EP3322400A1

EP3322400A1 - Compositions of fluorinated surfactants and antioxidants

Info

Publication number: EP3322400A1
Application number: EP16732943.2A
Authority: EP
Inventors: Manuela Loch; Reiner Friedrich
Original assignee: Merck Patent GmbH
Current assignee: Merck Patent GmbH
Priority date: 2015-07-14
Filing date: 2016-06-16
Publication date: 2018-05-23
Also published as: WO2017008877A1; US20180207080A1

Abstract

The invention relates to the use of specific fluorinated surfactants to increase the effect of antioxidants in particular in cosmetic, dermatological preparations and medicinal products, and to specific mixtures and preparations.

Description

COMPOSITIONS OF FLUORESIDES AND ANTIOXIDANTS

The invention relates to the use of special fluorosurfactants to increase the efficacy of antioxidants, especially in cosmetic, dermatological preparations and

Medical devices, as well as special mixtures and preparations.

There is a variety of surfactants for use in

known cosmetic preparations.

EP 2349989 describes, for example, alkyl sulfosuccinate monoesters and mixtures of alkyl sulfosuccinate monoesters as emulsifiers for cosmetic preparations, where the alkyl groups are linear or branched, saturated or unsaturated and have 6 to 22 C atoms. The compounds are furthermore described as being advantageous for the stabilization or dispersion of solid ingredients or active substances, for example of pigments or UV filters, in cosmetic preparations.

Another class of surfactants are fluorosurfactants. Fluorosurfactants have a superior ability to reduce the

Surface tension, for example, in the hydrophobization of surfaces e.g. of textiles, paper, glass, building materials or adsorbents. Their use as an interface mediator or emulsifier or viscosity reducer in cosmetic

Preparations are also known.

Special applications of sulfosuccinates and / or

Sulfotricarballylates with various fluorinated side chains are described in US 4,968,599 and US 4,988,610 and US 6,890,608 and in AR Pitt et al., Colloids and Surfaces A: Physicochemical and Engineering Aspects, 1996, 114, 321-335; AR Pitt, Progr. Colloid Polym. Sci., 1997, 103, 307-317 and Z.-T. Liu et al., Ind. Eng. Chem. Res. 2007, 46, 22-28. Other fluorosurfactants, in particular succinates and tricarballylates with fluorinated alkyl groups, are in WO

2009/149807, WO 2010/003567, WO 2010/149262, WO

2011/082770 and WO 2012/084118 described.

In WO 2010/149262, the fluorosurfactants described there include UV stabilizers for polymeric materials

(Plastics) or for filling materials described.

The object of the present invention was to provide further fields of application for known fluorosurfactants which, in particular in cosmetic or dermatological preparations or medical products, bring about improved properties of the preparation.

It has now surprisingly been found that particular Tricarballylate with fluorinated alkyl groups in combination with antioxidants increase their effectiveness. The increase in effectiveness can also be described as a boost effect.

A first subject of the present invention is therefore the use of compounds of the formula (I)

in which

X is a hydrophilic group, R is linear or branched alkylene having 1 to 12 C atoms, wherein one or more nonadjacent C atoms may be replaced by O, S and / or N,

r is 0 or 1,

B is a single bond, -O-, -NH-, -NR'-, -CH ₂ -, -C (O) -O-, -S-,

-CH 2 -O-, -OC (O) -, -O-C (O) -O-, -NC (O) -, -C (O) -N-, -O-C (O) -N- ,

C is (O) -N-, -Si (R ') ₂ -, -Si (R') ₂ -O-, -O-SO ₂ - or -SO 2 -O-,

R 'is a linear or branched alkyl group having 1 to 12 carbon atoms,

R ¹ and R ^{2 are} independently hydrogen or

-CH ₂ -COY ³ -L ³ - (A ³ ) n ₃ ,

Y ¹ , Y ² and Y ^{3 are} independently O, S or N,

L ¹ , L ² and L ^{3 are} independently linear or branched

Alkylene having 1 to 12 carbon atoms, wherein one or more non-adjacent C atoms may be replaced by O, S and / or N,

A ¹ , A ² and A ^{3 are} independently hydrogen or a group of the structure -Z ^ CR ^S R ^ miR, where i is 1, 2 or 3, Z 'is O, S or N and attached to a C atom of U is bound or is a single bond,

R ³ and R ^{4 are} independently hydrogen or a

are straight-chain or branched alkyl group having 1 to 12 carbon atoms,

Rf is a fluorine-containing radical,

n1, n2 and n3 are independently 1, 2 or 3,

m1, m2 and m3 are independently 0, 1, 2, 3, 4 or 5, and the compounds of formula (I) contain at least one Rf 'group to enhance the efficacy of antioxidants.

The abbreviation V here stands for the abbreviations L \ L ² and / or L ³ . When the term "one or more non-adjacent C atoms can be replaced by O, S and / or N" is used, it means that one or more non-adjacent C atoms are represented by O, S, NH and / or NR 'may be replaced, wherein R' has an aforementioned or preferred meaning.

Straight-chain or branched alkyl groups having 1 to 4, 1 to 6, 1 to 8 or 1 to 12 C atoms correspond to the formula C _P H2 _P +1 with p = 1, 2, 3 or 4, or 1, 2, 3, 4, 5 or 6, or 1, 2, 3, 4, 5, 6, 7 or 8, or 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 or 12, for example methyl , Ethyl, i-propyl, propyl, butyl, i-butyl or tert-butyl, and also pentyl, 1-, 2- or 3-methylbutyl, 1, 1-, 1, 2- or 2,2-dimethylpropyl, 1 -Ethyl propyl or hexyl, heptyl, octyl, and also nonyl, decyl, undecyl or dodecyl.

If an alkyl group is not specified, it is a straight-chain alkyl group. In perfluoroalkyl groups, all H atoms of an alkyl group are replaced by F atoms.

Linear or branched alkylene having 1 to 12 carbon atoms corresponds to the formula Cphtep and is derived from the previously described straight-chain or branched alkyl groups.

The effectiveness of the antioxidants is especially in

cosmetic or dermatological preparations or in

Medical products improved.

The effectiveness of the antioxidants is particularly preferably improved in cosmetic preparations. The effect of increasing the efficacy of the antioxidants, for example, recognized in the prevention of the decay of beta-carotene after irradiation with, for example, sun-like light, is surprisingly observed for various types of antioxidants. The fluorosurfactants themselves show no

Efficacy, as explained in the examples section. The fluorosurfactants of the formula (I) to be used according to the invention are preferably composed of a plurality of short-chain perfluoroalkyl groups having anionic, cationic, nonionic and amphoteric groups. In particular branched fluorosurfactants with short-chain

Perfluoroalkyl chains can be improved

ecotoxicological profile, since such compounds are non-toxic and show no bioaccumulation and no inhalation toxicity. Their use in cosmetics is particularly preferred because of this property.

Preferred compounds of the formula (I) are those in which two or three Rf 'groups are contained. But they are too

Compounds with at least four Rf groups possible, preferably with four, six or nine Rf 'groups.

As fluorinated groups Rf it is preferred to use branched or unbranched fluorine-containing alkyl radicals, in particular perfluorinated alkyl radicals. Fluorine-containing alkyl radicals having 1 to 0, preferably 1 to 6, in particular 1 to 4, C atoms are particularly preferred. Particular preference is given to using perfluorinated Rf groups having 1 to 6, in particular 1 to 4, C atoms. Preferably, Rf ¹ , Rf ² and Rf ^{3 have the} same meaning. Preferably, R and R ^{2 are} not simultaneously -CH ₂ -COY ³ -L ³ - (A ³ ) n ³ . In addition, preferred compounds of the formula (I) are those in which Y, Y ² and Y ^{3 are} preferably O or N, in particular O. Preferably, Y and Y ² or Y ¹ , Y ² and Y ^{3 have the} same meaning. The groups Rf are bonded to a group L ¹ , L ² or L ³ via a group -Z '(CR ³ R ⁴ ) mi. Z 'here is preferably O or N, in particular O. Preference is given to compounds in which all Z' are identical. Preferred compounds of the formula (I) are those in which n1, n-2 and n3 are preferably 1 or 2 independently of one another.

Particularly preferred compounds of the formula (I) are those in which n1, n2 and n3 are preferably each independently of one another. Preferred compounds of the formula (I) are also those in which m1, m2 and m3 are preferably, independently of one another, 0, 1, 2, 3 or 4, in particular 0 or 1.

Preferred compounds of the formula (I) are also those in which R ³ and R ⁴ independently of one another are hydrogen or a linear or branched alkyl group having 1 to 6 C atoms, in particular 1-4 C atoms. R ³ and R ⁴ independently of one another preferably represent hydrogen or an unbranched alkyl group having 1 to 3 C atoms.

Preference is given to compounds in which R ³ or R ^{4 are} identical

Is hydrogen. Preference is given to compounds in which all Z ', R ³ , R ⁴ and mi each have the same meaning.

L ¹ , L ² and L ³ may preferably be independently of one another linear or branched alkylene having 1 to 10 carbon atoms. In particular, L ¹ , L ² and L ^{3 are} independently linear or branched alkylene having 2 to 8 carbon atoms. Particularly preferred are L ¹ , L ² and L ³ independently of one another linear or branched alkylene having 2 to 6 C atoms. One or more nonadjacent C atoms of the groups L, L ² and L ³ may preferably be replaced by O or N, preferably by O. In a preferred embodiment of the compounds of the formula (I), L ¹ and L ^{2 are} identical. If L ^{3 is also} present, preferably L ¹ and L ² or L ¹ and L ³ or L ² and L ^{3 may be the} same. In a particularly preferred embodiment of the compounds of the formula (I), all groups L ¹ , L ² and L ^{3 are} identical.

Particular preference is given to compounds of the formula (I) in which at least one group U is - (CR ⁵ R ⁶ ) _C i (CR ⁷ R ⁸ ) c i -, where the indices ci and c'i are each independently 0 to 10, R ⁵ to R ⁸ independently of one another are hydrogen or a branched or linear alkyl group having 1 to 6 C atoms, with the

Condition that ci and c'i are not 0 at the same time. The sum ci and c'i is preferably 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10. Particularly preferred are ci and c'i 1. Particular preference is given to compounds of the formula (I), in in which in at least one group U, the group R ^{5 is} an alkyl group having 1 to 6 C atoms, in particular an alkyl group having 1 or 2 C atoms, and the groups R ⁶ and R ⁷ and R ^{8 is}

Hydrogen stand.

Also preferred are compounds of the formula (I) in which R ^{7 is} an alkyl group having 1 to 6 C atoms, in particular an alkyl group having 1 to 2 C atoms, and the groups R ⁵ and R ⁶ and R ^{8 is} Hydrogen stand.

In the compounds of the formula (I), the group R preferably represents linear or branched alkylene having 1 to 10 C atoms, in particular with 1 to 4 C atoms. Preferably, one or more non-adjacent C atoms may be replaced by O or S, preferably O. In the preferred compounds of the formula (I), r is preferably 0.

Preference is furthermore given to compounds of the formula (I) in which B is a single bond, -O-, -S-, -C (O) -O- or -O-C (O) -,

in particular, is a single bond.

Particularly advantageous compounds of the formula (I) are for

To increase the effectiveness of the antioxidants use, in which one or more of the variables Rf, Υ ', Ζ', U, R to R ⁸ , ci, c'i, di, ni, mi, R, r and B are the preferred meanings in particular those compounds in which the said

Variables that have particularly preferred meanings.

Particularly advantageous compounds of the formula (I) are for

To increase the effectiveness of the antioxidants to use, in which all the variables mentioned have the preferred, in particular the most preferred meanings.

In the compounds of the formula (I), X is a hydrophilic group, preferably an anionic, cationic, nonionic or amphoteric group.

A preferred anionic group X may be selected from - coo-,

-SO ₃ -, -OSOs-, -POS ^{2 "} , -OPOs ² -, - (OCH ₂ CH ₂ ) s -O- (CH ₂ ) t -COO-,

- (OCH ₂ CH ₂ ) _s -O- (CH 2) t -SO ₃ -, - (OCH ₂ CH ₂ ) _s O - (CH ₂ ) t -OSO ₃ -,

- (OCH ₂ CH ₂₎ s O- (CH2) t-P0 ₃ ² -, - (OCH2CH2) s-0- _(CH2) t-OP0 ₃ ² - or from the formulas (A ^*) to (C ^*) .

where s is an integer in the range from 1 to 1000, t is an integer selected from 1, 2, 3 or 4 and w is an integer selected from 1, 2 or 3.

Among the preferred anionic groups include

in particular -COO ^" , -SO3, -OSO3 ^' , -POs ^2" , -OPO3 ² -, the partial formula

(A ^* ), as well

- (OCH 2 CH ₂₎ s-0- _(CH2) t-COO-, - (OCH2CH2) s-0- _(CH2) t-SO3- and

- (OCH 2 CH 2) s-O- (CH 2) t -O OS 3 ^" , where each of these groups may be preferred per se.

The most preferred anionic groups are included

-SO3-, -OS0 ₃ -, -PO3 ² -, or OPO ₃ ^{2 "}

Sulfonate group -SO3 ^" is preferred.

Preferred counterion for anionic groups X is a monovalent cation, in particular H ⁺ , an alkali metal cation or N (R ^* ) ₄ ⁺ , where R * is H or a straight-chain or branched alkyl group having 1 to 6 C atoms and all R ^{* may be the} same or different. Particularly preferred are Na ⁺ , K ⁺ and NH ₄ ⁺ , more preferably Na ⁺ . A preferred cationic group X is selected from

- [NR ^r R ^{2 *} R ^{3 *} - Z-, - [PR ^{1 *} R ^{2 *} R ^{3 *} ] ⁺ Z ^" ,

where R is H or a straight-chain or branched alkyl group having 1 to 4 C atoms in any position,

Stands CHsSOs ^", CF3SO3-, CHsPhSO, ^PhSOs", R ^*, R ^{2 *} and R ^{3 *} are each independently H, a straight or branched alkyl group having 1 to 30 C - Z- is Cl-, Br, [ Atoms, Ar or -ChteAr stand and

Ar represents an unsubstituted or mono- or polysubstituted aromatic ring or fused ring systems having 6 to 30 carbon atoms, in which also one or two CH groups may be replaced by N.

The abbreviation Ph in the definition for Z ^" means phenyl.

Aryl having 6 to 30 carbon atoms denotes an aryl group having 6 to 30 carbon atoms and is an aromatic group having a common aromatic electron system having 6 to 30 carbon atoms,

optionally monosubstituted or polysubstituted by R ^{1 *} , OR, N (R ¹ ) 2, CN, NO 2 or halogen. An aryl group having 6 to 34 carbon atoms, preferably having 6 to 24 carbon atoms, is preferably substituted by R ^# , OR, N (R ^# ) 2, CN or halogen substituted or unsubstituted 1-, 2-, 3-, 4 -, 5- or 6-phenyl, 1-, 2-, 3-, 4-, 6-, 7- or 8-naphthyl, 1-, 2-, 3-, 4-, 6-, 7- or 8 Phenanthrenyl, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 anthracenyl, 1, 2, 3, 4, 5, 6 -, 7-, 8-, 9-, 10-, 11- or 12-tetracenyl, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10 , 11- or 12-benzo [a] anthracenyl, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-, 11-, 12-, 13- or 15-pentacenyl, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-, 11- or 12-chrysenyl, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9- or 10-pyrenyl, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8 -, 9-, 10-, 11- or 12-benzo [a] pyrenyl, 1-, 2-, 3-, 4-, 5-, 6-, 7- or 8-azulenyl, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9- or 10- fluoro-phenyl, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9 -, 10-, 11- or 12-

Perylenyl, 1-, 2-, 3-, 4-, 5-, 6- or 7-indenyl or 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8- or 9- fluorenyl.

The preferred cationic groups are included

in particular - NR R ^{2 *} R ^{3 *} ] ⁺ Z ^" and

each of these groups may be preferred per se.

A preferred nonionic group for X may be selected from a linear or branched alkyl group preferably having 1 to 20 carbon atoms, wherein one or more non-adjacent C atoms may be replaced by O, S, and / or N, -OH , -SH, -O- (glycoside) _0, -S- (glycoside) _0, -OCH 2 -CHOH-CH 2 OH,

-OCH ₂ Ar (-NCO) _P , -OAr (-NCO) _P ,

-CR "= CH ₂ , -OCOCR" = CH ₂ , amine oxide,

in which

u is an integer from the range from 1 to 6, preferably from 1 to 4,

o is an integer from the range of 1 to 10, p is 1 or 2,

R ^"are each independently of one another Ci-30-alkyl, Ar or -Ch Ar, preferably Ci-20-AlkyI, and

Ar represents an unsubstituted, mono- or polysubstituted aromatic ring or fused ring systems having from 6 to 30 carbon atoms.

Atoms, in which also one or two CH groups can be replaced by C = O,

Glycoside is an etherified carbohydrate, preferably a mono-, tri- or oligo-glucoside,

and R "is H or methyl.

The preferred nonionic groups X include in particular linear or branched alkyl having preferably 1 to 20 C atoms, where one or more nonadjacent C atoms may be replaced by O, S, and / or N, -OH, - OCOCR "= CH2 and -O- (glycoside) _0. If X is selected with the meaning linear or

branched alkyl, wherein one or more non-adjacent C- Atoms are replaced by O, S, and / or N, then this can be synonymously described by the formula R ^** - (B ^** -A ^** ) _m ** -, where R ^{** is} H or Ci-4 Is alkyl, in particular H or Chb, A * ^{* is} a linear or branched alkylene, preferably having 1 to 10 carbon atoms, especially 1 to 4

Carbon atoms, B ^{** is} O or S, preferably O, and m ^* * is an integer from 1 to 100, more preferably an integer from 1 to 30 stands.

Particularly preferably as a nonionic group X, the group R ^{** is} - (O-CH 2 CHR ^a ) _m -, where m ^{** is} an integer from 1 to 100, preferably an integer from 1 to 30, is in particular an integer from 1 to 15, and R ^** and R ^{a are} each independently H or Ci-4-alkyl, in each case independently of one another are H or Chh.

Particularly preferred is R ^** - (O-CH 2 CHR ^a ) _m ** - a polyethylene or polypropylene glycol unit.

A preferred amphoteric group may be selected from the functional groups of the acetyldiamines, the N-alkylamino acids, the betaines, or corresponding derivatives, in particular

selected from:

Particularly preferred compounds of the formula (I) are those which contain as hydrophilic group X one of the preferred anionic groups X, the preferred nonionic groups or the preferred zwitterionic groups. Particular preference is given to compounds of the formula (I) which contain the groups -SO ', -OSOs ^" , -POs ^2' or -OPO ₃ ² \ polyethylene glycols or polypropylene glycols, betaines or sulfobetaines.

Most particularly preferred are compounds of formula (I), which contain as the hydrophilic group X is the group -SO3. ^"Preferred

Counterions here are Na ⁺ , K ⁺ and NH ₄ ⁺ , in particular Na ⁺ .

According to the invention, compounds of the formula (I) for increasing the activity of antioxidants in which X is an anionic group, in particular -SO 3 ^~ , and one or more of the variables Rf, Υ ', Ζ', U, R ¹ , are particularly advantageously used to R ⁸ , ci, c'i, di, ni, mi, R, r and B have the preferred meanings described, in particular those compounds in which the variables mentioned have the particularly preferred meanings.

Preferred compounds are in particular those

Compounds in which all variables are the preferred ones

Meanings, especially the most preferred

Meanings, have.

In a particularly preferred group of compounds of formula (I), R ¹ and R ^{2 are} hydrogen and A ¹ and A ^{2 are} a -Z '(CR ³ R ⁴ ) miRf ⁱ group. These compounds are represented by formula (II). Particular preference is given to compounds of the formula (II) where Y, Y ² , Z ¹ and Z ^{2 are} identical to O.

In another preferred group of compounds of formula (I) R ^{1 is} H, R ^{2 is} -CH ₂ -COY ³ -L ³ - (A ³ ) n ³ and A ¹ , A ² and A ^{3 is} a -Z ⁱ (CR ³ R ⁴ ) miRf 'group. These connections are through Formula (III) shown. Particularly preferred are compounds of formula (III) with Y, Y ² , Y ³ , Z \ Z ² and Z ³ equal to O.

In a further preferred group of compounds of the formula (I), R ^{1 is} -CH 2 -COY ³ -L ³ - (A ³ ) n ³ , R ^{2 is} hydrogen and A ¹ , A ² and A ^{3 is} a -Z '( CR ³ R) miRf group. These compounds are represented by formula (IV). Particularly preferred

Compounds of formula (IV) with Y ¹ , Y ² , Y ³ , ZZ ² and Z ³ equal to O.

(IV) Particularly preferred compounds of formula (I) are

Compounds of formulas (II), (III) and (IV) in which X is an anionic group. Particular preference is given to compounds of the formulas (II), (III) and (IV) which contain the groups -SO ₃ ^" , -OSO ₃ , -PO 3 ² - or -OPO 3 ^2" , in particular -SO 3 ^"

Counterions here are Na ⁺ , K ⁺ and NH ₄ ⁺ , in particular Na ⁺ .

In the formulas (II), (III) and (IV), L ¹ , L ² and L ^{3 have} the general and preferred meanings given for the formula (I). In particular, compounds of formulas (II), (III) and (IV) are preferred in which all L 'are the same. Preference is also given to compounds of the formulas (II), (III) and (IV) with perfluorinated groups R having 1 to 4 C atoms. Preferably, Rf ¹ , Rf ² and Rf ^{3 have the} same meaning. Preferred examples of the group Rf are pentafluoroethyl, n-heptafluoropropyl, n-nonafluorobutyl

Another object of the invention is therefore the

Use as described above, characterized in that as compounds of the formula (I) compounds of the formulas (II), (III) and / or (IV) are used,

(IV)

in which

X is -SO ₃ -, -OSO ₃ -, -PO ₃ ² - or OPO 3 ^{2 "} , in particular -SO ₃ -,

Y ¹ , Y ² , Y ³ , Z ¹ , Z ² and Z ^{3 are} O, Rf, Rf ² and Rf ^{3 are} perfluorinated groups Rf having 1 to 4 carbon atoms,

n1, n2 and n3 are 1 or 2,

m1, m2 and m3 are 0, 1, 2, 3 or 4,

L, L ² and L ^{3 are} a linear or branched alkylene having 2 to 6 carbon atoms and

R ³ and R ^{4 are} hydrogen or an alkyl group having 1 to 3

C atoms are. In a preferred variant of the compounds of the formulas (II), (III) and (IV) R ³ and R ^{4 are} identical. Further preferred compounds are those in which R ³ or R ^{4 are} hydrogen and m 1, m 2 and m 3 are 0 or 1. Preference is given to compounds in which all Rf, R ³ , R ⁴ , ni and mi each have the same meaning.

Particular preference is given to compounds of the formulas (II), (III) and (IV) in which all variables have the preferred meanings, in particular the particularly preferred meanings.

Particular preference is given to using compounds of the formula (III) in which all variables have the preferred meanings, in particular the particularly preferred meanings.

Examples of compounds of the formula (I) or of the formula (III) whose use is particularly advantageous are compounds of the formulas (III-1) to (III-6):

Examples of compounds of the formula (I) whose use is particularly advantageous are compounds of the formulas (II 1-1) and (III-2), as described above.

The compounds of the formulas (I), (II), (III) and (IV) can also be used as mixtures of isomers (constitutional and / or

Configuration isomer mixtures). Especially

Diastereomeric and / or enantiomeric mixtures are possible. The formulas given include all of these forms.

The compounds of the formula (I) as described above or described as being preferred in which Y ¹ and Y ^{2 are} O may preferably be prepared by esterification of maleic acid and aconitic acid or their anhydrides or acid chlorides with one or more alcohols of the formula (V) getting produced,

(V) and subsequent addition to the double bond to introduce the X- (R) _r -B moiety as previously described. The compounds of the formula (I) may also be preferred by esterification of

Malic acid and citric acid with one or more Alcohols of formula (V) and subsequent functionalization of the hydroxy groups to introduce the grouping X- (R) rB are prepared. U and A 'in formula (V) have the meaning described for L \ L ² and L ³ or A ¹ , A ² and A ³ in formula (I), in particular also the preferred meanings. The alcohols of formula (V) may be one or more

Contain Rfi groups as previously described.

The alcohols used are commercially available and / or their preparation is familiar to the person skilled in the art (eg DE 10 2009 030 846 A1; Heilmann et al., J. Fluorine Chem. 1992, 59, 387; Janulis et al., US Pat. No. 5,157,159 (1992 Carbohydrate Research 1991, 219, 33).

The synthesis of the succinates or tricarballylates of the formula (I) is preferably carried out in a two-stage synthesis via the corresponding maleates or hydroxysuccinates or the corresponding aconitic or citric acid esters. These syntheses are described in WO 2010/149262, in particular in Examples 1, 5-9, WO 2011/082770 and WO 2012/084118. The disclosures in the cited references are hereby expressly also to

Disclosure of the present application. As described above, the compounds of the formula (I), (II), (III) or (IV) and those described as being preferred

Connect a boost effect of antioxidants.

Examples of antioxidants whose efficacy is enhanced are amino acids, imidazoles, peptides, carotenoids, carotenes,

Chlorogenic acid and its derivatives, lipoic acid and its derivatives, aurothioglucose, thiols, thiodipropionic acid and its derivatives, Sulfoximine compounds, (metal) chelators, unsaturated

Fatty acids and their derivatives, vitamin C and derivatives, tocopherols and derivatives, vitamin A and derivatives, rutinic acid and their

Derivatives, flavonoids and their derivatives, ferulic acid, furfurylidene glucitol, carnosine, butylhydroxytoluene, butylated hydroxyanisole,

Nordohydroguajaretic acid, trihydroxybutyrophenone, uric acid and its derivatives, mannose and its derivatives, stilbenes and their derivatives, derivatives of benzylidene-2,4-alkanedione, derivatives of benzylidenemalonic acid or derivatives of benzylmalonic acid.

Another object of the invention is therefore the

Use of compounds of the formula (I), (II), (III), (IV) or the preferred compounds as described above, wherein the

Efficacy of the antioxidants from the group of amino acids, imidazoles, peptides, carotenoids, carotenes, chlorogenic acid and its derivatives, lipoic acid and its derivatives, aurothioglucose, thiols, thiodipropionic acid and its derivatives, sulfoximine compounds, (metal) chelators, unsaturated fatty acids and their derivatives, vitamin C and derivatives, tocopherols and derivatives, vitamin A and derivatives, rutinic acid and derivatives thereof, flavonoids and their derivatives, ferulic acid, furfurylidene glucitol, carnosine,

Butylhydroxytoluene, butylhydroxyanisole, nordohydroguajaretic acid, trihydroxybutyrophenone, uric acid and its derivatives, mannose and its derivatives, stilbenes and their derivatives, derivatives of benzylidene-2,4-pentanedione, derivatives of benzylidenemalonic acid or derivatives of benzylmalonic acid.

Suitable amino acids are, for example, glycine, histidine, tyrosine, tryptophan, thiotain.

A suitable imidazole is, for example, urocanic acid and its derivatives. Suitable derivatives are, for example, salts with cosmetically acceptable cations, esters and ethers.

Suitable peptides are, for example, D, L-carnosine, D-carnosine, L-carnosine and their derivatives, for example anserine.

Suitable carotenes are, for example, α-carotene, β-carotene,

Lycopene.

A suitable derivative of the lipoic acid is dihydrolipoic acid.

Suitable thiols include thioredoxin, glutathione, cysteine, cystine, cystamine and their glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl, lauryl, palmitoyl, oleyl, a-linoleyl , Cholesteryl and glyceryl esters and their salts.

Suitable derivatives of thiodipropionic acid are, for example, dilauryl thiodipropionate, distearyl thiodipropionate, their ethers,

Peptides, lipids, nucleotides, nucleosides and their salts.

Suitable suloximine compounds are, for example

Buthionine sulfoximine, homocysteine sulfoxime, buthione sulfone, penta-, hexa- and heptathionine sulfoximine,

Suitable (metal) chelators are α-hydroxy fatty acids,

Palmitic acid, phytic acid, lactoferrin, α-hydroxy acids such as

Citric acid, lactic acid, malic acid, humic acid, bile acid, bile extracts, bilirubin, biliverdin, EDTA, EGTA or unsaturated fatty acids.

Suitable derivatives of vitamin C are ascorbyl palmitate,

Magnesium ascorbyl phosphate or ascorbyl acetate.

A suitable derivative of tocopherol is tocopherol acetate.

A suitable derivative of vitamin A is vitamin A palmitate.

The term "flavonoid" includes, in particular, compounds which, owing to their basic structure, can be assigned to the following groups:

• Chalets

• Chromones • Aurones

• Flavanones

Flavan-3-ols (catechins)

• Flavones

• Isoflavones

Flavan-3,4-diols (leucoanthocyanidins)

Flavonols (3-hydroxy-flaven-4-one)

• Flavanonols

Examples are the following flavonoids should be mentioned: 5-hydroxy-7,4 ^{'-dimethoxyflavon-8-sulfate,} 7,8-dihydroxyflavone, luteolin (flavone); Catechin, epicatechin, epigallocatechin gallate (EGCG, TEAVIGO ^® DSM) (flavan-3-ols and flavan-3-ol derivatives);

Fighter Oi (flavonol); Taxifolin (flavanonol), the isoflavones of the group Isoflavone, Daidzein, Genistein, Prunetin, Biochanin A, Orobol, Santa! or pratense, and naringenin (flavanone), and naringenin glycosides, for example naringin-7-neohesperidoside.

Preferred flavonoids are derived from the following groups:

• flavonols

• flavonol-o-glycosides

Flavonol-o-glycoside-containing extracts

The preferred flavonoids also include aglyka (sugarless structures) and aglycone conjugates. Possible aglycone conjugates are hydroxyl derivatives wherein the hydroxyl groups are wholly or partially alkylated, methylated, glycated, sulfated or esterified. Besides hydroxyl derivatives, C derivatives are also suitable as aglycone conjugates. Particularly preferred for the group of flavonols is the aglycone quercetin.

In the group of flavonol-o-glycosides are the flavono-3-glycosides such as rutin, α-glucosylrutin, tiliroside, isoquercetin,

Rutinsulfat, Trishydroxyethylrutin (troxerutin) and their sulfates and phosphates particularly preferred.

Flavonol 7 and 8 glycosides can also be used.

The term "rutin sulfate" includes mono-, di-, tri-, tetra- or

Polysulfates of rutin or mixtures of these rutin sulfates. The term "troxerutin" includes mono-, di-, tri- tetra- or

Polyethoxylates of rutin or mixtures of these Rutinethoxylate.

For the group of flavonol- or flavonol-o-glycoside-containing extracts, the active ingredient combinations Emblica, Licorice and / or horse chestnut extract are preferred. Emblica is obtained from the fruits of the deciduous tree Phyllanthus emblica (also Emblica officinalis) e.g. won in India, China, Pakistan or Nepal. The main ingredients of Emblica are the low-molecular tannins Emblicanin A and B, which form the iron in the form of skin

Bind complexes. Preferred emblica solutions are commercially available for example as EMBLICA ^® (MERCK) or CAPROS ^® available. In principle, all Emblica mixtures come alone or in combination as an antioxidant in question. The licorice extract contains the flavonoid glabridin (a stearyl glycyrhetinate) and / or licochalcone A.

The horse chestnut extract contains e.g. Esculin and more

Flavonol and / or flavonol glycoside components. Such vegetable substance mixtures can be obtained in a manner familiar to the person skilled in the art, for example by expressing or extracting the corresponding plants. In a preferred embodiment of the invention, the

Effectiveness of flavonoids selected from the group quercetin, rutin, rutin sulfate, a-glucosylrutin, tiliroside, troxerutin and / or isoquercetin increased.

In a further preferred embodiment of the invention, the activity of derivatives of benzylidene-2,4-alkanedione, derivatives of Benzylidenmalonsäure or derivatives of the

Benzylmalonsäure reinforced, which are described by the formulas (A) and (B).

Another object of the invention is therefore the use of compounds of formula (I), (II), (III), (IV) or preferred

Compounds, as described above, for increasing the

effectiveness of compounds of formula (A) and / or (B),

wherein

R 1 -C (O) R _6> -CO 2 R ₆ or -C (O) N (R) 2,

R 2 denotes linear or branched alkyl having 1 to 30 C atoms,

X is O, NH or a bond,

R 3 is H or linear or branched alkyl having 1 to 20 C atoms,

R ₄ and R 5 are each independently of one another H, linear or branched alkyl having 1 to 12 C atoms or linear or branched alkoxy having 1 to 12 C atoms,

R6 is linear or branched alkyl having 1 to 30 carbon atoms and Rzjeweils independently H or linear or branched alkyl having 1 to 8 carbon atoms.

Preferred derivatives of the benzylidene-2,4-alkanedione are

Compounds of the formula (A) in which R 1 -C (O) R 6 and X form a bond, corresponding to the formula (A-1),

wherein R2, R3, R4, R5, R6 and R7 have a formula (A) previously mentioned meaning.

In compounds of the formula (A-1), R 3 is preferably a linear or branched alkyl group having 1 to 4 C atoms.

In compounds of the formula (A-1), R ₄ and R 5 are preferably the same and a linear or branched alkoxy group having 1 to 4 C atoms. In compounds of the formula (A-1), R 6 and R 2 are preferably the same and a linear or branched alkyl group having 1 to 4 C atoms. Particularly preferred compounds of the formula (A-1) are

Compounds in which preferably a linear or branched alkyl group having 1 to 4 C atoms R3, _R4 and R5 preferably identical and are a linear or branched alkoxy group having 1 to 4 carbon atoms, and R6 and R 2 are preferably identical and are a linear or branched alkyl group having 1 to 4 carbon atoms.

Preferred compounds of the formula (A) -1 are, for example, 3- (3,4,5-trimethoxybenzylidene) -2,4-pentanedione, 3- (3,4,5-triethoxybenzylidene) -2,4-pentanedione, 3- ( 3,4,5-tripropoxybenzylidene) - 2,4-pentanedione, 3- (3,4,5-tributoxybenzylidene) -2,4-pentanedione, 3- (3,4,5-trimethoxybenzylidene) -2,4-heptanedione , 3- (3,4,5- Triethoxybenzylidene) -2,4-heptanedione, 3- (3,4,5-tripropoxybenzylidene) -2,4-heptanedione, 3- (3,4,5-tributoxybenzylidene) -2,4-heptanedione, 3- (3, 4,5-trimethoxybenzylidene) -2,4-nanoanedione, 3- (3,4,5-triethoxybenzylidene) -2,4-nonanedione, 3- (3,4,5-tripropoxybenzylidene) -2,4-nonanedione, 3 - (3,4,5-Tributoxybenzyliden) -2,4-nonanedione.

A particularly preferred compound of formula (A-1) is 3- (3,4,5-trimethoxybenzylidene) -2,4-pentanedione. This compound is commercially available under the trade name Synoxyl® HSS from Sytheon Ltd.

Preferred derivatives of benzylidenemalonic acid are compounds of the formula (A) where R 1 is -CO 2 R 6 and X is O,

according to the formula (A-2),

wherein R2, R3, R4, Rs, R6 and R7 have a meaning previously given for formula (A).

In compounds of formula (A-2), R3 is preferably H or a linear or branched alkyl group having 1 to 4 carbon atoms.

In compounds of the formula (A-2), R 3 is particularly preferably H.

In compounds of the formula (A-2), R _{4 is} preferably H or a linear or branched alkoxy group having 1 to 4 C atoms.

In compounds of the formula (A-2), R _{4 is} particularly preferably a linear or branched alkoxy group having 1 to 4 C atoms.

In compounds of formula (A-2), Rs is preferably H or a linear or branched alkoxy group having 1 to 4 carbon atoms. in compounds of the formula (A-2), R 5 is particularly preferably a linear or branched alkoxy group having 1 to 4 C atoms.

In compounds of the formula (A-2), R 6 and R 2 are preferably the same and a linear or branched alkyl group having 1 to 2 C atoms.

Particularly preferred compounds of the formula (A-2) are

Compounds in which R3 is preferably H or a linear or branched alkyl group having 1 to 4 carbon atoms, R4 is preferably H or a linear or branched alkoxy group having 1 to 4 carbon atoms, R5 is preferably H or a linear or branched alkoxy group Is 1 to 4 carbon atoms and R6 and R2 are preferably the same and are a linear or branched alkyl group having 1 to 12 carbon atoms. Preferred compounds of formula (A-2) are 2- (4-hydroxy-3,5-dimethoxybenzylidene) -malonic acid bis (2-ethylhexyl) ester, 2- (4-hydroxy-3,5-diethoxybenzylidene) -malonic acid bis (2-ethylhexyl) ester, 2- (4-hydroxy-3,5-dipropoxybenzylidene) malonic acid bis (2-ethylhexyl) ester, 2- (4-hydroxy-3,5-dimethoxybenzylidene) malonic acid bis-methyl ester, 2- (4-hydroxy-3,5-diethoxybenzylidene) malonic acid bis-methyl ester, 2- (4-hydroxy-3,5-dipropoxybenzylidene) malonic acid bis-methyl ester, 2- (4- Hydroxy-3,5-dimethoxybenzylidene) malonic acid bis-isopropyl ester, 2- (4-hydroxy-3,5-diethoxybenzylidene) -malonic acid bis-isopropyl ester, 2- (4-hydroxy-3,5-dipropoxybenzylidene) -malonic acid bis-isopropyl ester, 2- (4-

Hydroxy-3-methoxybenzylidene) malonic acid bis-isopropyl ester, 2- (4-hydroxy-3-ethoxybenzylidene) malonic acid bis-isopropyl ester, 2- (4-hydroxy-3-propoxybenzylidene) malonic acid bis-isopropyl ester, 2 - (4-Hydroxy-3-methoxybenzylidene) -malonic acid bis-methyl ester, 2- (4-hydroxy-3-ethoxybenzylidene) -malonic acid bis-methyl ester, 2- (4-hydroxy-3-propoxybenzylidene) -malonic acid bis methyl ester, 2- (4-hydroxy-3-methoxybenzylidene) malonic acid bis (2-ethylhexyl) ester, 2- (4-Hydroxy-3-ethoxybenzylidene) -malonic acid bis (2-ethylhexyl) ester, 2- (4-hydroxy-3-propoxybenzylidene) -malonic acid bis (2-ethylhexyl) ester, 2- (4 -Methoxybenzylidene) -malonic acid bis (2-ethylhexyl) ester, 2- (4-ethoxybenzylidene) -malonic acid bis (2-ethylhexyl) ester, 2- (4-propoxybenzylidene) -malonic acid bis (2-ethylhexyl ) bis, 2- (4-methoxybenzylidene) malonic acid, bismethyl 2- (4-ethoxybenzylidene) malonate, bismethyl 2- (4-ethoxybenzylidene) malonate, bismethyl 2- (4-propoxybenzylidene) malonate, 2- (4- Methoxybenzylidene) -malonic acid bis-isopropyl ester, 2- (4-ethoxybenzylidene) -malonic acid bis-isopropyl ester, 2- (4-propoxybenzylidene) -malonic acid bis-isopropyl ester.

Particularly preferred compounds of the formula (A-2) are 2- (4-hydroxy-3,5-dimethoxybenzylidene) malonic acid bis (2-ethylhexyl) esters, 2- (4-hydroxy-3-methoxybenzylidene) -malonic acid bis-isopropyl ester and 2- (4-methoxybenzylidene) -malonic acid bis (2-ethylhexyl) ester.

A most preferred compound of formula (A-2) is 2- (4-hydroxy-3,5-dimethoxybenzylidene) -malonic acid bis (2-ethylhexyl) ester, which is an active ingredient of the Oxynex® ST Liquid brand product of the company Merck is marketed.

Preferred derivatives of benzylmalonic acid are compounds of the formula (B) where R 1 is -CO 2 R 6 and X is O, corresponding to the formula B-1),

(B-1) wherein R2, R3, R4, R5, R6 and R7 have a formula (B) previously mentioned meaning.

In compounds of the formula (B-1), R 3 is preferably H or a linear or branched alkyl group having 1 to 4 C atoms.

In compounds of the formula (B-1), R 3 is particularly preferably H.

In compounds of the formula (B-1), R _{4 is} preferably H or a linear or branched alkoxy group having 1 to 4 C atoms.

In compounds of the formula (B-1), R _{4 is} particularly preferably a linear or branched alkoxy group having 1 to 4 C atoms.

In compounds of the formula (B-1), R 5 is preferably H or a linear or branched alkoxy group having 1 to 4 C atoms.

In compounds of the formula (B-1), R 5 is particularly preferably a linear or branched alkoxy group having 1 to 4 C atoms.

In compounds of the formula (B-1), R 6 and R 2 are preferably the same and a linear or branched alkyl group having 1 to 12 C atoms.

Particularly preferred compounds of the formula (B-1) are

Compounds in which R ₃ is preferably H or a linear or branched alkyl group having 1 to 4 C atoms, R _{4 is} preferably H or a linear or branched alkoxy group having 1 to 4 C atoms, R _{5 is} preferably H or a linear or branched Alkoxy group having 1 to 4 carbon atoms and R6 and R2 is preferably the same and a linear or branched alkyl group having 1 to 12 carbon atoms.

Preferred compounds of formula (B-1) are 2- (4-hydroxy-3,5-dimethoxybenzyl) -malonic acid bis (2-ethylhexyl) ester, 2- (4-hydroxy-3,5-diethoxybenzyl) -malonic acid bis (2-ethylhexyl) ester, 2- (4-hydroxy-3,5-dipropoxybenzyl) -malonic acid bis (2-ethylhexyl) ester, 2- (4-Hydroxy-3,5-dimethoxybenzyl) -malonic acid bis-methyl ester, 2- (4-hydroxy-3,5-diethoxybenzyl) -malonic acid bis-methyl ester, 2- (4-hydroxy-3,5-dipropoxybenzyl ) -malonic acid bis-methyl ester, 2- (4-hydroxy-3,5-dimethoxybenzyl) -malonic acid bis-isopropyl ester, 2- (4-hydroxy-3,5-diethoxybenzyl) -malonic acid bis-isopropyl ester, 2- (4-hydroxy-3,5-dipropoxybenzyl) malonic acid bis-isopropyl ester, 2- (4-hydroxy-3-methoxybenzyl) -malonic acid bis-isopropyl ester, 2- (4-hydroxy-3-ethoxybenzyl) -malonic acid bis-isopropyl ester, 2- (4-hydroxy-3-propoxybenzyl) -malonic acid bis-isopropyl ester, 2- (4-hydroxy-3-methoxybenzyl) -malonic acid bis-methyl ester, 2- (4-

Hydroxy-3-ethoxybenzyl) -malonic acid bis-methyl ester, 2- (4-hydroxy-3-propoxybenzyl) -malonic acid bis-methyl ester, 2- (4-hydroxy-3-methoxybenzyl) -malonic acid bis (2- ethylhexyl) ester, bis (2-ethylhexyl) 2- (4-hydroxy-3-ethoxybenzyl) -maionate, 2- (4-hydroxy-3-propoxybenzyl) -malonic acid bis (2-ethylhexyl) ester, 2- (4-methoxybenzyl) -malonic acid bis (2-ethylhexyl) ester, 2- (4-ethoxybenzyl) -malonic acid bis (2-ethylhexyl) ester, 2- (4-propoxybenzyl) -malonic acid bis- (2-ethylhexyl) ester, 2- (4-methoxybenzyl) -malonic acid bis-methyl ester, 2- (4-ethoxybenzyl) -matic acid bis-methyl ester, 2- (4-propoxybenzyl) maloric acid bis-methyl ester, 2 - (4-methoxybenzyl) -malonic acid bis-isopropyl ester, 2- (4-ethoxybenzyl) -malonic acid bis-isopropyl ester, 2- (4-propoxybenzyl) -malonic acid bis-isopropyl ester. A very particularly preferred compound of formula (B) is 2- (4-hydroxy-3,5-dimethoxybenzyl) -malonic acid-bis- (2-ethylhexyl) ester, which is marketed under the brand name RonaCare AP ^® from Merck , The compounds of the formula (A), (A-1), (A-2), (B) and (B-1) described above or described as preferred Reinforced according to the invention in a particularly preferred manner in their effect.

Another object of the invention is therefore the

Effectiveness of the antioxidants from the group 2- (4-hydroxy-3,5-dimethoxybenzylidene) -malonic acid bis (2-ethylhexyl) ester, 2- (4-hydroxy-3,5-dimethoxybenzyl) -malonic acid bis ( 2-ethylhexyl ester, 2- (4-hydroxy-3-methoxybenzylidene) -malonic acid bis-isopropyl ester, 2- (4-hydroxy-3-methoxybenzyl) -malonic acid bis-isopropyl ester, 2- (4-methoxybenzylidene) - malonic acid bis (2-ethylhexyl) ester and / or 3- (3,4,5-trimethoxybenzylidene) -2,4-pentanedione is amplified. Another object of the invention is therefore the

Effectiveness of the antioxidants from the group 2- (4-hydroxy-3,5-dimethoxybenzylidene) -malonic acid bis (2-ethylhexyl) ester and / or 2- (4-hydroxy-3,5-dimethoxybenzyl) -malonic acid bis - (2-ethylhexyl) ester is amplified.

For practicing the invention, the compounds of formula (I), (II), (III), (IV) or the preferred compounds as described above may be mixed with the antioxidants as previously described or preferred. Such mixtures are then preferably incorporated into a cosmetic or dermatological preparation or a medical device. Such mixtures may be a premix for a

Be prepared, for example, powdered ingredients, as a powder mixture as such with at least one suitable Carrier and optionally other ingredients for the preparation of the cosmetic or dermatological preparation or the medical device is used.

Typical carriers for a pulverulent mixture are sorbitol, lactose, talc, silicic acid, aluminum hydroxide,

Calcium silicate, polyamide powder or mixtures of these substances.

Suitable mixtures may also be a premix for a preparation, for example in the form of a paste or solution of the ingredients, which is used as a mixture as such with at least one suitable carrier and optionally other ingredients for the preparation of the cosmetic or dermatological preparation or the medical device.

The mixture of the compounds of formula (I), (II), (IM), (IV) or the preferred compounds as described above, with the

Antioxidants, as described or preferred described above, may include, contain, consist essentially of, or consist of the necessary or optional ingredients mentioned. Any compounds or components which may be used in the compositions are either known and commercially available or may be synthesized by known methods.

A further subject of the invention is likewise a mixture comprising a compound of the formula (I),

in which

X is a hydrophilic group,

R is linear or branched Aikylen having 1 to 12 C atoms, wherein one or more non-adjacent C atoms may be replaced by O, S, and / or N,

r is 0 or 1,

B is a single bond, -O-, -NH-, -NR'-, -CH ₂ -, -C (O) -O-, -S-, -CH ₂ -O-, -OC (O) -, -0 -C (O) -O-, -NC (O) -, -C (O) -N-, -O-C (O) -N-, -N-C (O) -N-, -Si ( R ') is ₂ -, -Si (R 0 -, -O-SO ₂ - or -SO 2 -O-,

where R 'is a linear or branched alkyl group having 1 to 12 C atoms,

R ¹ and R ^{2 are} independently hydrogen or

-CH ₂ -COY ³ -L ³ - (A ³⁾ _n3 are

Y ¹ , Y ² and Y ^{3 are} independently O, S or N,

L ¹ , L ² and L ^{3 are} independently linear or branched Aikylen having 1 to 12 carbon atoms, wherein one or more non-adjacent carbon atoms may be replaced by O, S, and / or N, A ¹ , A ² and A ^{3 are} independently hydrogen or a group of the structure -Z ⁱ (CR ³ R ⁴ ) miRf ⁱ , where i is 1, 2 or 3, Z 'is O, S or N and attached to a C atom of U. or is a single bond,

R ³ and R ^{4 are} independently hydrogen or a

are straight-chain or branched alkyl group having 1 to 12 carbon atoms,

Rf is a fluorine-containing radical,

n1, n2 and n3 are independently 1, 2 or 3,

m1, m2 and m3 are independently 0, 1, 2, 3, 4 or 5, and the compounds of formula (I) contain at least one Rf group, and at least one antioxidant, as previously described or preferably described. A further subject of the invention is likewise a mixture containing a compound of the formula (I)

in which

X is a hydrophilic group,

R is linear or branched alkylene having 1 to 12 C atoms, wherein one or more nonadjacent C atoms may be replaced by O, S, and / or N,

r is 0 or 1,

B is a single bond, -O-, -NH-, -NR ^! -, - CH ₂ -, -C (O) -O-, -S-, -CH ₂ -O-, -OC (O) -, -OC (O) -O-, -NC (O) -, - C (O) -N-, -O-C (O) -N-, -N-C (O) -N-, -Si (R ') 2-, -Si (R') ₂ -O-, Is -O-SO 2 - or -SO 2 -O-,

where R 'is a linear or branched alkyl group having 1 to 12 C atoms,

R and R ^{2 are} independently hydrogen or

Are -CH ₂ -COY ³ -L ³ - (A ³ ) n ³ ,

Y ¹ , Y ² and Y ^{3 are} independently O, S or N,

L ¹ , L ² and L ^{3 are} independently linear or branched

Alkylene having 1 to 12 carbon atoms, wherein one or more non-adjacent C atoms may be replaced by O, S, and / or N,

A ¹ , A ² and A ^{3 are} independently hydrogen or a group of the structure -Z ⁱ (CR ³ R ⁴ ) _m iRf ⁱ , where i is 1, 2 or 3,

Z 'is O, S or N and is bonded to a C atom of U or one

Single bond is,

R ³ and R ^{4 are} independently hydrogen or a

are straight-chain or branched alkyl group having 1 to 12 carbon atoms,

Rf is a fluorine-containing radical, n1, n2 and n3 are independently 1, 2, or 3,

m1, m2 and m3 are independently 0, 1, 2, 3, 4 or 5, and the compounds of the formula (I) contain at least one Rf 'group, and one or more compounds of the formula (A) and / or ( B)

wherein

R 1 is -C (O) R ₆ , -CO _{2 is} Re or -C (O) N (R ₇ ) 2,

R 2 denotes linear or branched alkyl having 1 to 30 C atoms,

X is O, NH or a bond,

R 3 denotes H or linear or branched alkyl having 1 to 20 C atoms,

R6 is linear or branched alkyl having 1 to 30 carbon atoms and

Each R ₇ is independently H or linear or branched alkyl having 1 to 8 carbon atoms.

Preferred mixtures are mixtures of preferred

Compounds of formula (I), (II), (III) or (IV) with preferred compounds of formula (A), (A-1), (A-2), (B) or (B-1).

Particularly preferred mixtures are mixtures of

preferred compounds of the formula (I), (II), (III) or (IV) with the compounds 2- (4-hydroxy-3,5-dimethoxybenzylidene) -malonic acid bis (2-ethylhexyl) esters, 2- (4-hydroxy-3,5-dimethoxybenzyl) malonic acid bis (2-ethylhexyl) esters, 2- (4-hydroxy-3-methoxybenzylidene) malonic acid bis- isopropyl ester, 2- (4-hydroxy-3-methoxybenzyl) -malonic acid bis-isopropyl ester, 2- (4-methoxybenzylidene) -malonic acid bis (2-ethylhexyl) ester and / or 3- (3,4,5-bis) trimethoxybenzylidene) -2,4-pentanedione.

Another object of the invention are mixtures containing 2- (4-hydroxy-3,5-dimethoxybenzylidene) -malonic acid bis (2-ethylhexyl) ester and / or 2- (4-hydroxy-3,5-dimethoxybenzyl) - malonic acid bis (2-ethylhexyl) ester and the compound of formula (UM):

The mixtures may preferably contain adjuvants such as cosmetic oils (e.g., Caprylic / Capric

Triglycerides, C12-15 alkyl benzoates, isopropyl myristate, arylalkyl benzoates, e.g. Phenethylbenzoate (X-Tend 226) or

Cosmacol brand oil components such as dimyristyl tartrate, tri C14-C15 alkyl citrate, C12-C13 alkyl lactate, tridecyl salicylate, C12-C13 alkyl octanoate, C12-C13 alkyl maleate, C12-C13 alkyl citrate, C12-C13 alkyl tartrate), or polar protic auxiliaries (for example propylene glycol, butylene glycol, glycerol, isopropanol, ethanol) or so-called solubilizers (eg butylphthalimides, isopropylphthalimides, dimethylisosorbides). Most preferred cosmetic oils are C12-C13 alkyl lactates, commercially available as Cosmacol ELI and phenethyl benzoate, commercially available as X-Tend 226. Preference is given to the compound 2- (4-hydroxy-3,5-dimethoxybenzylidene) -malonic acid bis (2-ethylhexyl) ester without a further auxiliary and a compound of the formula (I), (II), (III) or ( IV), in particular with the compound of formula (III-1), used in the mixture. A preferred excipient is a mixture of caprylic and capric triglyceride with the INCI name caprylic / capric triglyceride.

Alternatively, the compound 2- (4-hydroxy-3,5-dimethoxybenzylidene) -malonic acid bis (2-ethylhexyl) ester together with a cosmetic excipient and a compound of formula (I), (II), (III) or (IV), in particular with the compound of formula (III-1), used in the mixture. A preferred excipient is a mixture of caprylic and capric triglyceride with the INCI name caprylic / capric triglyceride. An alternative adjuvant is 1-methoxy-2-propanol.

Preference is given to the compound 2- (4-hydroxy-3,5-dimethoxybenzylidene) -malonic acid bis (2-ethylhexyl) ester together with 2- (4-hydroxy-3,5-dimethoxybenzyl) -malonic acid bis (2 - ethylhexyl) ester and a compound of formula (I), (II), (III) or (IV), in particular with the compound of formula (111-1), used in the mixture. Preference is given to the compound 2- (4-hydroxy-3,5-dimethoxybenzyl) malonic acid bis (2-ethylhexyl) ester without a further auxiliary and a compound of the formula (I), (II), (III) or ( IV), in particular with the compound of formula (III-1), used in the mixture. The mixture is then preferably a solution. Another object of the invention is therefore a mixture consisting of 2- (4-hydroxy-3,5-dimethoxybenzyl) -malonic acid bis (2-ethylhexyl) ester and the compound of formula (ltl-1):

Another object of the invention is also a mixture consisting of 2- (4-hydroxy-3,5-dimethoxybenzyl) -malonic acid bis (2-ethylhexyl) ester 2- (4-hydroxy-3,5-dimethoxybenzyl) -malonic acid bis-2-eth l l l l ester and the Verbindun of formula 111-1:

Another object of the invention is also a mixture consisting of 2- (4-hydroxy-3,5-dimethoxybenzylidene) -malonic acid bis (2-ethylhexyl) ester and the compound of formula (111-1):

A further subject of the invention is likewise a mixture consisting of 2- (4-hydroxy-3,5-dimethoxybenzylidene) -malonic acid bis (2-ethylhexyl) ester, 1-methoxy-2-propanol and the compound of formula (III-1):

Preferably, the mixture as previously described or preferably described contains a compound of formula (I) and an antioxidant in a weight ratio of 1: 1 to 1:20, preferably in a weight ratio of 1: 4 to 1: 15., More preferably in a weight ratio of 1: 9. If several compounds of the formula (I) or several antioxidants are used together, the total amount for the weight ratio is decisive.

A further subject of the invention are likewise preparations, in particular cosmetic or dermatological preparations or medical products, containing at least one compound of the formula (I), as described above or described as being preferred,

at least one antioxidant, as previously described or preferred, or a blend of the invention as previously described or described as preferred.

Another object of the invention are also preparations containing at least one compound of formula (I), as described above or described as preferred, at least one

A compound of the formula A and / or B as described above or preferably described or a mixture according to the invention as described above or described as being preferred. The preparation preferably contains, as described above or preferably described, a compound of the formula (I) and an antioxidant in a weight ratio of 1: 1 to 1:20, preferably in a weight ratio of 1: 4 to 1:15, particularly preferably in a weight ratio of 1: 9. If several compounds of the formula (I) or several antioxidants are used together, the total amount for the weight ratio is decisive.

The preparation preferably contains, as described above or preferably described, the mixture according to the invention in an amount of from 0.01% by weight to 20% by weight, preferably 0.5% by weight to 10% by weight, particularly preferably 0.75% by weight. % to 2% by weight, most preferably one

Weight. All information is based on the total amount of the preparation.

The preparation according to the invention preferably contains at least one organic or inorganic UV filter.

The preparations are preferably topically applicable cosmetic or dermatological preparations or medical products. The preparations in this case contain a cosmetically or dermatologically suitable carrier and optionally further suitable depending on the desired property profile

Ingredients. If it is a medical device, then a compatible carrier for the medical device is selected.

Topically applicable means according to the invention that the preparation is applied externally and locally, ie that the preparation must be suitable in order to be applied to the skin, for example. For the purposes of the present invention, in addition to the term

Preparation synonymous, the term means or

Formulation used.

The preparations may comprise or contain the said necessary or optional ingredients

Essentially exist or consist of. Any compounds or components which may be used in the compositions are either known and commercially available or may be synthesized by known methods.

Further preferred combinations of embodiments are disclosed in the claims.

According to the invention are cosmetic or dermatological

Preparations preferred. According to the invention, cosmetic preparations are particularly preferred.

Another object of the invention is the preparation, as described above, containing at least one organic or inorganic UV filter.

Another object of the invention is the preparation as described above, characterized in that it contains a cosmetic, dermatological or for medical devices compatible carrier.

Another object of the invention is a method for

Preparation of the preparation as described above, characterized in that the at least one compound of formula (I) as described or preferred described above, at least one antioxidant or a mixture as described above or is preferably described and a carrier, optionally mixed with an organic and / or inorganic UV filter and optionally with other active or excipients. The preparations may preferably contain excipients, for example cosmetic oils (eg Caprylic / Capric

Cosmacol brand oil components such as dimyristyl tartrate, tri C14-C15 alkyl citrate, C12-C13 alkyl lactate, tridecyl salicylate, C12-C13 alkyl octanoate, C12-C13 alkyl maleate, C12-C13 alkyl citrate, C12-C13 alkyl tartrate), or polar protic auxiliaries (eg propylene glycol, glycerol, isopropanol, ethanol) or so-called.

Solubilizers (e.g., butylphthaiimides, isopropylphosphinimides, dimethylisosorbides). Most preferred cosmetic oils are C12-C13 alkyl lactates, commercially available as Cosmacol ELI and phenethyl benzoate, commercially available as X-Tend 226.

In the described preparations may also continue

Color pigments may be included, wherein the layer structure of the pigments is not limited.

Preferably, the color pigment should be 0.5 to 5% by weight skin-colored or brownish. The selection of a

corresponding pigment is familiar to the expert.

The described preparations, as described above, may contain hydrophilic or lipophilic sunscreen filters which are active in the UVA range and / or UVB range and / or IR and / or VIS range (absorber). These substances may in particular be derived from cinnamic acid derivatives, salicylic acid derivatives,

Camphor derivatives, triazine derivatives, β, β-diphenyl acrylate derivatives, p-aminobenzoic acid derivatives and also polymeric filters and silicic acid derivatives. be confiltern, which are described in the application WO -93 / 04665, be selected. Further examples of organic filters are disclosed in patent application EP-A 0 487 404 and WO2009 / 077356

specified.

Suitable organic UV-protective substances are preferably selected from the following list:

para-aminobenzoic acid and its derivatives: PABA, ethyl PABA, ethyldihydroxypropyl PABA, ethylhexyldimethyl PABA, e.g. B.

sold under the name "Escalol 507" from the company ISP, glyceryl PABA, PEG-25 PABA, z. B. sold under the name "Uvinul P25" from the company. BASF.

Salicylates: homosatates sold under the name "Eusolex HMS" by Merck; Ethyl hexyl salicylates, e.g. B. marketed under the name "Neo Heliopan OS" by Fa. Symrise, Dipropylene- glycolsalicylate, z. B. sold under the name "Dipsal" from the company. Scher, TEA salicylates, z. B. marketed under the name "Neo Heliopan TS" of the Fa. Symrise. β, β-diphenylacrylate derivatives: octocrylenes, e.g. B. sold under the name "Eusolex® OCR" from Merck, "Uvinul N539" from BASF, Etocrylene, for example, sold under the name "Uvinul N35" from BASF Further, for example, Methoxycrylen, sold under the name Solastay S1 from the company Hallstar.

Benzophenone Derivatives: Benzophenone-1, e.g. Sold under the name "Uvinul 400"; Benzophenone-2, e.g. Sold under the name "Uvinul D50"; Benzophenone-3 or oxybenzone, e.g. Sold under the name "Uvinul M40"; benzophenone-4, e.g. Sold under the name "Uvinul MS40"; Benzophenone-9, e.g. B. marketed under the name "Uvinul DS-49" of: the Fa. BASF, Benzophenone-5, Benzophenone-6, e.g. B. marketed under the name "Helisorb 11" by the company Norquay, Benzophenone-8, z. B. sold under the name "Spectra-Sorb UV-24" from the Fa.

American cyanamide, benzophenone-12-n-hexyl-2- (4-diethylamino-2-hydroxybenzoyl) benzoate or 2-hydroxy-4-methoxybenzophenone, sold by Merck, Darmstadt under the name

Eusolex® 4360.

Benzylidene camphor derivatives: 3-benzylidenecamphor, e.g. B.

sold under the name "Mexoryl SD" from the company. Chimex, 4-Methylbenzylidenecamphor, z. B. sold under the name "Eusolex 6300" from the company Merck, Benzylidenecamphorsulfonsäure, z. B. marketed under the name "Mexoryl SL" from the company Chimex, Camphorbenzalkoniummethosulfate, z. Sold under the name "Mexoryl SO" from the company Chimex,

Terephthalylidenedicamphorsulfonic acid, e.g. Sold under the name "Mexoryl SX" by Chimex,

Polyacrylamidomethylbenzylidenecamphor sold under the name "Mexoryl SW" from Chimex.

Phenylbenzimidazole derivatives: phenylbenzimidazolesulfonic acid, e.g. B. sold under the name "Eusolex 232" from the company. Merck, disodium phenyldibenzimidazoletetrasulfonate, z. B. marketed under the name "Neo Heliopan AP" by Fa. Symrise.

Phenylbenzotriazole derivatives: drometrizoletrisiloxanes, e.g. B. marketed under the name "Silatrizole" by the company. Rhodia Chimie,

Methylenebis (benzotriazolyl) tetramethylbutylphenol in solid form, e.g. B. sold under the name "MIXXIM ΒΒ / 1Ό0" from the Fa.

Fairmount Chemical, or in micronized form as aqueous

Dispersion, e.g. B. marketed under the name "Tinosorb M" from BASF. Triazine derivatives: ethylhexyltriazone, e.g. B. sold under the name "Uvinul T150" from BASF,

Diethylhexylbutamidotriazone, e.g. B. marketed under the name "Uvasorb HEB" from the company. Sigma 3V. Further triazine derivatives are exemplified by 2,4,6-tris (diisobutyl 4'-aminobenzalmalonate) -s-triazines, or 2,4,6-tris (biphenyl) -1,3,5-triazines, butyl 4 - ({4 - {[4- (butoxycarbonyl) phenyl) amino} -6 - [(3- {, 3,3,3-tetramethyl-1 - [(trimethylsilyl) oxy] disiloxanyl} propyl) amino] -1, 3.5- triazin-2-yl} amino) benzoates sold under the name Mexoryl SBS.

Structure of Mexor l SBS:

and bis-ethylhexyloxyphenolmethoxyphenyltriazines, e.g. sold under the name Tinosorb S by BASF.

Anthraniline derivatives: menthyl anthranilates, e.g. B. marketed under the name "Neo Heliopan MA" by Fa. Symrise.

Imidazole derivatives: ethylhexyldimethoxybenzylidenedioxoimidazoline propionate. Benzalmalonate Derivatives: Polyorganosiloxanes containing functional benzalmalonate groups, such as polysilicone-15, z. 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

Containing mixtures of these.

Pi erazine derivatives such as the compound

or the UV filters of the following structures

Preferably, it may also be combined with UV filters based on polysiloxane copolymers having a random distribution according to the following formula, e.g. a = 1, 2; b = 58 and c = 2 8 are:

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

The preparations may also contain inorganic UV filters, so-called particulate UV filters.

Common methods for aftercare (or synonymous with

Coating) of particulate UV filters are described, for example, in Cosmetics & Toiletries, February 1990, Vol. 53-64

described. This may include one or more of the following Aftertreatment components may be chosen: 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, like

Sodium hexametaphosphate or glycerin.

Preferred particulate UV filters are: untreated titanium dioxides, e.g. the products Microtitanium Dioxide MT 500 B from Tayca; Titanium dioxide P25 of the Fa.

Degussa,

Aftertreated titanium dioxides with Aiuminiumoxid and

Silica aftertreatment such as e.g. the product

Microtitanium Dioxide MT 100 SA from Tayca; or the product "Tioveil Fin" from Uniqema,

Aftertreated Titanium Dioxide with Aluminum Oxide and / or Aluminum Stearate / Laurate Aftertreatment, e.g.

Microtitanium Dioxide MT 100 T from Tayca,

Post-treated titanium dioxides with iron oxide and / or

Iron stearates aftertreatment such as e.g. the product "Microtitanium Dioxide MT 100 F" from Tayca,

Aftertreated titanium dioxides with silicas,

Alumina and silicone aftertreatment such as e.g. the

Product "Microtitanium Dioxide MT 100 SAS" from Tayca, aftertreated titanium dioxides with sodium hexametaphosphates, e.g. the product "Microtitanium Dioxide MT 150 W" from Tayca,

aftertreated titanium dioxides with aluminum oxide and finally with a manganese-containing layer, for example the product Eusolex T-PRO from Merck, aftertreated titanium dioxide with silica such as the product Eusolex T-AVO,

post-treated titanium dioxides with alumina and simeticones, e.g. the product Eusolex T-2000 from Merck,

Post-treated titanium dioxides with aluminum oxide and

Stearic acid, e.g. the product Eusolex T-S from Merck or

post-treated titanium dioxides with alumina or

Silica and monocetyl phosphate, e.g. the product Eusolex T-EASY from Merck.

The treated titanium dioxides to be used for the 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-Titan M 60 from Sachtleben,

Aluminum and glycerin; such as. the product UV-Titan from the company Sachtleben,

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

Sodium hexamethaphosphate and polyvinylpyrrolidone,

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

Polydimethylhydrogensiloxanes, e.g. the product

Microtitanium Dioxide USP Grade Hydrophobia "from Color Techniques.

The treated zinc oxides to be used for the combination may be selected, for example, from the following group: Untreated zinc oxides such. For example, the product Z-Cote from BASF (Sunsmart), Nanox from the company Elementis

After-treated zinc oxides, e.g. the following products: o ZnO aftertreated with polymethylhydrogenosiloxanes, o Nanogard Zinc Oxide FN from Nanophase

Technologies

o "SPD-Z1" from Shin-Etsu (ZnO aftertreated with a silicone-grafted acrylic polymer dispersed in

cyclodimethylsiloxanes

o "Escalol Z100" from ISP (alumina

aftertreated ZnO dispersed in an ethylhexylmethoxycinnamate / PVP-hexadecenes / methicone copolymer mixture)

o "Fuji ZNO-SMS-10" from Fuji Pigment (ZnO post-treated with silica and polymethylsilsquioxane); o Untreated cerium oxide micropigment e.g. with the

Designation "Colloidal Cerium Oxide" from Rhone

Poulenc

Untreated and / or post-treated iron oxides with the name Nanogar from the company Arnaud.

By way of example, mixtures of various metal oxides, e.g. Titanium dioxide and cerium oxide with and without aftertreatment, e.g. the product Sunveil A of the company Ikeda.

These combinations with particulate UV filters are possible both as a powder and as a dispersion or paste.

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

These inorganic UV filters are usually incorporated in the formulations in an amount of from 0.1 percent by weight to 25 percent by weight, preferably 2 percent by weight to 10 percent by weight.

By combination of one or more of the mentioned

Compounds with UV filter effect can be optimized the protective effect against harmful effects of UV radiation.

All mentioned UV filters can also be in encapsulated form

be used. In particular, it is advantageous to use organic UV filters in encapsulated form.

Preferred formulations may also contain at least one other cosmetic active ingredient, for example selected from self-tanning, anti-aging, anti-wrinkle, anti-dandruff, anti-acne, deodorizing, anti-cellulite, skin lightening or vitamins.

Suitable self-tanning agents are dihydroxyacetome. Glycerol aldehyde, hydroxymethylglyoxal, γ-diadehyde, erythrulose, 6-aldo-D-fructose, ninhydrin, 5-hydroxy-1,4-naphthoquinone (juglone) or 2-hydroxy-1,4-naphthoquinone (Lawson) or a mixture thereof

Links. Such self-tanning agents are based on the principle of action of the Maillard reaction.

Furthermore, the preparations may contain at least one self-tanner as an additional ingredient which controls the melanogenesis of the

Stimulates skin cells. An advantageous self-tanner of this class is, for example, hexadecanoic acid 5-hydroxy-2-methyl-4-oxo-4H- chromen-7-yl ester, which is marketed under the brand name RonaCare® Bronzyl by Merck.

Suitable anti-aging active substances, in particular for skin-care preparations, are preferably so-called compatible solutes.

Preferably, as compatible solutes, substances are selected from the group consisting of pyrimidinecarboxylic acids (such as ectoine and hydroxyectoine), proline, betaine, glutamine, cyclic

Diphosphoglycerate, N. acetylornithine, trimethylamine N-oxide di-myo-inositol phosphate (DIP), cyclic 2,3-diphosphoglycerate (cDPG), 1, 1-diglycerol phosphate (DGP), β-mannosylglycerate (Firoin) , .beta.-mannosylglyceramide (firoin-A) or / and di-mannosyl-di-inositol phosphate (DMIP) or an optical isomer, derivative, eg an acid, a salt or ester of these compounds or combinations thereof.

Additional can be used as anti-aging active ingredients Merck products such. 5,7-dihydroxy-2-methyl-chromone, marketed under the trade name RonaCare® Luremine, or

RonaCare® cyclopeptides 5 are used.

Suitable skin lightening agents are melanogenesis inhibitors such as e.g. Hydroquinone, niacinamide, arbutin, alpha-arbutin, beta-arbutin, deoxy-arbutin, vitamin C, ascorbyl palmitate, magnesium ascorbyl phosphate, sodium ascorbyl phosphate, azelaic acid, potassium 4-methoxysalicylate, trans-4- (aminomethyl) cyclohexanecarboxylic acid (Tranexamic acid), liquorice extract, ascorbyl glucoside, 3-O-ethyl ascorbyl ether, 2-O-ethyl ascorbyl ether, kojic acid, kojisuredipalmitate, resorcinol, glutathione, cysteine, mulberry extract, hydrogen peroxide, zinc peroxide,

Sodium peroxide, benzoyl peroxide, glucosamine, aloesin, oleic acid-4-isopropyl catechol, emblica, glycoic acid, eilagic acid, Ferulic acid, resveratrol, oxyresveratrol, quercetin, kaempferol, bile acid, hesperidin, p-coumaric acid, epicatechingallate, epigallocatechin gallate, α-hydroxycarboxylic acids (eg, lactic acid, salicylic acid, malic acid), α-tocopherol, (E) -3- (4-methoxy-phenyl ) - acrylic acid (R) -2 - ((R) -3,4-dihydroxy-5-oxo-2,5-dihydro-furan-2-yl) -2-hydroxyethyl ester or 1- [4- (1, 1-dimethylethyl) phenyl] -3- (4-methoxyphenyl) -1,3-propanediol. preferred

Melanogenesis inhibitors are ascorbic acid and its derivatives, niacinamide, emblica, ellagic acid, mulberry extract, kojic acid, licorice root extract, rucinol, hydroquinone, azelaic acid, arbutin, magnesium ascorbyl phosphate (E) -3- (4-methoxy-phenyl) -acrylic acid (RJ ^ -iiR S -dihydroxy-S-oxo ^, S-dihydro-furan ^ -xy-hydroxyethyl ester or 1- [4- (l, 1-dimethylethyl) phenyl] -3- (4-methoxyphenyl) -1, 3-propanediol.

The preparations to be used may contain vitamins as further ingredients.

Preference is given to vitamins and vitamin derivatives selected from vitamin B, thiamin chloride hydrochloride (vitamin Bi), riboflavin (vitamin B2), nicotinamide, vitamin D, ergocalciferol (vitamin D2), vitamin Ki, esculin (vitamin P active ingredient), thiamine (vitamin Bi ), Nicotinic acid (niacin), pyridoxine, pyridoxal, pyridoxamine, (vitamin Ββ),

Pantothenic acid, biotin, folic acid and cobalamin (vitamin B12), particularly preferably nicotinic acid, pantothenic acid and biotin. Vitamins are usually included with the preparations

Cosmetic application in ranges of 0.01 to 5.0 wt .-%, based on the total weight added.

Retinoids are also effective anti-cellulite agents. Another well-known anti-cellulite drug is caffeine. Furthermore, the compounds of the formula (I) and the antioxidants in the preparations according to the invention can be combined with all active ingredients and auxiliaries, as are systematically listed in WO2009 / 098139. In particular, these substances belong to the use categories listed therein "Moisturizers and

Humectants, desquamating agents, agents for improving the barrier function, depigmenting agents, antioxidants, dermo-relaxing or dermo-decontracting agents, anti-glycation agents, agents for stimulating the synthesis of dermal and / or epidermal macromolecules and / or for which "No synthase inhibitors", "Agents for stimulating fibroblast or keratinocyte proliferation and / or keratinocyte differentiation", "Agents for promoting the maturation of the horny envelope", "Peripheral benzodiazepine receptor (PBR) antagonists", "Agents for increasing the activity of the sebaceous glands", "Agents for stimulating the energy metabolism of cells", "Tensioning agents", "Fat-reducing agents", "Sliming agents", "Agents for promoting the cutaneous microcirculation", "Calmative or anti-irritants", "Sebo-regulating or anti-seborrhoeic agents", "Astringents", "Cicatrizing agents", "Anti-inflammatory agents", "Antiacne agents" Content of WO 2009/098139 belongs t expressly also to the disclosure of the present

Registration.

The said components of the preparation can be incorporated in the usual way, by means of techniques that the

Skilled are well known.

Suitable preparations for external application, for example as a cream or milk (O / W, W / O, O / W / O, W / O / W), as a lotion or emulsion, in the form of oily-alcoholic, oily-aqueous or aqueous-alcoholic gels or solutions to the skin can be sprayed on. They can be present as solid pens or be packaged as aerosol.

As an application form of the preparations to be used are preferably mentioned: solutions, suspensions, emulsions, PIT

Emulsions, Pickering emulsions, pastes, ointments, gels, creams, lotions, powders, soaps, surfactant-containing cleansing preparations, oils, aerosol patches, envelopes, bandages and sprays. Preferred excipients come from the group of preservatives, stabilizers, solubilizers, colorants,

Odor.

Ointments, pastes, creams and gels may contain the usual excipients suitable for topical administration, e.g. animal and vegetable fats, waxes, paraffins, starch, tragacanth, cellulose derivatives, polyethylene glycols, silicones, bentonites,

Silica, talc and zinc oxide or mixtures of these substances. Powders and sprays may contain the usual carriers, e.g.

Lactose, talc, silicic acid, aluminum hydroxide, calcium silicate and polyamide powder or mixtures of these substances. Sprays may additionally contain the usual volatilized, liquefied propellants, e.g. Chlorofluorocarbons, propane / butane or dimethyl ether. Also, compressed air is advantageous to use.

Solutions and emulsions, the usual carriers such as solvents, solubilizers and emulsifiers, for example water, ethanol, isopropanol, ethyl carbonate, ethyl acetate, benzyl alcohol, benzyl benzoate, propylene glycol, 1, 3-butyl glycol, 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.

Pickering emulsions are emulsifier-free emulsions with

particulate constituents, for example zinc oxide or titanium dioxide, and the customary carriers such as solvents or solubilizers, e.g. Water, ethanol, isopropanol, ethyl carbonate,

Ethyl acetate, benzyl alcohol, benzyl benzoate, propylene glycol,

1, 3-butylglycol, oils, especially cottonseed oil, peanut oil, corn oil, olive oil, castor oil and sesame oil.

A preferred solubilizer in general is 2-isopropyl-5-methylcyclohexanecarbonyl-D-alanine methyl ester. Suspensions may include the usual carriers such as liquid diluents, e.g. Water, ethanol or propylene glycol, suspending agents, e.g. ethoxylated isostearyl alcohols,

Polyoxyethylensorbitester and Polyoxyethylensorbitanester, microcrystalline cellulose, aluminum metahydroxide, bentonite, agar-agar and tragacanth or mixtures of these substances.

Soaps can be the usual carriers 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, glycerine, sugars or mixtures of these substances.

Surfactant-containing cleaning products, the usual carriers such as salts of fatty alcohol sulfates, fatty alcohol ether sulfates,

Sulfosuccinic acid semi-esters, fatty acid protein hydrolysates, isothionates, imidazolinium derivatives, methyl taurates, sarcosinates, fatty acid amide ether sulfates, alkylamido betaines, fatty alcohols, Fatty acid diethanolamides, vegetable and synthetic oils, lanolin derivatives, ethoxylated glycerol 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 are included. Further typical cosmetic application forms are also

Lipsticks, lip balms, powder, emulsion and wax make-up and sunscreen, pre-sun and after-sun preparations.

The preferred preparation forms include, in particular, emulsions.

Emulsions are advantageous and contain z. As the said fats, oils, waxes and other fatty substances, and water and an emulsifier, as is customary for such a type of

Preparation is used.

The lipid phase can advantageously be selected from the following substance group:

- mineral oils, mineral waxes

- Oils such as triglycerides of capric or caprylic, further natural oils such. Castor oil;

Fats, waxes and other natural and synthetic fats, preferably esters of fatty acids with lower C-number alcohols, e.g. with isopropanol, propylene glycol or glycerol, or esters of fatty alcohols with alkanoic acids of low C number or with fatty acids;

Silicone oils, such as dimethylpolysiloxanes, diethylpolysiloxanes,

Diphenylpolysiloxanes and mixed forms thereof. The oil phase of the emulsions, oleogels or hydrodispersions or lipodispersions in the context of the present invention is advantageously selected from the group of esters of saturated and / or unsaturated, branched and / or unbranched

Alkan carboxylic acids having a chain length of 3 to 30 carbon atoms and saturated and / or unsaturated, branched and / or

unbranched alcohols of a chain length of 3 to 30 carbon atoms, from the group of esters of aromatic carboxylic acid and saturated and / or unsaturated, branched and / or

unbranched alcohols of a chain length of 3 to 30 carbon atoms.

The aqueous phase of the preparations to be used may contain advantageously low molecular weight Aikohoie, Dioie or Poiyoie, and their ethers, preferably ethanol, isopropanol, propylene glycol, glycerol, ethylene glycol, ethylene glycol monoethyl or monobutyl ether, propylene glycol monomethyl, monoethyl or monobutyl ether, diethylene glycol monomethyl or monoethyl ether and analogous products, furthermore lower C number alcohols, e.g. B.

Ethanol, isopropanol, 1, 2-propanediol, glycerol and in particular one or more thickening agents, which or which can be advantageously selected from the group silicon dioxide,

Aluminum silicates, polysaccharides or their derivatives, e.g.

Hyaluronic acid, xanthan gum, hydroxypropylmethylcellulose, particularly advantageously from the group of the polyacrylates, preferably a polyacrylate from the group of the so-called carbopols,

for example, Carbopols types 980, 981, 1382, 2984, 5984, each individually or in combination. The preparation may contain cosmetic adjuvants which are commonly used in this type of preparation, such as thickeners, emollients, moisturizers, surfactants, emulsifiers, preservatives, antifoaming agents, perfumes, waxes, lanolin, propellants, dyes and / or pigments, and other ingredients commonly used in cosmetics.

Even without further statements, it is assumed that a person skilled in the art can use the above description to the greatest extent. The preferred embodiments and examples are therefore to be considered as merely illustrative, in no way limiting, disclosure. The complete

Disclosure of all applications and publications cited above and below are incorporated by reference into this application. The weight percentages of the individual

Ingredients in the preparations of the examples include

expressly to the disclosure of the description and can therefore be used as features.

Other important features and advantages of the invention will become apparent from the dependent claims and from the examples.

It is understood that the above and the

hereinafter to be explained features not only in the particular combination given, but also in other combinations or alone, without departing from the scope of the present invention.

Preferred embodiments of the invention are illustrated in the examples and will be explained in more detail in the following description, without the scope of the present invention

restrict.

Examples: Example 1: Synthesis of the compound of the formula (II 1-1)

According to the patent application DE 10 2009 030 846 A1, the chain-extended alcohol is prepared from the educts 2,2,3,3,3-pentafluoropropan-1-ol (ABCR) and butylene carbonate (TCI). This intermediate is esterified with aconitic acid (Alfa Aesar) according to the procedure described above and then in the last

Reaction step by means of an aqueous sodium hydrogen sulfite solution (Merck KGaA) sulfonated. Example 2: Synthesis of the compound of the formula (I1I-2)

According to the patent application DE 10 2009 030 846, the chain-extended alcohol is prepared from the educts 2,2,3,3,4,4,4-heptafluorobutan-1-ol (ABCR) and propylene carbonate (Merck KGaA). This intermediate is described after

Esterified with aconitic acid and then sulfonated in the last reaction step by means of an aqueous sodium hydrogen sulfite solution.

Example 3: Determination of the (photo) Antioxidant Activity

various mixtures by reducing the ß-carotene degradation after irradiation.

Mixtures of the test substances, as described below, are applied to a support material with .beta.-carotene and irradiated. The stabilizing effect on beta-carotene is determined by both the sample with test substance and a

Comparison batch irradiated with beta-carotene without test substance. The photodegradation of beta-carotene is determined in comparison to an analogous dark batch. A three-fold determination is carried out on PMMA sheets (17.5 × 2.5 × 0.5 cm, Fa. Schönberg, Roughness), in each case 2 pL / cm ² on the PMMA sheets applied. The solvent used is o-xylene. The

Irradiation dose in Suntester Atlas CPS + is 150kJ / m ² at 500 W / m ² power (about 3MED). Equipment:

Analytical balance (Satorius Extend), ultrasonic bath (Bandelin), shaker (Heidolph Mufti Reax), pipette (Transferpettor, Brand: Handystep Electronic), Suntester CPS + (Atlas),

Spectrophotometer (Agilent Technologies, Gary 60).

Mixtures, by weight

Mixture A: 0.5% solution of β-carotene in o-xylene

Mixture B: 0.5% solution of β-carotene in o-xylene containing 6

Percent by weight of butylene glycol, based on the total amount of

Mixture.

Mixture C: 0.5% solution of β-carotene in o-xylene with 6

Percent by weight of butylene glycol and 0.3% of the compound of formula (III-1), based on the total amount of the mixture.

Mixture D: 0.5% solution of β-carotene in o-xylene with 2.5

Weight percent 2- (4-hydroxy-3,5-dimethoxybenzyl) -malonic acid bis (2-ethylhexyl) ester (RonaCare® AP), based on the

Total amount of the mixture.

Mixture E: 0.5% solution of β-carotene in o-xylene with 2.5

Weight percent 2- (4-hydroxy-3,5-dimethoxybenzyl) -malonic acid bis (2-ethylhexyl) ester and 0.3 weight percent of the compound of formula (III-1), based on the total amount of the mixture.

Mixture F: 0.5% solution of β-carotene in o-xylene with 2.5

Weight percent 2- (4-hydroxy-3,5-dimethoxybenzyl) -malonic acid bis (2-ethylhexyl) ester and 0.3 weight percent 1-methoxy-2-propanol, based on the total amount of the mixture. Mixture G: 0.5% solution of β-carotene in o-xylene with 2.5

Weight percent 2- (4-hydroxy-3,5-dimethoxybenzyl) -malonic acid bis (2-ethylhexyl) ester, 0.3 weight percent of the compound of formula (III-1) and 0.3 weight percent 1-methoxy-2- propanol, based on the total amount of the mixture.

Mixture H: 0.5% solution of β-carotene in o-xylene with 2.5

Weight percent 2- (4-hydroxy-3,5-dimethoxybenzylidene) malonic acid bis (2-ethylhexyl) ester (Oxynex® ST) and 0.3

Weight percent of 1-methoxy-2-propanol, based on the

Total amount of the mixture.

Mixture I: 0.5% solution of β-carotene in o-xylene with 2.5

Weight percent 2- (4-hydroxy-3,5-dimethoxybenzylidene) malonic acid bis (2-ethylhexyl) ester, 0.3 weight percent of

Compound of formula (III-1) and 0.3% by weight of 1-methoxy-2-propanol, based on the total amount of the mixture.

Execution:

Production of measuring solutions:

Fresh daily production of A by dissolving the ß-carotene in o-xylene by treatment with ultrasound (ultrasonic bath Bandelin) for 10 minutes.

Blends B-1 are prepared by weighing the individual substances into the sample container and adding stock solution A. For complete homogenization, the samples are shaken for 15 minutes using the Heidolph Multi Reax.

Preparation of the measurement:

For each Al solution, 2pL7cm ^{2 of} solution is applied evenly on a total of 6 PMMA plates using a pipette.

3 plates are stored in the dark, 3 plates using the atlas Suntester CPS + irradiated (150kJ / m ² at 500 W / m ² power corresponds to approximately 3MED).

All plates are individually rinsed with 50ml isopopanol in a 50ml graduated cylinder. The graduated cylinders are sonicated for 15 minutes.

Measurement of the absorption spectrum:

From each solution, 3 times ca. 2ml filled in a quartz cuvette and the absorbance between 350 and 550 nm by means of a ^'Agilent Cary measured 60th The absorption value at the wavelength of 452nm (absorption maximum of ß-carotene in isopropanol) is used for the calculation. It must be ensured that the blank value of the measurement is pure isopropanol. Calculation of degradation of β-carotene of stock solution A (a):

Ao: absorption at 452nm before irradiation:

Ai: absorption at 452nm after irradiation

a = (Ao - Ai) / Ao Calculation Degradation ß-carotene of the samples, here the example B (b): Bo: Absorption at 452nm before irradiation:

Bi: absorption at 452nm after irradiation

b = (Bo - Bi) / Bo Calculation of the protection of β-carotene of the samples compared to stock solution A:

P = (a - b) / a

Table 1 summarizes the results for the fluorosurfactant of formula (III-1).

Table 1 : Degradation of ß- Protection Influence of

antioxidant

Carotene in% [%] Fluorosurfactants ^*

A - 70 - -

B - 66 7 -

C - 67 5 2%

A - 76 - -

RonaCare

D 27 65 - AP

RonaCare

E 22 71 39%

AP

A - 70 - -

RonaCare

F 35 50 - AP

RonaCare

G 33 53 8%

AP

A - 70 - -

Oxynex®

H 39 45 - ST

Oxynex®

I 30 58 31%

ST

^* calculated on the sample without fluorosurfactant normalized to 1 (maximum degradation)

The result of mixture C demonstrates that the fluorosurfactant of the formula (III-1) has no influence on the stability of beta-carotene. The breakdown of beta-carotene is minimal of that

adjuvant used butylene glycol.

The result of blends A, D and E compared to blends A, F and G shows that adjuvant 1 -methoxy-2- propanol has an influence on the stability of beta-carotene. Nevertheless, the use of the compound of formula (II 1-1) leads to an increase in the efficacy of the antioxidant with an influence of 8% (mixture G). The compound of the formula (III-1) in a mixture with the antioxidant 2- (4-hydroxy-3,5-dimethoxybenzyl) malonic acid bis (2-ethylhexyl) ester (mixture E) to increase the efficacy of the Antioxidants of 39%, based on the

Mixture without fluorosurfactant. The result of the mixtures A, H and I shows that, despite the destabilizing influence of the excipient 1-methoxy-2-propanol, the activity of the compound 2- (4-hydroxy-3,5-dimethoxybenzylidene) -malonic acid bis (2 Ethylhexyl) ester by the presence of the compound of formula (111-1) is increased by 31%, based on the mixture without fluorosurfactant.

In the following, exemplary formulations for cosmetic preparations are given which contain compounds according to Example 1 or 2. Corresponding preparations can be prepared in the same way with all compounds according to the invention.

Incidentally, the INCI names of the commercial

Compounds indicated.

UV-Pearl, OMC stands for the preparation with the INCI name: Water (for EU: Aqua), Ethylhexyl Methoxycinnamate, Silica, PVP, Chlorphenesin, BHT; this formulation is commercially available under the designation Eusolex®UV Pearl ™ OMC from Merck KGaA, Darmstadt.

The other UV pearls listed in the tables are each of analogous composition, with OMC being replaced by the UV filters specified. Formulation Example 1: W / O Emulsions (Number% by Weight)

Table 1

1-1 1-2 1-3 1-4

Titanium dioxide 5

4-hydroxy-3,5-dimethoxy-benzyl-1

malonic acid di 2-ethylhexyl ester

Compound of the formula (II 1-1) 0.1

Mixture of 4-hydroxy-3,5-dimethoxy-1 2 2-benzyl-malonic acid di 2-ethylhexyl ester

and Compound (III-1) (9: 1)

Zinc oxide 5

UV-Pearl, OMC 15 15 15 15

Polyglyceryl-3-Dimerate 3 3 3 3

Cera Alba 0.3 0.3 0.3 0.3

Hydrogenated Castor Oil 0.2 0.2 0.2 0.2

Paraffinium Liquidum 7 7 7 7

Caprylic / Capric Triglycerides 7 7 7 7

Hexyl Laurate 4 4 4 4

PVP / eicosene copolymer 2 2 2 2

Propylene glycol 4 4 4 4

Magnesium sulphates 0.6 0.6 0.6 0.6

Tocopherol 0.5

Tocopheryl acetate 0.5

Cyclomethicone 0.5 0.5 0.5 0.5

Propylparabene 0.05 0.05 0.05 0.05

Methyl parabens 0.15 0.15 0.15 0.15

Water ad 100 ad 100 ad 100 ad 100 Table 1 (continued)

1-5 1 -6 1-7 1 -8

Titanium dioxide 3 2 5

Benzylidene malonates polysiloxanes 1 0.5

4-Hydroxy-phenyl-propionic acid 2-ethyl-1 1 0.5

hexyl

4-Hydroxy-3,5-dimethoxy-benzylidene-1-malonic acid di 2-ethyl-hexyl ester

A mixture of 4-hydroxy-3,5-dimethoxy-5 3 1 1 benzyl malonic acid di 2-ethylhexyl ester and

the compound of the formula (III-1) (9: 1)

Polyglyceryl-3-Dimerate 3 3 3

Cera Alba 0,3 0,3 0,3 2

Hydrogenated Castor Oil 0.2 0.2 0.2

Paraffinium Liquidum 7 7 7

Caprylic / Capric Triglycerides 7 7 7

Hexyl Laurate 4 4 4

PVP / eicosene copolymer 2 2 2

Propylene glycol 4 4 4

Magnesium sulphates 0.6 0.6 0.6

Tocopherol 0.5

Tocopheryl Acetate 1

Cyclomethicone 0,5 0,5 0,5

Propylparabene 0.05 0.05 0.05 0.05

Methyl parabens 0.15 0.15 0, 15 0, 15

Dicocoyl Pentyerythrityl Citrate (and) Sorbitan 6 Sesquioleate (and) Cera Alba (and)

Aluminum stearate

PEG-7 Hydrogenated Castor Oil 1

Zinc Stearate 2

Oleyl Erucate 6

Decyl Oleate 6

Dimethicone 5

Tromethamine 1

Glycerol 5

Allantoin 0.2 water ad 100 ad 100 ad 100 ad 100 Table 1 (continued)

1-9 1-10 1-11 1-12

Titanium dioxide 3 3

Benzylidene malonates polysiloxanes 1 1

Methylene bis-benztriazolyl 1 1 tetramethylbutylphenol

Zinc oxide 5 2

4-Hydroxy-phenyl-propionic acid 2-ethyl-3 3 3 6 hexyl ester

Mixture of 4-hydroxy-3,5-2,2,2-dimethoxybenzyl malonic acid di-2-ethylhexyl ester and the compound

of the formula (III-2) (9: 1)

UV Pearl, OCR 5

4-Hydroxy-3,5-dimethoxy-benzylidene-10 2 -5-malonic acid di 2-ethyl-hexyl ester

UV Pearl, Homosalates, BP-3 10

UV-Pearl, Ethylhexyl salicylate, BP-3 10

BMDBM 2

Polyglyceryl-3-Dimerate 3 3 3 3

Cera Alba 0.3 0.3 0.3 0.3

Hydrogenated Castor Oil 0.2 0.2 0.2 0.2

Paraffinium Liquidum 7 7 7 7

Caprylic / Capric Triglycerides 7 7 7 7

Hexyl Laurate 4 4 4 4

PVP / eicosene copolymer 2 2 2 2

Propylene glycol 4 4 4 4

Magnesium sulphates 0.6 0.6 0.6 0.6

Tocopherol 0.5

Tocopheryl acetate 0.5

3,4-Dihydroxyphenyl-propionic acid 0.5-0.5 0.5 0.5 phenethyl ester

Propylparabene 0.05 0.05 0.05 0.05

Methyl parabens 0.15 0.15 0.15 0.15

Water ad 100 ad 100 ad 100 ad 100 Formulation Example 2: O / W emulsions, numbers in% by weight

Table 2:

2-1 2-2 2-3 2-4

Titanium dioxide 5 3 1

Methylene bis-benztriazolyl 2

Tetramethylbutylphenol

3,4-Dihydroxyphenyl-1-propionic acid

phenethyl ester

4-Hydroxy-phenyl-propionic acid 2-ethylhexyl ester

Mixture of 4-hydroxy-3,5-dimethoxy-1 1 2 2-benzyl malonic acid di 2-ethylhexyl ester

and the compound of the formula (III-1)

(9: 1)

4-hydroxy-3,5-dimethoxy-benzylidene-1

malonic acid di 2-ethylhexyl ester

2-cyano-3,3, -diphenyl-propionic acid -di 4 7 1 2 2-ethylhexyl ester

4-Methylbenzylidene Camphor 3 3

BMDBM 3

Phenylbenzimidazole sulfonic acid 4

Stearyl Alcohol (and) Steareth-7 (and) 3 3 3

Steareth-10

Glyceryl stearate (and) ceteth-20 3 3 3

Glyceryl Stearate 3 3 3

Microwax 1 1 1

Cetearyl Octanoates 11, 5, 11, 5 11.5

Caprylic / Capric triglycerides 6 6 6 14

Oleyl Oleate 6 6 6

Propylene glycol 4 4 4

Glyceryl Stearate SE 6

Stearic Acid 2

Persea Gratissima 8

Propylparabene 0.05 0.05 0.05 0.05

Methyl parabens 0.15 0.15 0, 15 0, 15

Tromethamine 1, 8 1, 8

Glycerol 3

Water ad 100 ad 100 ad 100 ad 100 Formulation Example 3: Gels, numbers in wt%

Table 3:

3-1 3-2 3-3 3-4 3-5 3-6

Titanium dioxide 2

5, 6, 7-Tri h y d roxy fla of 1 1

4-hydroxy-3,5-dimethoxy-benzylidene-1

malonic acid di 2-ethylhexyl ester

A mixture of 4-hydroxy-3,5- 1 1 1 2 2 1 dimethoxybenzyl malonic acid di 2-ethylhexyl ester and the compound

of the formula (III-2) (9: 1)

2-cyano-3,3, -diphenylpropionic acid - 5 5 5 5 5 5 di 2-ethylhexyl ester

4-Hydroxy-phenyl-propionic acid 2-ethyl-1 5 2 hexyl ester

Benzylidene malonates polysiloxanes 1 1

Methylene bis-benztriazolyl 1 1 1 tetramethylbutylphenol

Zinc oxide 2 5 2

UV-Pearl, ethylhexyl methoxycinnamate 30 15 15 15 15 15

Butylmethoxydibenzoylmethane 1

Prunus Dulcis 5 5 5 5 5 5

Tocopheryl acetate 0.5

Caprylic / Capric Triglycerides 3 3 3 3 3 3

Octyldodecanol 2 2 2 2 2 2

Decyl Oleate 2 2 2 2 2 2

PEG-8 (and) tocopherol (and) ascorbyl 0.05 0.05 0.05 0.05 0.05 0.05 Palmitate (and) Ascorbic Acid (and)

Citric Acid

Sorbitol 4 4 4 4 4 4

Polyacrylamides (and) C13-14 3 3 3 3 3 3 Isoparaffin (and) Laureth-7

Propylparabene 0.05 0.05 0.05 0.05 0.05 0.05

Methyl parabens 0.15 0.15 0.15 0.15 0.15 0.15

Water ad 100 ad ad ad ad ad

100 100 100 100 100 Formulation Example 4: Hair Mascara

manufacturing:

Heat phase B to 75 ° C, phase C to 80 ° C. Add Phase B slowly to Phase C with stirring. Cool with stirring to 65 ° C and homogenize. Cool to 40 ° C and add phases D, E and F to Phase B / C with stirring and homogenize again. Now add the pearlescent pigment with stirring. On

Cool the room temperature and adjust the pH to 6.0-6.5.

Formulation 5: Conditioner with IR3535®

Method of preparation: Mix phases A and B separately, phase B to

Add phase A with stirring. Add phase C.

Formulation Example 6 Hair conditioner with pearlescent pigment

Ingredients [%]

A

PEARL PLANT 3,00

DISODIUM EDTA 0.05

AQUA (WATER) ad 100

B

CETEARYLALCOHOL, BEHENTRIMONIUM 5.00

METHOSULFATE

OCTYLDODECANOL 1, 10

CETYL ALCOHOL 1.00

GLYCERINE 1, 00

BEHINDRIMONIUM CHLORIDE 0,70

METHOXY PEG / PPG-7/3 AMINOPROPYL 0.70

dimeticones

QUATERNIUM 80 0 - 2.5

MIXTURE OF 4-HYDROXY-3,5-D! METHOXY- Λ n _ -3 n

BENZYLIDENALMALONIC ACID 2-ETHYLENE

HEXYLESTER AND THE CONNECTION OF THE

FORMULA (111-1) (9: 1)

C

COCODIMONIUM HYDROXYPROPYL-0,70

SILIKAMINO ACIDS

PHENOXYETHANOL, BENZOIC ACID, 0.40

DEHYDROACETIC ACID

CITRIC ACID 0.20

PERFUME 0.60 Hers part procedure:

Disperse the pearlescent pigment and Titriplex III in phase A water. Heat the components of phases A and B to 75 ° C. Add phase B to phase A with stirring and homogenize. Cool to 40 ° C and add the ingredients of Phase C. Cool to 30 ° C and homogenize again for about 30 sec. Adjust the pH to 3.6-4.0.

Remarks: Recommended pearlescent pigments are TIMIRON® silver pigments and TIMIRON® interference pigments from Merck.

Formulation Example 7: O / W Tanning Cream

Production method:

First, phases A and B are heated separately to 75 ° C. Thereafter, phase A is slowly added to phase B with gentle stirring. It is homogenized at 65 C for one minute. The mixture is then cooled with stirring to 40 ° C and the phase C was added with stirring, cooled to 35 ° C and the phase D was added, and further cooled.

First, phases A and B are heated to 80 ° C. Thereafter, phase B is slowly added with stirring to phase A and homogenized. It is then cooled and the phase C at 40 ° C was added.

Formulation Example 8: O / W Tanning Lotion

Production method:

First, phases A and B are mixed separately and heated to 75 ° C. Thereafter, phase C is added to phase B and added to phase A with stirring. It is homogenized. Then it will be cooled with stirring and the phases D and E at 40 ° C.

added.

Formulation Example 9: O / W tanning cream with UV A / B protection

Production method:

First, phases A and B are mixed separately and heated to 80 ° C. Thereafter, phase B is slowly added with stirring to phase A. It is homogenized and cooled to 40 ° C and added phase C, then cooled to room temperature. Formulation Example 10: Sunscreen Soft Cream (O / W)

production:

Heat phase A and phase B to 80 ° C. Slowly add phase B to phase A while stirring, homogenize and cool with stirring.

Formulation Example 11: Sunscreen Lotion (O W)

RAW MATERIAL (INCI)%

A

OCTOCRYLENE 6.0

BUTYL METHOXYDIBENZOYL METHANE 2.0

POLYGLYCERYL-3 METHYLGLUCOSE 4.0

DISTEARATE

ETHYLHEXYL STEARATE 8.0

CETEARYL ISONONANOATE 2.0

PVP / EICOSENE COPOLYMER 1.0

MIXTURE OFF 3- (3,4,5- 1,0

TRIMETHOXYBENZYLLIDES) -2,4-PENTANDION AND THE CONNECTION OF THE

FORMULA (111-1) (9: 1)

TOCOPHERYL ACETATE 1, 0

B

XANTHAN GUM 0.3 SODIUM CETEARYL SULFATE 1.0

GLYCERIN 5.0

WATER AD 100

C

TITANIUM DIOXIDE 4.0

D

PRESERVATIVE Q.S.

production:

Heat phase A to 80 ° C. Pre-swell the Keltrol of phase B in the water, then add the remaining raw materials and heat to 80 ° C. Homogenize phase A to phase B and homogenize for 2 minutes (hand blender): cool with stirring and add phase C at 35 ° C. Homogenize again for 1 min (hand blender). Cool to room temperature and stir in phase D.

Formulation Example 12: Sunscreen spray with

tanning intensification

Preparation: Phase B is slowly added to Phase A with stirring at room temperature. Thereafter, Phase C is added. Subsequently, the phase D is added. INCI CERALÜTION® C:

Aqua (and) Capric / Caprylic triglycerides (and) Glycerin (and)

Ceteareth-25 (and) Sodium Dicocoylethylenediamine PEG-15 Sulfate (and) Sodium Lauroyl Lactylate (and) Behenyl Alcohol (and) Glyceryl Stearate (and) Glyceryl Stearate Citrate (and) Gum Arabic (and) Xanthan Gum (and) Phenoxyethanol (and ) Methylparaben (and) Ethylparaben (and) Butylparaben (and) Isobutylparaben

Formulation Example 13: Pump hair tint spray

Preparation: Pre-dissolve phase A until a clear solution is obtained. Add phase B to phase A with stirring. Premix phase C and add to the rest, stirring until a homogeneous mixture has formed. Formulation Example 14: Hair Care Formulation

Component mass [%]

Disodium EDTA 0.1

Oxynex® ST 2.0

Compound of the formula (M 1-1> 0.1

Dye 1.5

Cetyl pyridinium chlorides 0

Pitera® 10

Ascorbyl glycosides 0

Niacinamide 5.0

Polyquaternium 37 0

Isohexadecane 2.5

Isopropyl isostearate 1.3

Sucrose polycottonseedate 0.67

Polymethylsilsesquioxane 0.25

Cetearyl glucoside + cetearyl alcohol 0.2

Behenyl alcohol 0.4

Ethylparaben 0.2

Propylparaben 0.1

Cetyl alcohol 0.32

Stearyl alcohol 0.48

Tocopheryl acetate 0.5

PEG-100 stearate 0.1

Glycerol 7.0

Titanium dioxide 0.6

Polyacrylamide + C13-14 isoparaffin + laureth-7 2.0

Panthenol 1.0

Benzyl alcohol 0.4

Dimethicone + dimethiconol 2.0

Water ad 100

Formulation 15: Hair rinse

Formulation Example 16 :. hair conditioner

Formulation Example 17 :. hair mousse

The formulation can be used as a leave-on or rinse-off formulation and is in aerosol relative proportions

Formulation / propellant gas = 90/10 packed in a pressure vessel. As propellants, for example, propane or butane or mixtures thereof can be used.

Formulation Example 18: Shampoo

Formulierungsbeispie! 19: Hair dyeing formulations

Component mass [%]

Benzyl Alcohol 2.5

Propylene Carbonates 10

Ethanol 5.0

Hydroxyethylcellulose 2.0

Pirenoxine Sodium CAS 51410-30-1 2.0

4-Methoxy matsäure-6-O-ascorbate 1, 0

Mixture of 4-hydroxy-3,5-dimethoxy-1,0-benzyl malonic acid di 2-ethylhexyl ester

and the compound of the formula (III-1) (9: 1)

Perfume 1, 0

Preservatives q.s.

Citric Acid q.s. ad pH 5.5

Aqua ad 100

Claims

claims

1. Use of compounds of the formula (I)

in which

X is a hydrophilic group,

r is 0 or 1,

B is a single bond, -O-, -NH- -NR'-, -CH2-, -C (O) -O-, -S-,

-CH 2 -O-, -O-C (O) -, -O-C (O) -O-, -N-C (O) -, -C (O) -N-, -O-C (O) -N-, -

NC (O) -N-, -Si (R ') ₂ -, -Si (R') ₂ -O-, -O-SO2- or -SO2-O-,

R 'is a linear or branched alkyl group having 1 to 12 carbon atoms,

R ¹ and R ^{2 are} independently hydrogen or

-CH ₂ -COY ³ -L ³ - (A ³ ) n ₃ ,

Y, Y ² and Y ³ independently of one another are O, S or

L ¹ , L ² and L ^{3 are,} independently of one another, linear or branched alkylene having 1 to 12 C atoms, where one or more nonadjacent C atoms may be replaced by O, S, and / or N,

A \ A ² and A ^{3 are} independently hydrogen or a group of the structure -Z ⁱ (CR ³ R ⁴ ) miRf ⁱ , where i is 1, 2 or 3,

Z 'is O, S or N and is bonded to a C atom of U or is a single bond, R ³ and R ⁴ independently of one another are hydrogen or a straight-chain or branched alkyl group having 1 to 12 C atoms,

R is a fluorine-containing radical,

n1, n2 and n3 are independently 1, 2 or 3, m1, m2 and m3 are independently 0, 1, 2, 3, 4 or 5, and the compounds of formula (I) contain at least one Rf group, for Increase the effectiveness of antioxidants.

2. Use according to claim 1, characterized in that compounds of the formulas (II), (III) and / or (IV) are used as compounds of the formula (I),

(IV)

in which

X represents -SOs-, -OSO ₃ -, -POs ^{2 "} or OPO ₃ ^2" ,

Y ¹ , Y ² , Y ³ , Z, Z ² and Z ^{3 are} O, Rf ¹ , Rf ² and Rf ³ for perfluorinated groups Rf with 1 to 4

C atoms are,

n1, n2 and n3 are 1 or 2,

m1, m2 and m3 are 0, 1, 2, 3 or 4,

L, L ² and L ^{3 represent} a linear or branched alkylene having 2 to 6

C atoms are and

R ³ and R ^{4 are} hydrogen or an alkyl group having 1 to 3 carbon atoms. 3. Use according to claim 1 or 2, characterized in that compounds of the formulas (III-1) to (III-6) are used as compounds of the formula (I):

Use according to one or more of claims 1 to 3, characterized in that the effectiveness of the antioxidants selected from the group of amino acids, imidazoles, peptides, carotenoids, carotenes, chlorogenic acid and its derivatives, lipoic acid and derivatives thereof, aurothioglucose, thiols, thiodipropionic acid and their derivatives

Sulfoximine compounds, (metal) chelators, unsaturated fatty acids and their derivatives, vitamin C and derivatives, tocopherols and derivatives, vitamin A and derivatives, rutinic acid and derivatives thereof, flavonoids and their derivatives, ferulic acid, furfurylidene glucitol, carnosine, butylhydroxytoluene, butyl hydroxyanisole, nordohydroguajaretic acid, trihydroxybutyrophenone, uric acid and its derivatives, mannose and its derivatives, silibens and their derivatives, derivatives of Benzylidene-2,4-alkanedione, derivatives of benzylidene maleate

or derivatives of benzylmalonic acid is amplified.

5. Use according to one or more of claims 1 to 4, characterized in that the effectiveness of

Compounds of the formula (A) and / or (B) is enhanced,

wherein

R 1 -C (O) R ₆ , -CO 2 R ₆ or -C (O) N (R ₇ > 2 means

R 2 denotes linear or branched alkyl having 1 to 30 C atoms,

X is O, NH or a bond,

R 3 denotes H or linear or branched alkyl having 1 to 20 C atoms,

R6 is linear or branched alkyl having 1 to 30 carbon atoms and

6. Use according to one or more of claims 1 to 5, characterized in that the effectiveness of

Compounds 2- (4-hydroxy-3,5-dimethoxybenzylidene) malonic acid bis (2-ethylhexyl) ester, 2- (4-hydroxy-3,5-dimethoxybenzyl) malonic acid bis (2-ethylhexyl) ester , 2- (4-hydroxy-3-methoxybenzylidene) -malonic acid bis-isopropyl ester, 2- (4-hydroxy-3-methoxybenzyl) -malonic acid bis-isopropyl ester, 2- (4-methoxybenzylidene) -malonic acid bis (2-ethylhexyl) ester and / or 3- (3,4,5-trimethoxybenzylidene) -2,4-pentanedione is amplified.

7. Mixture comprising a compound of the formula (I)

in which

X is a hydrophilic group,

r is 0 or 1,

B is a single bond, -O, -NH-, -NR'-, -CH ₂ -, -C (O) -O-, -S-, -CH ₂ -O-, -OC (O) -, -OC ( 0) -O-, -NC (O) -, -C (O) -N-, -O-C (O) -N-, - NC (0) -N-, -Si (R ') 2- -Si (R ') _{2 is} -O-, -O-SO ₂ - or -SO 2 -O-, R' is a linear or branched alkyl group having 1 to 12 C atoms,

R ¹ and R ^{2 are} independently hydrogen or

Are -CH ₂ -COY ³ -L ³ - (A ³ ) n ³ ,

Y ¹ , Y ² and Y ^{3 are} independently O, S or N,

L ¹ , L ² and L ^{3 are} independently linear or branched

A ¹ , A ² and A ^{3 are} independently hydrogen or a group of the structure -Z ⁱ (CR ³ R ⁴ ) _mi Rf ⁱ , where i is 1, 2 or 3, Z 'is O, S or N and is attached to a C atom of LJ or is a single bond,

R ³ and R ⁴ independently of one another are hydrogen or a straight-chain or branched alkyl group having 1 to 12 C atoms,

Rf 'is a fluorine-containing radical,

n1, n2 and n3 are independently 1, 2 or 3, m1, m2 and m3 are independently 0, 1, 2, 3, 4 or 5 and the compounds of formula (I) contain at least one Rf 'group, and at least one antioxidant.

8. Mixture according to claim 7, wherein the at least one

Antioxidant of a compound of formula (A) and / or (B),

wherein

R 1 is -C (O) R ₆ , -CO _{2 is} Re or -C (O) N (R ₇ ) 2,

R 2 denotes linear or branched alkyl having 1 to 30 C atoms,

X is O, NH or a bond,

R 3 denotes H or linear or branched alkyl having 1 to 20 C atoms,

R ₄ and R 5 each, independently of one another, denote H, linear or branched alkyl having 1 to 12 C atoms or linear or branched alkoxy having 1 to 12 C atoms,

R6 is linear or branched alkyl having 1 to 30 carbon atoms and

Each R ₇ is independently H or linear or branched alkyl having 1 to 8 carbon atoms. Mixture according to claim 7 or 8, wherein the compound of the forms! (A) and / or of the formula (B) from the group 2- (4-hydroxy-3,5-dimethoxybenzylidene) -malonic acid bis (2-ethylhexyl) ester, 2- (4-hydroxy-3,5- dimethoxybenzyl) malonic acid bis (2-ethylhexyl) ester, 2- (4-hydroxy-3-methoxybenzylidene) malonic acid bis-isopropyl ester, 2- (4-hydroxy-3-methoxybenzyl) malonic acid bis-isopropyl ester, 2- (4-methoxybenzylidene) -malonic acid bis (2-ethylhexyl) ester and / or 3- (3,4,5-trimethoxybenzylidene) -2,4-pentanedione.

10. Mixture according to one or more of claims 7 to 9, containing 2- (4-hydroxy-3,5-dimethoxybenzylidene) malonic acid bis (2-ethylhexyl) esters and / or 2- (4-hydroxy-3,5 - dimethoxybenzyl) -malonic acid bis (2-ethylhexyl) ester and the compound of formula (111-1):

11. Cosmetic or dermatological preparation or

Medical device containing at least one compound of formula (I) as described in one or more of claims 1 to 3 and at least one antioxidant or a

Mixture according to claim 7.

12. The preparation according to claim 11, wherein the at least one antioxidant of the compound of the formula (A) and / or (B) corresponds as described in claim 5 or 6 or containing a mixture according to claim 8.

A preparation according to claim 11 or 12 comprising at least one organic or inorganic UV filter.

Preparation according to one or more of Claims 11 to 13, characterized in that it contains a cosmetic,

dermatological or medical device-compatible carrier.

A process for preparing a preparation according to one or more of claims 11 to 14, characterized in that the at least one compound of formula (I) as described in one or more of claims 1 to 3, at least one antioxidant or a mixture of one or more of claims 7 to 10 and a carrier, optionally with an organic and / or inorganic UV filter and optionally with further active or auxiliary substances, is mixed.