid, bile acids, bile extracts, biirubin, biliverdin, EDTA, EGTA and their derivatives, unsaturated fatty acids and their derivatives, vitamin C and derivatives (eg ascorbyl palmitate, magnesium ascorbyl phosphate, ascorbyl acetate), tocopherols and derivatives (eg Vitamin E acetate), vitamin A and derivatives (eg vitamin A palmitate) and benzylic benzylic resin, rutinic acid and its derivatives, α-glycosylrutin, ferulic acid, furfurylidene glucitol, carnosine,

Butylhydroxytoluene, butylhydroxyanisole, nordohydroguajaretic acid, trihydroxybutyrophenone, quercitin, uric acid and its derivatives, mannose and its derivatives, zinc and its derivatives (eg ZnO, ZnSO ₄ ), selenium and its derivatives (eg selenium methionine), stilbenes and their derivatives

(eg stilbene oxide, trans-stilbene oxide). Mixtures of antioxidants are also suitable for use in the compositions or preparations according to the invention. Known and commercially available mixtures are, for example, mixtures containing as active ingredients lecithin, L - (+) - ascorbyl palmitate and citric acid (eg (eg

^® Oxynex AP), natural tocopherols, L - (+) - ascorbyl palmitate, L - (+) - ascorbic acid and citric acid (for example Oxynex ^® K LIQUID), tocopherol extracts from natural sources, L - (+) - ascorbyl palmitate, L (+) - ascorbic acid and citric acid (for example Oxynex ^® L LIQUID), DL-α-tocopherol, L - (+) - Ascorbylpalrnitat, citric acid and lecithin (for example Oxynex ^® LM) or butylhydroxytoluene (BHT), L - (+ ) -Ascorbylpalmitat and citric acid (eg Oxynex ^® 2004). Such antioxidants are usually used with compounds of the formula I in such compositions in ratios in the range from 1000: 1 to 1: 1000, preferably in amounts of 100: 1 to 1: 100.

The preparations may contain vitamins as further ingredients. Preferably, vitamins and vitamin derivatives are selected from

Vitamin A, Vitamin A Propionate, Vitamin A Palmitate, Vitamin A Acetate,

Retinol, vitamin B, thiamin chloride hydrochloride (vitamin B-i), riboflavin

(Vitamin B ₂ ), nicotinic acid amide, vitamin C (ascorbic acid), vitamin D, ergocalciferol (vitamin D ₂ ), vitamin E, DL-α-tocopherol, tocopherol-E-acetate, tocopherol hydrogen succinate, vitamin Ki, esculin (vitamin P)

Active ingredient), thiamin (vitamin B-i), nicotinic acid (niacin), pyridoxine, pyridoxal,

Pyridoxamine, (vitamin Be), pantothenic acid, biotin, folic acid and cobaltamine (vitamin Bi ₂ ) in the cosmetic preparations according to the invention, particularly preferably retinol, nicotinamide, vitamin A palmitate, vitamin C and its derivatives, DL-α- Tocopherol, tocopherol E

Acetate, nicotinic acid, pantothenic acid and biotin, most preferably retinol or nicotinic acid amide. Vitamins are included Compounds of the formula I are usually used in ratios in the range from 1000: 1 to 1: 1000, preferably in amounts of from 100: 1 to 1: 100.

The preparations may contain fragrances as further ingredients, such as "S. Arctander, Perfume and Flavor Materials, Vol. I and II,

Montclair, N.J., 1969, "Selbstverlag" or "K. Bauer, D. Garbe and H. Surburg, Common Fragrance and Flavor Materials, 4th ed., Wiley-VCH, Weinheim 2001". Furthermore, all the fragrances described in US7354893 B2 may be included.

Particularly preferred anti-aging agents are pyrimidinecarboxylic acids,

Aryloxime, bioflavonoids, bioflavonoid-containing extracts, chromones or retinoids.

Pyrimidinecarboxylic acids occur in halophilic microorganisms and play a role in the osmoregulation of these organisms (EA Galinski et al., Eur. J. Biochem., 149 (1985) page 135-139). In particular, ectoine ((S) -1, 4,5,6-tetrahydro-2-methyl-4-pyrimidinecarboxylic acid) and hydroxyectoine ((S ₁ S) -1,5,6-tetrahydro-5 are among the pyrimidinecarboxylic acids The preparations contain such pyrimidinecarboxylic acids preferably in amounts of up to 15% by weight. The pyrimidincarboxylic acids are preferably added in proportions of from 100: 1 to 1: 100 Compounds of the formula I are used, with ratios in the range from 1:10 to 10: 1 being particularly preferred.

Among the aryl oximes, 2-hydroxy-5-methyllaurophenone oxime, which is also referred to as HMLO, LPO or F5, is preferably used. The preparations preferably contain from 0.01 to

10 wt .-% of Aryloxims, it being particularly preferred if the

Preparation contains 0.05 to 5% by weight of aryloxime. Known bioflavonoids are, for example, troxerutin, tiliroside, α-glucosylrutin, rutin or isoquercetin, the said selection not being intended to be restrictive.

Bioflavonoidhaltige extracts are for example Gingko Biloba or Emblica.

Known anti-aging substances are also chromones, as described, for example, in EP 1508327 or retinoids, for example retinol (vitamin A), retinoic acid, retinaldehyde or else synthetically modified compounds of vitamin A.

The described chromones and retinoids are also effective anti-cellulite agents. Another well known anti-cellulite drug is caffeine.

The preparations may also contain one or more further skin-lightening active ingredients or synonymously depigmentation active ingredients. In principle, skin-lightening active ingredients can be all active ingredients known to the person skilled in the art. Examples of compounds with skin-lightening activity are hydroquinone, kojic acid, arbutin, aloesin or rucinol.

The said constituents of the preparation can be incorporated in the usual way, by means of techniques which are well known to the person skilled in the art.

Suitable preparations are for an external (synonymous to topical) application, for example as a cream, lotion, gel, or as a solution that can be sprayed on the skin. Inventive ascorbic acid derivatives are particularly suitable for protecting dyed hair from UV-induced fading or UV-related color changes. This protective effect for hair dyes is especially given when treating the undyed hair with the preparation and only in the subsequent step performs the hair dyeing process.

The protective effect is particularly formed when pretreating the hair with alcoholic solutions containing at least one ascorbic acid derivative of the formula I. Also, the color effect can be obtained by so-called permanent colors under UV irradiation. Oxidation dyes are formed, for example, from dye precursors, the so-called oxidation bases (developers) and the nuancers (couplers). Under oxidizing conditions (e.g., use of hydrogen peroxide), the dye precursors on the hair react with each other to form the dye, which is incorporated into the hair.

As an application form of the preparations to be stabilized, e.g. called: solutions, suspensions, emulsions, PIT emulsions, pastes, ointments, gels, creams, lotions, powders, soaps, surfactant-containing cleaning preparations, oils, aerosols and sprays. Other applications are e.g. Sticks, shampoos and shower baths. Any customary carrier substances, adjuvants and optionally further active ingredients can be added to the preparation.

Preferable excipients come from the group of preservatives, solubilizers, colorants, odor improvers.

Ointments, pastes, creams and gels may contain the usual excipients, for example animal and vegetable fats, waxes, paraffins, starch, tragacanth, cellulose derivatives, polyethylene glycols, silicones, bentonites, silicic acid, talc and zinc oxide or mixtures of these substances. Powders and sprays may contain the usual excipients, for example lactose, talc, silicic acid, aluminum hydroxide, calcium silicate and polyamide powder or mixtures of these substances. Sprays may additionally contain the customary propellants, for example chlorofluorohydrocarbons, propane / butane or dimethyl ether.

Solutions and emulsions may contain the usual excipients such as solvents, solubilizers and emulsifiers, e.g. Water, ethanol, isopropanol, ethyl carbonate, ethyl acetate, benzyl alcohol, benzyl benzoate, propylene glycol, 1, 3-butyl glycol, dimethyl capramide, dimethyl isosorbide. Oils, especially cottonseed oil, peanut oil, corn oil, olive oil, castor oil and sesame oil, glycerol fatty acid esters, polyethylene glycols and fatty acid esters of sorbitan or mixtures of these substances. In a preferred application, the ascorbic acid derivatives according to the invention, as described, are converted into an application-appropriate formulation shortly before application. For example, the substance is dissolved in a carrier as described above and applied directly to skin or preferably to hair. Particularly suitable carriers in this sense are Arlasolve DMI (dimethylisosorbide), butylene glycol, Finsolv® PG-22 (dipropylene glycol dibenzoate) or Pelemol® BIP (butylphthalimide isopropylphthalimide).

Suspensions may include the usual carriers such as liquid diluents, e.g. Water, ethanol or propylene glycol, suspending agents, e.g. ethoxylated isostearyl alcohols, polyoxyethylene sorbitol esters and polyoxyethylene sorbitan esters, microcrystalline cellulose, aluminum metahydroxide, bentonite, agar-agar and tragacanth or mixtures of these substances.

Soaps may contain the usual excipients such as alkali metal salts of fatty acids, salts of fatty acid monoesters, fatty acid protein hydrolysates, isothionates, lanolin, fatty alcohol, vegetable oils, plant extracts, glycerol, sugars or mixtures of these substances. Surfactant-containing cleaning products may include the usual excipients such as salts of fatty alcohol sulfates, fatty alcohol ether sulfates, sulfosuccinic acid esters, fatty acid protein hydrolysates, isothionates, imidazolinium derivatives, methyl taurates, sarcosinates, fatty acid amide ether sulfates, alkyl amidobetaines, fatty alcohols, fatty acid glycerides, fatty acid diethanolamides, vegetable and synthetic oils, lanolin derivatives, ethoxylated glycerol - Contain fatty acid esters or mixtures of these substances.

Facial and body oils may contain the usual excipients such as synthetic oils such as fatty acid esters, fatty alcohols, silicone oils, natural oils such as vegetable oils and oily vegetable extracts, paraffin oils, lanolin oils or mixtures of these substances.

Other typical cosmetic application forms are also lipsticks, lip balm, mascara, eyeliner, eye shadow, rouge, powder, emulsion and wax make-up and sunscreen, pre-sun and after-sun preparations.

The preferred preparation forms according to the invention include in particular emulsions.

Emulsions of the invention are advantageous and contain z. As mentioned fats, oils, waxes and other fatty substances, and water and an emulsifier, as it is commonly used for such a type of preparation.

As emulsifiers, for example, the known W / O and O / W emulsifiers can be used. It is advantageous to use further customary co-emulsifiers in the preferred O / W emulsions according to the invention. A preferred embodiment of the invention is an emulsion, which is present as a protective cream or milk and in addition to the compounds of formula I, for example fatty alcohols, fatty acids, fatty acid esters, especially triglycerides of fatty acids, lanolin, natural and synthetic oils or waxes and emulsifiers in the presence of

Contains water.

Further preferred embodiments are oily lotions based on natural or synthetic oils and waxes, lanolin, fatty acid esters, in particular triglycerides of fatty acids, or oily alcoholic lotions based on a lower alcohol such as ethanol or a glycerol such as propylene glycol and / or a polyol such as Glycerol, and oils, waxes and fatty acid esters, such as triglycerides of fatty acids.

The preparation may also be in the form of an alcoholic gel comprising one or more lower alcohols or polyols, such as ethanol, propylene glycol or glycerin, and a thickening agent, such as silica. The oily alcoholic gels also contain natural or synthetic oil or wax.

The solid sticks consist of natural or synthetic waxes and oils, fatty alcohols, fatty acids, fatty acid esters, lanolin and other fatty substances.

If a preparation is formulated as an aerosol, the customary propellants, such as alkanes, fluoroalkanes and chlorofluoroalkanes, are generally used.

In the following the invention is explained in more detail by means of examples, the invention is executable throughout the claimed range and not limited to the examples mentioned here. Examples:

Test method for documentation of stabilization of the preparation: General description: A 2% solution of a compound of formula I in butanediol is prepared. 18.8 μl each of this solution are applied to the roughened side of a PMMA support (Plexiglas) and irradiated for 34 minutes in the solar simulator (Suntest CPS, Atlas instrument output 500 W / m ² ). After irradiation, the samples are extracted with isopropanol and transferred to 50 ml volumetric flasks. The volumetric flasks are filled to the mark with isopropanol and then measured spectrophotometrically. The absorbance at the absorption maximum of the investigated compound of the formula I is noted and compared with the corresponding comparative value. The comparative samples are prepared analogously, with the difference that no irradiation is carried out here. The reference samples are stored in the dark during the irradiation (= dark value).

The difference between the measured value for the extinction after irradiation (irradiation value) and the dark value serves as a measure of the light stability of the investigated preparation.

Example 1: Examination of compound 4-diethylaminobenzoic acid ascorbic acid ester (DAB)

Solutions are prepared as described under the general procedure, namely a) 2% solution of DAB with butanediol b) solution of a) with 2% by weight of 1- (4-tert-butylphenyl) -3- (4-methoxyphenyl ) propane-1,3-dione (Avobenzone) c) solution of a) with 2% by weight of bis-ethylhexylhydroxydimethoxybenzyl malonate (RonaCare® AP) d) solution of a) with 3% by weight of 2-ethylhexyl-2 cyano-3,3-diphenylacrylate (octocrylene).

The measurement of the extinction takes place at 315 nm. Results:

The data obtained show that, starting from a), improved absorption is achieved by using different stabilizers from b) through c) to d).

The improved effect measured in b) is surprising since here the

Combined with a photolabile UV filter is present, which in turn makes an absorption contribution at 315nm, so is already integrated into the summary mining value at 315nm.

The effect measured in c) is surprising since the stabilizer used

Compound has no self-absorption here.

In d) complete photostability is achieved, an absorption decrease in the

Maximum of DAB is not measurable.

Nominally increasing absorption in this range could be due to unknown processes that are slightly photoinduced and support absorption at 315 nm.

Decisive for the product performance is that the absorption power of the

Sytems is preserved. Formulation Examples: Sunscreen Lotions (O / W)

production:

First, the ascorbic acid derivatives of the formula I, for example DAB and / or PMCA, are pre-dissolved in isopropanol. Optionally, other or alternative alcohols and glycols are used, such as ethanol, glycerol or decyl alcohol. This preliminary solution is added to the other components of phase A. Subsequently, phase A is heated to 50-60 ⁰ C. Now heat phase B to 60 ° C., then to disperse phase C with stirring. Stir phase A into phase B / C with vigorous stirring. Cool with stirring and at 40 ⁰ C phase D to increase. Cool homogenize and Rürhen to 25 ⁰ C. Note: Described pre-solution may alternatively be added to the final emulsion with stirring at room temperature. Since ascorbic acid derivatives of the formula I have oxidation-sensitive groups, it is advisable to formulate or produce under conditions which are as inert as possible.

Hair color from different components: names of the substances used as INCI designations

Tocopherol, linalool, geraniol, disodium EDTA ₁ , perfume, toluene-2,5-diamine sulfate, ascorbic acid, alcohol denate, sodium sulfite, sodium hydroxide, sodium cocoyl isethionate, bis-ethylhexyl hydroxydimethoxy benzylmalonate, 2-methylresorcinol, 6- Amino-m-cresol, 4-amino-2-hydroxy-toluene, 4-amino-m-cresol, sodium lauryl sulfate, ammonia, lanolin alcohol, glycol distearate, sodium laureth sulfate, glyceryl stearate, ceteary alcohol, aqua.

Component B: Aqua, hydrogen peroxide, cetearyl alcohol, PPG-38-buteth-37, petrolatum, laureth-2, sodium cetearyl sulfate, salicylic acid, disodium phosphate, phosphoric acid, etidronic acid.

Component C (% = wt.%): 2% ethanolic solution of

Diethylaminobenzoic acid ascorbic acid ester (DAB) containing 1% bishexylhexyl hydroxydimethoxy benzyl malonates.

Application: Hair dyeing is preferably carried out in the following order: First, the hair is pretreated with component C. Subsequently, components A and B are mixed and applied to the hair. Another application variant is to integrate DAB directly into component A.

Claims

claims

1. Use of a compound selected from the group

Diphenylacrylate UV filters, dibenzoylmethane UV filters, phenolic antioxidants or mixtures thereof, for improving the UV stability of a preparation comprising at least one ascorbic acid derivative of the formula I,

in which

R ¹ or R ^{2 are} each independently of one another hydroxy, -O-alkyl, -OC (O) -alkyl, -OPO ₃ M or O-glycosyl,

Alkyl C 1 -C 6 -alkyl,

M alkali or alkaline earth metal cation or H,

R ³ or R ⁴ are each independently hydroxyl or a radical B, and B is a substituent of the formula II, III, IV, V, Vl ₁ VII, VIII, IX, X, Xl and / or

XII means

in which

R ⁵ to R ^{16 are} each independently H, -OH, -OA, -A, -NH ₂ , -NHA,

-NA ₂ , -NH- (CH ₂ -CH ₂ -O) _n -H, -Nf (CH ₂ -CH ₂ -O) _n -H] ₂ , - [NHA ₂ ] X, - [NA ₃ ] X , -

SO _{3 is} H, - [SO ₃ ] X or 2H-benzotriazol-2-yl and

A is alkyl having 1 to 20 C atoms, n is an integer from 1 to 25,

X is the counterion to the cations [NHA ₂ J ⁺ and [NA ₃ ] ⁺ or the anion

[SO ₃ ] ^" is and

Rest B stands.

Use according to claim 1, wherein the diphenylacrylate UV filter is 2-ethylhexyl-2-cyano-3,3-diphenylacrylate.

Use according to claim 1, wherein the dibenzoylmethane UV filter is 1- (4-tert-butylphenyl) -3- (4-methoxyphenyl) propane-1,3-dione.

4. Use according to claim 1, wherein the phenolic antioxidant is bishexyl hydroxydimethoxybenzylmalonate or bis-ethylhexylhydroxydimethoxybenzylidenemalonate.

5. Use according to claim 1, wherein in the compound of formula I of

Substituent B of the formula II, wherein the radicals R ⁵ to R ⁹ , R ¹¹ and R ^{12 is} H and R ^{10 is} -OH, -OA, -A, -NH ₂ , -NHA, -NA ₂ , -NH- (CH ₂ -CH ₂ -O) _n -H, -N [CCH ₂ -CH ₂ -O) _n -H] ₂ , - [NHA ₂ ] X, - [NA ₃ ] X ₁ -SO ₃ H, - [SO ₃ ] X or 2H

Benzotriazol-2-yl.

6. Use according to claim 1, wherein in the compound of the formula I, the substituent B corresponds to the formula IM, where the radicals R ⁵ , R ⁶ , R ⁸ and R ^{9 are} H and R ^{7 is} -OH, -OA, -A, - NH ₂ , -NHA, -NA ₂ , -NH- (CH ₂ -CH ₂ -O) _n -H, - N [(CH ₂ -CH ₂ -O) _n -H] ₂ , - [NHA ₂ ] X , - [NA ₃ ] X, -SO ₃ H, - [SO ₃ ] X or 2H-benzotriazol-2-yl.

7. Use according to claim 1, wherein in the compound of the formula I, the substituent B corresponds to the formula IV where the radicals R ⁵ , R ⁸ and R ^{9 are} H, R ^{6 is} H or 2H-benzotriazol-2-yl and R ⁷ - OH, -OA, -A, -NH ₂ , -NHA, -

NA ₂ , -NH- (CH ₂ -CH ₂ -O) _n -H, -Nf (CH ₂ -CH ₂ -O) _n -H] ₂ , - [NHA ₂ ] X, - [NA ₃ ] X, - SO ₃ H, - [SO ₃ ] X or 2H-benzotriazol-2-yl mean.

8. Use according to claim 1, wherein in the compound of formula I, the substituent B corresponds to the formula V, wherein the radicals R ⁶ , R ⁸ , R ¹¹ and R ¹³ H and the substituents R ⁵ , R ⁷ , R ⁹ , R ¹⁰ , R ¹² and R ¹⁴ respectively are independently H, -OH, -OA, -A, -NH _2, -NHA, -NA _2, -NH- (CH ₂ - CH ₂ -O) _n -H, -NKCH ₂ -CH ₂ -O) _n -H] ₂ , - [NHA ₂ ] X, - [NA ₃ ] X, -SO ₃ H, - [SO ₃ ] X or 2H-benzotriazol-2-yl.

9. Use according to claim 1, wherein in the compound of formula I, the substituent B corresponds to the formula VI, wherein the radicals R ⁶ , R ⁸ , R ⁹ , R ¹² , R ¹³ and R ¹⁶ H and the substituents R ⁵ , R ⁷ , R ¹⁰ , R ¹¹ , R ¹⁴ and R ^{15 are} each independently H, -OH, -OA, -A, -NH ₂ , -NHA, -NA ₂ , -NH- (CH ₂ -CH ₂ -O) _n -H, -Nf (CH ₂ -CH ₂ -O) _n -H] ₂ , - [NHA ₂ ] X, - [NA ₃ ] X, -SO ₃ H, - [SO ₃ ] X or 2H-benzotriazole Mean -2-yl.

10. Use according to claim 1, wherein in the compound of the formula I the substituent B corresponds to the formula VII where the radicals R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ^{10 are} H and Z is ascorbyl, hydroxy, -O-2-ethylhexyl, -O-hexyl, - OA or -NH-C (CH ₃ ) ₃ .

11. Use according to claim 1, wherein in the compound of formula I, the substituent B corresponds to the formula VIII, wherein the radicals R ⁵ , R ⁶ , R ⁷ and R ⁸ H and the substituent R ⁹ -OH, -OA, -A , -NH ₂ , -NHA, -NA ₂ , -NH- (CH ₂ -CH ₂ -O) _n -H, -NKCH ₂ -CH ₂ -O) _n -H] ₂ , - [NHA ₂ ] X, - [NA ₃ ] X, -SO ₃ H, -

[SO ₃ ] X or 2H-benzotriazol-2-yl mean.

12. Use according to claim 1, wherein in the compound of formula I, the substituent B corresponds to the formula IX, wherein the radicals R ⁵ , R ⁶ , R ⁷ and R ⁸ H and the substituent R ⁹ -OH, -OA, -A , -NH ₂ , -NHA, -NA ₂ , -NH-

(CH ₂ -CH ₂ -O) _n -H, -NI (CH ₂ -CH ₂ -O) _n -H] ₂ , - [NHA ₂ ] X, - [NA ₃ ] X, -SO ₃ H, -

[SO ₃ ] X or 2H-benzotriazol-2-yl mean.

13. Use according to claim 1, wherein in the compound of formula I of

Substituent B of the formula X, wherein the radicals R ⁵ , R ⁷ and R ⁸

H and R ^{6 are} -OH, -OA, -A ₁ -NH ₂ , -NHA, -NA ₂ , -NH- (CH ₂ -CH ₂ -O) _n -H, - Nt (CH ₂ -CH ₂ -O) _n -H] ₂ , - [NHA ₂ ] X, - [NA ₃ ] X, -SO ₃ H, - [SO ₃ ] X or 2H-benzotriazol-2-yl ,

14. Use according to claim 1, wherein in the compound of the formula I, the substituent B corresponds to the formula XI, where the radicals R ⁵ , R ⁶ , R ⁷ ,

R ⁸ , R ⁹ , R ¹¹ and R ^{12 are} H and R ^{10 is} H, -OH, -OA, -A, -NH ₂ , -NHA, -NA ₂ , -NH- (CH ₂ -CH ₂ -O) _n -H, -Nf (CH ₂ -CH ₂ -O) _n -H] ₂ , - [NHA ₂ ] X, - [NA ₃ ] X, -SO ₃ H, - [SO ₃ ] X or 2H-benzotriazole 2-yl mean.

15. Use according to claim 1, wherein in the compound of the formula I, the substituent B corresponds to the formula XII, where the radicals R ⁵ , R ⁶ , R ⁸ and R ^{9 are} H and R ^{7 is} -OH, -OA, -A, - NH ₂ , -NHA, -NA ₂ , -NH- (CH ₂ -CH ₂ -O) _n -H, -Nf (CH ₂ -CH ₂ -O) _n -H] ₂ , - [NHA ₂ ] X, - [NA ₃ ] X, -SO ₃ H, - [SO ₃ ] X or 2H-benzotriazol-2-yl.