WO2016142026A1

WO2016142026A1 - Fluorine surfactants in emulsions

Info

Publication number: WO2016142026A1
Application number: PCT/EP2016/000204
Authority: WO
Inventors: Michael TERMER; Frank Pfluecker; Lilia Heider
Original assignee: Merck Patent Gmbh
Priority date: 2015-03-06
Filing date: 2016-02-08
Publication date: 2016-09-15

Abstract

The invention relates to the use of fluorine surfactants of formula (I) in emulsions, containing nanoparticulate UV filters for increasing the light stability of said emulsions. Also disclosed are the corresponding emulsions.

Description

Fluorosurfactants in emulsions

The present invention relates to the use of fluorosurfactants of the formula (I) in emulsions containing particulate inorganic UV filters to increase the light protection of these emulsions and such

Emulsions.

It is known that light radiation having a wavelength in the range of 280 to 320 nm, which is known by the name UV-B, causes erythema and skin burns.

It is also known that UV-A radiation having a wavelength in the range of 320 to 400 nm may cause a change in the skin, especially in the case of sensitive skin or skin that is continuously exposed to solar radiation. In particular, UV-A radiation causes loss of elasticity of the skin and the appearance of wrinkles, leading to premature aging. It favors the triggering of a

Erythema formation or intensifies this reaction in some individuals. UVA radiation can even be the cause of light-triggered toxic or allergic reactions. It is therefore desirable to filter out both UV-B radiation and UV-A radiation.

Reports of an increase in UV radiation reaching the biosphere and increasing numbers of skin cancers increase awareness of the harmful effects of sun exposure. The observed formation of reactive

Intermediates in the application of sunscreen products with organic sunscreen filters, led to an increased use of inorganic sunscreen filters. In cosmetic preparations, for example in sunscreen products containing inorganic sunscreen filters, a large number of substances must be stable and homogeneous. For example, the stable and easy emulsification of oil and water in different

Emulsion types containing sunscreen filters or other cosmetic agents have a continuing task.

Surfactants are one of the most important classes within adjuvants for cosmetic preparations that accomplish this task. They act as

Solubilizer, for example, to homogenize nonpolar agents and excipients in aqueous solutions.

A variety of surfactants are known for use in 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 will continue to be beneficial to the

Stabilization or dispersion of solid ingredients or active ingredients, for example of pigments or UV filters, in cosmetic

Preparations described.

Another class of surfactants are fluorosurfactants. Fluorosurfactants have a superior surface tension lowering ability, 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 is also known.

Specific applications of sulfosuccinates and / or sulfotinyl carballylates with different fluorinated side chains are described in US 4,968,599 and US 4,988,610 and US 6,890,608 and in A.R. 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. Further

Fluorosurfactants, in particular succinates and tricarballylates with fluorinated alkyl groups, are described in WO 2009/149807, WO 2010/003567,

WO 2010/149262, WO 2011/082770 and WO 2012/084118.

The object of the present invention was to provide advantageous alternative surfactants which, in particular in cosmetic preparations, in combination with inorganic particulate UV filters, bring about improved properties of the cosmetic preparation.

It has now surprisingly been found that an increase in the light protection effect is achieved by the use of certain fluorosurfactants as adjuvants in sunscreen products, preferably in emulsions containing particulate inorganic UV filters. In particular, an increase in the UV protection is achieved. This effect can be recognized, for example, by increasing the sun protection factor (SPF) of the corresponding sunscreen products or the corresponding emulsions. A first subject of the present invention is therefore an emulsion comprising at least one compound of the formula (I),

in which

X is a hydrophilic group,

R is linear or branched alkylene, 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, 0-C (O) -N, NC (0) -N, SiR ' ₂ -, SiR' ₂ -O, O-S0 ₂ or S0 ₂ -O wherein R 'is linear or branched alkyl .

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 alkylene, wherein one or more non-adjacent carbon atoms may be replaced by 0, 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 ) _mi Rf ⁱ , where i is 1, 2 or 3,

Z 'is O, S or N and is attached to a C atom of L' or one

Single bond is,

R ³ and R ^{4 are} independently hydrogen or an alkyl group,

Rf is a fluorine-containing radical,

n1, n2 and n3 are independently 1-6,

m1, m2 and m3 are independently 0-5

and the compounds of formula (I) contain at least one Rf group, and at least one particulate inorganic UV filter, wherein both the compound of formula (I) and the particulate inorganic UV filter are in substantially the same phase of

Emulsion are located.

The emulsion may contain the necessary or optional

Components include, contain, consist essentially of, or consist of. All compounds or components in the

Emulsions can be used are either known and commercially available or can be synthesized by known methods. Another object of the invention is the use of

Compounds of the formula (I)

in which

X is a hydrophilic group,

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

OC (0) -0, NC (O), C (0) -N, OC (0) N, NC (0) -N, SiR _'2 -, SiR' ₂ -0, 0-S0 ₂ or S0 _{2 is} -O, where R 'is linear or branched alkyl,

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

-CH ₂ -COY ³ -L ³ - (A ³⁾ _n3 are

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

L ¹ , L ² and L ^{3 are} independently linear or branched alkylene, wherein one or more non-adjacent C atoms may be replaced by O, S, and / or N,

A, A ² and A ³ independently of one another are 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 L' or is a single bond,

R ³ and R ^{4 are} independently hydrogen or an alkyl group,

Rf is a fluorine-containing radical,

n1, n2 and n3 are independently 1-6,

m1, m2 and m3 are independently 0-5 and the compounds of formula (I) at least one Rf 'group

in emulsions containing particulate inorganic UV filters, wherein the compound of formula (I) and the particulate inorganic UV filter are in substantially the same phase of the emulsion.

The abbreviation L ¹ stands here for the abbreviations L ¹ , L ² and / or L ³ .

The term "substantially in the same phase of the emulsion" means that the major proportion of the at least one compound of formula (I), as previously described, and the major portion of the particulate inorganic UV filters are in the same phase of the emulsion If, for example, the compound of the formula (I) is incorporated into the oil phase when the emulsion is prepared, the particulate inorganic UV filter is likewise added to the oil phase

Formula (I) when preparing the emulsion incorporated into the water phase, the particulate inorganic UV filter is also added to the water phase. By doing so, the emulsions show increased light protection, especially increased UV protection, compared to sunscreen products without a compound of formula (I). If this is done, the emulsions additionally show increased light protection, in particular increased UV protection, in comparison to

Sunscreen products with alternative surfactants. One can recognize this increase in UV protection, for example, by increasing the sun protection factor.

The sun protection factor (LFS) is also referred to as SPF, synonymous with the English term "sun protection factor." This factor evaluates the effectiveness of sunscreen.

For the measurement of the sun protection factor in vivo are a variety of

Methods available. In Europe, the SPF determination according to ISO 244444: 2010 is recognized as standard. In the US, an FDA Method established (FDA = Food and Drug Administration). Standards were also introduced in Japan and Australia. Basically, the methods differ only in the order quantity of the sunscreen formulation to be investigated, the radiation source and the number of subjects on which the examinations take place.

For the measurement of the sun protection factor in vitro, a variety of methods are also available. The method used to document the effect of the fluorosurfactants of the compounds of formula (I)

is derived from the ISO 24443: 2012 method for the in-vitro determination of the UVA protection performance of sunscreens and includes the measurement of the diffuse transmission of the emulsion.

The measurement takes place in the UV range between 290nm and 400nm. The sample is distributed on a UV-transparent plate and irradiated with a defined UV radiation source. The transmittance of the formulation is detected by means of a UV spectrophotometer. The in-vitro SPF is calculated with the integrated software of the photometer. The devices used are described in the example section.

The effect of increasing light protection, for example, as recognized by the increase in in vitro SPF _A , is surprisingly observed in various types of emulsions. By using the compounds of formula (I) as described above and below, an in vitro SPF increase of 5 to 50% is observed.

Emulsions are disperse systems of two or more

different, immiscible liquids. The outer or

continuous phase, also called dispersing agent, encloses at least one or more internal or dispersed phases, which in

Form of fine droplets are distributed in it. The mean particle diameter the droplet in emulsions is between 100 nanometers and 1

Millimeter.

O / W emulsions (oil-in-water) are liquid systems in which the outer closed phase consists of water and the inner disperse phase consists of partially different oily components.

In W / O emulsions (water-in-oil), the outer phase consists of oily components while the dispersed phase is water.

In addition to the O / W and W / O emulsions so-called multiple emulsions exist. These are complex systems in which droplets of the dispersed phase themselves contain additional smaller droplets similar to the continuous phase. In O / W / O, there are dispersed water droplets in an outer oily phase which in turn constitute the dispersant for an oily phase. For W / O / W emulsions the arrangement is opposite.

The emulsion according to the invention is preferably an O / W emulsion or a W / O emulsion. The emulsion according to the invention is particularly preferably a W / O emulsion.

Another object of the invention is therefore the emulsion as described above, characterized in that it is an oil-in-water emulsion or a water-in-oil emulsion.

Another object of the invention is therefore the emulsion as described above, characterized in that it is a water-in-oil emulsion.

Another object of the invention is therefore the use of a compound of formula (I), as described above in an emulsion, characterized in that it is an oil-in-water emulsion or a water-in-oil emulsion.

Another object of the invention is therefore the use of a compound of formula (I), as described above in an emulsion, characterized in that it is a water-in-oil emulsion.

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 fluoro-surfactants with short-chain perfluoroalkyl chains can lead to an improved ecotoxicological profile, since such compounds are non-toxic and show no bioaccumulation and no inhalative toxicity. Their use in cosmetics is particularly preferred because of this property.

By using the fluorosurfactants of the formula (I), in addition to the increase in light protection, which can be recognized by the increase in the in-vitro SPF, good dispersibility of the inorganic particulate UV filters can be observed at the same time. Likewise, the invention remain

Emulsions, as described above, even after eight weeks storage homogeneous and therefore stable. An influence of the compounds of the formula (I) on the pH of the aqueous phase of the emulsion as described above or described below is not observed. By the

Compounds of formula (I), as described above or preferably described below, a better wetting behavior for organic sunscreen is possible. Due to the higher hydrophobicity of the

Compounds of the formula (I), as described above or preferably described below, have the emulsions according to the invention a higher water repellency. Preferred compounds of formula (I) are those in which two or three Rf groups are included. However, compounds with at least four Rf groups are also possible, preferably with four, six or nine R groups.

The fluorinated groups Rf * used are preferably branched or unbranched, fluorine-containing alkyl radicals, in particular perfluorinated alkyl radicals. Particularly preferred are fluorine-containing alkyl radicals having 1 to 10, preferably 1 to 6, in particular 1 to 4 C-atoms. 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 ¹ and R ^{2 are} not simultaneously -CH ₂ -COY ³ -L ³ - (A ³ ) _n3 . Preferred compounds of the formula (I) are also those in which Y ¹ , Y ² and Y ^{3 are} preferably O or N, in particular O. Preferably, Y ¹ and Y ² or Y ¹ , Y ² and Y ^{3 have the} same meaning.

The groups Rf are linked to a group L ¹ , L ² or L ³ via a group -Z '(CR ³ R) _m j. Z 'here is preferably O or N, in particular O. Preference is given to compounds in which all Z ^{1 are the} same.

Preferred compounds of the formula (I) are those in which n1, n2 and n3 are preferably, independently of one another, 0-4, in particular 1 or 2.

Preferred compounds of the formula (I) are also those in which m1, m2 and m3 are preferably, independently of one another, 0 to 4, in particular 1, 2, 3 or 4. Preferred compounds of the formula (I) are also those in which R ³ and R ⁴ independently of one another are hydrogen or an alkyl group having 1 to 6 C atoms, in particular 1-4 C-atoms. R ³ and R ⁴ are each independently preferably hydrogen or unbranched

Ci-C _ß alkyl group. Preference is given to compounds in which R ³ or R ⁴ is hydrogen. m1, m2 and m3 are preferably independently of one another 1, 2 or 3. 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 3 to 8 carbon 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 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 Ü is - (CR ⁵ R ⁶ ) ci (CR ⁷ R ⁸ ) _C j) di-, where the

Indices ci and c'i independently represent 0 to 10, the subscript di from 0 to 5, R ⁵ to R ⁸ independently represent hydrogen or a branched or linear alkyl group, with the proviso that ci and c'i do not stand for 0 at the same time.

Particular preference is given to compounds of the formula (I) in which, in at least one group L ', the group R ^{5 is} an alkyl group having 1 to 6

C atoms, in particular an alkyl group having 1 to 4 carbon atoms, and the groups R ⁶ and R ⁷ and R ^{8 are} hydrogen.

Also preferred are compounds of the formula (I) in which R ^{7 is} an alkyl group having 1 to 6 C atoms, in particular one Alkyl group having 1 to 4 carbon atoms, and the groups R ⁵ and R ⁶ and R ^{8 are} hydrogen.

In the compounds of the formula (I), the group R preferably represents linear or branched alkylene having 1 to 12 carbon atoms, in particular having 1 to 4 carbon 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 may preferably be 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 one

Single bond.

It is particularly advantageous to use compounds of the formula (I) according to the invention in emulsions in which one or more of the variables Rf, Υ ', Ζ', L ', R to R ⁸ , ci, c'i, di, ni, mi, R, r and B are the preferred ones

Have meanings, in particular those compounds in which the variables mentioned have the particularly preferred meanings. According to the invention, it is particularly advantageous to use compounds of the formula (I) in emulsions in which all the variables mentioned have the preferred meanings, in particular the particularly 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 -, -OSO ₃ ^" , -PO ₃ ^{2 "} , -OPO ₃ ^{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- (CH ₂ ) t-PO ₃ ^{2 "} , - (OCH ₂ CH ₂ ) s O- (CH ₂ ) t -OPO 3 ^2" or from the

Formulas A to C,

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

The preferred anionic groups include in particular -COO ^" , -S0 ₃ ^" , -OS0 ₃ ^" , -PO3 ^2" , -OPO ₃ ^{2 "} , the partial formula A, and

- (OCH ₂ CH ₂ ) s O- (CH ₂ ) t -COO- ₎ - (OCH ₂ CH ₂ ) s O - (CH ₂ ) t -SO ₃ ^" and

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

The most preferred anionic groups include -SO ₃ ^" , -OSO 3 ^" , -PO ₃ ^{2 "} , or OPO 3 ^2" . In particular, a sulfonate group -SO ₃ ^" 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 C1-C6-alkyl and all R ^{* may be} identical or different.

Particularly preferred are Na ⁺ , K ⁺ and NhV, more preferably Na ⁺ .

A preferred cationic group X may be selected from

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

where R is H or C-alkyl in any position,

Z ^" stands for CI ^" , Bf, Γ, CH ₃ S0 ₃ ^" , CF ₃ S0 ₃ ^" , CH ₃ PhSO ₃ -, PhS0 ₃ ^"

R, R ^{2 *} and R ^{3 *} are each independently H, Ci _-3 o- alkyl, Ar or -CH ₂ Ar and

Ar is an unsubstituted or mono- or polysubstituted

substituted aromatic ring or fused ring systems having 6 to 18 carbon atoms, wherein also one or two CH groups may be replaced by N.

The preferred cationic groups include 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 linear or branched alkyl, wherein one or more nonadjacent 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 1 to 4 o 'is an integer from the range from 1 to 10,

p 'is 1 or 2,

Each R independently represents C 1-30 alkyl, Ar or -ChkAr, preferably d-20 alkyl, and

Ar is an unsubstituted, mono- or polysubstituted aromatic ring or fused ring systems having 6 to 18 carbon atoms, in which also one or two CH groups may be replaced by C = 0, glycoside is an etherified carbohydrate, preferably a mono- di-, tri- or oligo-glucoside,

and R "is H or methyl.

The preferred nonionic groups X belong here

in particular linear or branched alkyl, wherein one or more non-adjacent carbon atoms replaced by O, S and / or N may be replaced, -OH, - OCOCR '= CH ₂ and -O- (glycoside) _0th

When X is selected to mean alkyl, where one or more nonadjacent C atoms are replaced by O, S, and / or N, then this may be expressed synonymously by the formula R ** - (B ^** -A ^** ) _m - be described, wherein R ^{** is} H or Ci-4-alkyl, in particular H or CH ₃ , A * ^{* is} a linear or branched alkylene, preferably having 1 to 10

Carbon atoms, in particular having 1 to 4 carbon atoms, B ^{** is} O or S, preferably represents O, and m ** is an integer from 1 to

100, more preferably an integer from 1 to 30 stands.

Particularly preferred as a nonionic group X is the group R ** - (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 C ^ alkyl, in each case independently of one another are H or CH ₃ . Particularly preferred

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, as the hydrophilic group X, are one of the preferred anionic groups X, the preferred nonionic groups or the preferred

contain zwitterionic groups.

Particular preference is given to compounds of the formula (I) which contain the groups -SO 3,

-OSO3 ^" , -PO3 ^2" or -OPO3 ^{2 "} , polyethylene or polypropylene glycols, betaines, or sulfobetaines.

Very particular preference is given to compounds of the formula (I) which contain the group -SO ₃ ^" as the hydrophilic group X. Preferred counterions here are Na ⁺ , K ⁺ and NH, in particular Na ⁺ . According to the invention, compounds of the formula (I) in the emulsion in which X is an anionic group, in particular -SO 3 ^" , and one or more of the variables R f, Υ ', Ζ', L ', R ¹ to R are particularly advantageously used ⁸ , ci, c'i, di, ni, mi, R, r and B have the preferred meanings described, in particular those compounds in which the said variables have the particularly preferred meanings Preferred compounds are in particular those compounds in which all variables have the preferred meanings, in particular the particularly preferred meanings.

In a particularly preferred group of compounds of the formula (I), R ¹ and R ^{2 are} hydrogen and A ¹ and A ^{2 are} each one

These compounds are represented by formula (II). Particular preference is given to compounds of the formula (II) where Y, Y ² , Z and Z ^{2 are} identical to O.

Are In another preferred group of compounds of formula (I) R ¹ is H, R ² is -CH ₂ -COY ³ -L ³ - (A ³⁾ _n3, and A ^1, A ² and A ³ represents a -Z ' (CR ³ R ⁴ ) _m iRf group. These compounds are represented by formula (III). Particular preference is given to compounds of the formula (III) where Y ¹ , Y ² , Y ³ , Z ¹ , Z ² and Z ³ are 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) _m iRf' group. These compounds are represented by formula (IV). Particular preference is given to compounds of the formula (IV) where Y ¹ , Y ² , Y ³ , Z ¹ , Z ² and Z ³ are O.

(IV)

Particularly preferred compounds of the formula (I) are compounds of the 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 ^" . Preferred 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). Preferably, L ¹ , L ² and L ^{3 are} independently linear or branched

C ₁ -C 10 -alkylene, in particular linear or branched C ₃ -C 8 -alkylene, preferably equal to linear or branched C ₃ -C 6 -alkylene. 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 Rf having 1 to 4 C atoms. Preferably, Rf ¹ , Rf ² and Rf ^{3 have the} same meaning. In the formulas (II), (III) and (IV), n1, n2 and n3 are preferably independently 1 or 2. m1, m2 and m3 are preferably 1 to 4 independently of each other.

A further subject of the invention is accordingly an emulsion as described above or preferably described, characterized in that as compounds of the formula (I) compounds of the formulas (II), (III) and / or (IV) are used,

(IV)

in which

X represents -SO ₃ ^" , -OSO ₃ ^" , -PO 3 ^{2 "} or OPO ₃ ^~ , in particular represents -SO ₃ ^" , Y ¹ , Y ² , Y ³ , Z ¹ , Z ² and Z ³ stand for O. .

Rf ¹ , 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 1, 2, 3 or 4, L, L ² and L ^{3 are} a linear or branched C ₃ -C ₆ alkylene and R ³ and R ^{4 are} hydrogen or an alkyl group having 1 to 3 carbon atoms.

A further subject of the invention is accordingly the use, as described above, characterized in that compounds of the formulas (II), (III) and / or (IV) are used as compounds of the formula (I),

(IV) where

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 is} O. stand,

m1, m2 and m3 are 1, 2, 3 or 4, L ¹ , L ² and L ^{3 are} a linear or branched C ³ -C 6 -alkylene and R ³ and R ^{4 are} hydrogen or an alkyl group having 1 to 3 carbon atoms. Preferred compounds of the formulas (II), (III) and (IV) are also those in which R ³ and R ⁴ independently of one another denote hydrogen or an alkyl group having 1 to 3 C atoms.

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 1, 2 or 3.

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.

Particularly advantageous compounds of the formula (III) are used in the inventive use in emulsions 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 in emulsions is particularly advantageous are compounds of the formulas (III-1) to (III-6):

Examples of compounds of the formula (I), their use in

Emulsions are particularly advantageous compounds of the formulas (111-1) and / or (III-2), as previously described.

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) _r B are prepared. U and A 'in the formula (V) have the meaning described for L ¹ , 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 contain one or more 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 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 aconit or

Zitronensäureester. These syntheses are described in WO 2010/149262,

WO 2011/082770 and WO 2012/084118 described. The disclosures in the cited references are hereby also expressly incorporated into the disclosure of the present application.

The content of the compounds of the formula (I), (II), (III) or (IV) in the emulsions according to the invention is usually 0.01% by weight to 2% by weight, preferably 0.05% by weight to 1% by weight. %, in particular 0.1 - 0.5

Wt .-% based on the total emulsion. The compounds are particularly preferably contained in an amount of from 0.1 to 0.5% by weight, based on the total amount of the emulsion. Most preferably, the compounds are contained in an amount of 0.5 wt .-%, based on the total amount of the emulsion. Another object of the invention is therefore an emulsion as described above, characterized in that the compounds of formula (I) in 0.01 to 2 weight percent are contained, based on the total amount of the emulsion.

In addition to the compounds of the formula (I), (II), (III) or (IV) to be used according to the invention, as described above, at least one further emulsifier is contained in the emulsions, which generally also determines the type of emulsion.

As emulsifiers, for example, the known W / O and O / W emulsifiers can be used. It is advantageous to use further customary co-emulsifiers in the emulsions according to the invention. Advantageously selected as emulsifiers, for example O / W emulsifiers, mainly from the group of substances with HLB values of 11-16, very particularly advantageous with HLB values of 14.5-15.5, if the O / W Emulsifiers have saturated radicals R and R '. If the O / W emulsifiers have unsaturated radicals R and / or R ', or if isoalkyl derivatives are present, the preferred HLB value may be those of

Emulsifiers also lower or above.

It is advantageous to choose the fatty alcohol ethoxylates from the group of the ethoxylated stearyl alcohols, cetyl alcohols, cetylstearyl alcohols (cetearyl alcohols).

It is also advantageous to choose the fatty acid ethoxylates of the following group:

Polyethylene glycol (20) stearate, polyethylene glycol (21) stearate,

Polyethylene glycol (22) stearate, polyethylene glycol (23) stearate,

Polyethylene glycol (24) stearate, polyethylene glycol (25) stearate,

Polyethylene glycol (12) isostearate, polyethylene glycol (13) isostearate, Polyethylene glycol (14) isostearate, polyethylene glycol (15) isostearate,

Polyethylene glycol (16) isostearate, polyethylene glycol (17) isostearate,

Polyethylene glycol (18) isostearate, polyethylene glycol (19) isostearate,

Polyethylene glycol (20) isostearate, polyethylene glycol (21) isostearate,

Polyethylene glycol (22) isostearate, polyethylene glycol (23) isostearate,

Polyethylene glycol (24) isostearate, polyethylene glycol (25) isostearate,

Polyethylene glycol (12) oleate, polyethylene glycol (13) oleate,

Polyethylene glycol (14) oleate, polyethylene glycol (15) oleate,

Polyethylene glycol (16) oleate, polyethylene glycol (17) oleate,

Polyethylene glycol (18) oleate, polyethylene glycol (19) oleate,

Polyethylene glycol (20) oleate.

As the ethoxylated alkyl ether carboxylic acid or its salt, the sodium laureth-11-carboxylate can be advantageously used. As the alkyl ether sulfate, sodium laureth-4 sulfate can be advantageously used. As the ethoxylated cholesterol derivative, polyethylene glycol (30) cholesteryl ether can be advantageously used. Also polyethylene glycol (25) soybean oil has been proven. As ethoxylated triglycerides, the polyethylene glycol (60) Evening Primrose Glycerides can advantageously be used (Evening Primrose = evening primrose).

It is furthermore advantageous to use the polyethylene glycol glycerol fatty acid esters from the group consisting of polyethylene glycol (20) glyceryl laurate, polyethylene glycol (21) glyceryl laurate, polyethylene glycol (22) glyceryl laurate, polyethylene glycol (23) glyceryl laurate, polyethylene glycol (6) glyceryl caprate / citrate, polyethylene glycol (20) glyceryl oleate, polyethylene glycol (20) glyceryl isostearate, polyethylene glycol (8) glyceryl oleate (cocoate).

It is also favorable to choose the sorbitol esters from the group of polyethylene glycol (20) sorbitan monolaurate, polyethylene glycol (20) sorbitan monostearate, polyethylene glycol (20) sorbitan monoisostearate, polyethylene glycol (20) sorbitan monopalmitate, polyethylene glycol (20) sorbitan monooleate. As advantageous W / O emulsifiers can be used:

Fatty alcohols containing 8 to 30 carbon atoms, monoglycerol esters of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids having a chain length of 8 to 24, in particular 12 to 18, carbon atoms,

Diglycerol esters of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids of a chain length of 8 to 24, in particular 12-18 C-atoms, monoglycerol ethers of saturated and / or unsaturated, branched and / or unbranched alcohols

Chain length of 8 to 24, in particular 12-18 C-atoms, diglycerol ethers of saturated and / or unsaturated, branched and / or unbranched alcohols of a chain length of 8 to 24, in particular 12-18 C-atoms, propylene glycol esters of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids having a chain length of 8 to 24, in particular 12-18 carbon atoms and sorbitan esters of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids having a chain length of 8 to 24, in particular 12-18, carbon atoms.

Particularly advantageous W / O emulsifiers are glyceryl monostearate, glyceryl monoisostearate, glyceryl monomyristate, glyceryl monooleate,

Diglyceryl monostearate, Diglycerylmonoisostearat, propylene glycol monostearate, propylene glycol monoisostearate, propylene glycol monocaprylate, propylene glycol monolaurate, sorbitan monoisostearate, sorbitan monolaurate, sorbitan monocaprylate, Sorbitanmonoisooleat, sucrose distearate, cetyl alcohol, stearyl alcohol, arachidyl alcohol, behenyl alcohol, Isobehenyl- alcohol, selachyl alcohol, chimyl alcohol, polyethylene glycol (2) stearyl ether (steareth 2), glyceryl monolaurate, glyceryl monocaprinate, glyceryl mono- caprylate or PEG-30 dipolyhydroxystearate. In the emulsion according to the invention are also particulate

inorganic UV filters included. The particulate inorganic UV filters are preferably particulate metal oxides, which may optionally be doped or coated. The metal oxides are preferably micronized.

Another object of the invention is therefore an emulsion as described above, characterized in that at least one particulate metal oxide is contained as a particulate inorganic UV filter, which can carry at least one coating.

Suitable particulate metal oxides for use in the emulsion according to the invention are metal oxides with UVA and UVB

absorbent properties are used. Suitable metal oxides are, for example, titanium dioxide, iron oxides, zinc oxide or else cerium oxides.

Suitable particulate metal oxides are also mixed oxides, for example mixed oxides of titanium dioxide and zinc oxide, titanium dioxide and silicon dioxide, titanium dioxide and tin oxide, titanium dioxide and manganese oxide, zinc oxide and tin oxide.

Preferably, the particulate inorganic UV filters are particulate

Metal oxides selected from titanium dioxide, iron oxides, zinc oxide or cerium oxide.

Particularly preferred are the particulate metal oxides titanium dioxide and zinc oxide in the emulsions according to the invention as particulate

inorganic UV filters included. Titanium dioxide is as metal oxide

particularly preferred according to the invention. Titanium dioxide can be present in the form of rutile or anatase or in amorphous form, but preferably in the form of rutile and / or anatase. The primary particle size is preferably in the range from 5 to 50 nm, whereby the primary particles are preferably round, in particular in anatase, while rutile primary particles frequently occur in needle or spindle form as far as ovals ("egg-shaped"), but also round rutile primary particles Furthermore, mixtures of rutile and anatase can be used. The crystallite size of the particulate metal oxide, as described above or described as preferred, determined by the Scherrer method, is in the range of 5 nm to 100 nm, preferably in the range of 8 to 50 nm and particularly preferably below 25 nm - Electron microscope can be determined dimensions of the particulate

Metal oxides are usually at a length of 5 to 150 nm and a width of 5 to 60 nm. Preferably, the length is in the range of 20 to 60 nm and the width in the range of 8 to 30 nm. Particulate metal oxide, which according to the invention as particulate inorganic UV filter used in the emulsion, as described above or described as preferred, can be obtained by various methods well known to those skilled in the art.

For example, production may be by a pyrogenic process (such as by flame pyrolysis), by a sol-gel process, a plasma process by a hydrothermal process, or by a combination of the various process variants.

In this case, the metal oxide may also be doped. Under a doping is in the sense of the present application, the presence

corresponding small amounts of ions understood as impurities in the crystal lattice of the metal oxide. Preferred dopants are those with iron, manganese, tin, zinc or cerium ions. Very particular preference is given to doping of the metal oxide, as described above or as preferably described, with iron ions.

Another object of the invention is therefore an emulsion, characterized in that at least one particulate metal oxide or mixed oxide is contained as a particulate inorganic UV filter, as described above. Another object of the invention is therefore an emulsion, characterized in that at least one particulate metal oxide from the group titanium dioxide, iron oxides, zinc oxide or cerium oxides is contained as a particulate inorganic UV filter, which may be doped.

Another object of the invention is therefore an emulsion, characterized in that at least one particulate metal oxide from the group of titanium dioxide or zinc oxide is contained, which is doped.

Another object of the invention is therefore an emulsion, characterized in that at least one particulate titanium dioxide or zinc oxide is contained, which may be doped and which may carry at least one coating.

Another object of the invention is therefore an emulsion, characterized in that at least one particulate titanium dioxide is contained, which may be doped and which carries at least one coating.

Common methods for the aftertreatment (or synonymous with the coating) of particulate metal oxides are described, for example, in Cosmetics &

Toiletries, February 1990, Vol. 105, pp. 53-64. In this case, one or more of the following aftertreatment components may be selected: amino acids, beeswax, fatty acids, fatty acid alcohols, anionic surfactants, lecithin, phospholipids, sodium, potassium, zinc, iron or aluminum salts of fatty acids, polyethylenes, silicones,

Proteins (especially collagen or elastin), alkanolamines, silica, alumina, other metal oxides, phosphates, such as sodium hexametaphosphate or glycerol. Preferred particulate UV filters are: untreated titanium dioxides such as the products Microtitanium Dioxide MT 500 B from Tayca; Titanium dioxide P25 from Degussa, aftertreated titanium dioxides with aluminum oxide and silicon dioxide aftertreatment such as, for example, the product "Microtitanium Dioxide MT 100 SA from Tayca; or the product "Tioveil Fin" from Uniqema, aftertreated titanium dioxides with aluminum oxide and / or

Aluminum stearates / ilaurate aftertreatment, e.g. Microtitanium Dioxide MT 100 T from Tayca,

Post-treated titanium dioxides with iron oxide and / or iron stearates. 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", the company Tayca,

Post-treated titanium dioxides with sodium hexametaphosphates, e.g. the product "Microtitanium Dioxide MT 150 W" from the company Tayca, aftertreated titanium dioxides with aluminum oxide and finally with a manganese-containing layer such as e.g. the product Eusolex T-Pro from Merck,

post-treated titanium dioxides with silica such as e.g. 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 alumina 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 ones to be used for combination in the emulsion

Titanium dioxides 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 M160 of the company Sachtleben,

Aluminum and glycerin; such as. the product UV titanium of the Fa.

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. Microtitanium Dioxide USP Grade Hydrophobie "from Color Techniques.

The treated ones to be used for combination in the emulsion

Zinc oxides may be selected, for example, from the following group:

Untreated zinc oxides such. B. the product Z-Cote Fa. BASF

(Sunsmart), Nanox of the company Elementis

Post-treated zinc oxides such as the following products:

o ZnO aftertreated with polymethylhydrogenosiloxanes,

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 the company ISP (aluminum oxide aftertreated

ZnO dispersed in an ethylhexyl methoxycinnamate / PVP hexadecenes / methicone copolymer blend)

o "Fuji ZNO-SMS-10" from Fuji Pigment (ZnO aftertreated with silica and polymethylsilsquioxane); o Untreated cerium oxide micropigment eg with the name "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 inorganic particulate UV filters are usually in one

Amount of 0.1 wt .-% to 25 wt .-%, preferably 2 wt .-% - 10 wt%, incorporated into the emulsion according to the invention.

Particularly preferred particulate UV filters to be used according to the invention for the production of the W / O emulsions according to the invention are: titanium dioxides with a post-treatment of aluminum oxide with

Stearic acid, alumina with manganese dioxide or alumina with Simeticone. Particular preference is given to using particulate UV filters according to the invention for the preparation of the W / O emulsions according to the invention, the titanium dioxides being marketed as Eusolex® T-Pro, Eusolex T-S and Eusolex T-2000.

Particularly preferred particulate UV filters to be used according to the invention for the production of the O / W emulsions according to the invention are: titanium dioxides with an after-treatment of silica, alumina with manganese dioxide or aluminum oxide with simeticone. Particulate UV filters which are very particularly preferably used according to the invention for the production of the O / W emulsions according to the invention are:

Titanium dioxides with a post-treatment of alumina with

Manganese dioxide, especially the titanium dioxide marketed under the

Brand names Eusolex T-Pro. Eusolex T-Avo is a titania silica coated silica prepared by the process described in US 8,758,501.

Eusolex T-Pro is a manganese-based titanium dioxide produced by the process described in US Pat. No. 8,753,684.

Eusolex T-2000 is a titanium dioxide with at least 78% T1O2, at least 8% alumina and about 2% simeticone content. The middle

Particle size is about 30 nm.

Eusolex T-S is a titanium dioxide with at least 75% T1O2, at least 8% alumina and about 8% stearic acid content. The primary particle size is about 10 nm. Because of the high specificity

Surface of the primary particles Eusolex T-S has a strong tendency to agglomeration.

The emulsion of the invention may in addition to the at least one

Compound of formula (I), (II), (III) or (IV), the particulate

inorganic UV filters and other emulsions as before

optionally containing further organic UV filters, so-called hydrophilic or lipophilic sunscreen filters, which are in the UVA range and / or UVB range and / or IR and / or VIS range

(Absorber) are effective. These substances may in particular be derived from cinnamic acid derivatives, salicylic acid derivatives, camphor derivatives,

Triazine derivatives, β, β-diphenyl acrylate derivatives, p-

Aminobenzoesäurederivaten and polymeric filters and silicone filters, which are described in the application WO -93 / 04665, be selected.

Further examples of organic as well as inorganic UV filters are disclosed in patent applications EP-A 0487 404 and WO2009 / 077356

specified. In the following, the named organic UV filters are usually named according to the INCI nomenclature.

In particular suitable for a combination are:

para-aminobenzoic acid and its derivatives: PABA, ethyl PABA, ethyl dihydroxypropyl PABA, ethylhexyl dimethyl 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: Homosalates sold under the name "Eusolex HMS" by Merck; Ethyl hexyl salicylates, e.g. B. sold under the name

"Neo Heliopan OS" from the Fa. Symrise, Dipropylene glycol salicylate, 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" by BASF Furthermore, for example, Methoxycrylen, sold under the name Solastay S1 of 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. sold under the

Name "Uvinul DS-49" from BASF, Benzophenone-5, Benzophenone-6, z. B. marketed under the name "Helisorb 11" from the Fa.

Norquay, Benzophenone-8, e.g. Sold under the name "Spectra-Sorb UV-24" from American Cyanamid, Benzophenone-12 n-hexyl 2- (4-diethylamino-2-hydroxybenzoyl) benzoate or 2-hydroxy-4-methoxybenzophenone, marketed by from Merck, Darmstadt under the name Eusolex® 4360.

Benzylidene camphor derivatives: 3-benzylidenecamphor, e.g. Sold under the name "Mexoryl SD" from the company. Chimex, 4-Methylbenzylidene- camphor, z. B. sold under the name "Eusolex 6300" from the company Merck, Benzylidenecamphorsulfonsäure, z. B. sold under the name "Mexoryt SL" from the company. Chimex, Camphor benzalkonium methosulfate, z. Sold under the name "Mexoryl SO" from the company Chimex,

Terephthalylidenedicamphorsulfonic acid, e.g. Sold under the name "Mexoryl SX" from the company Chimex, polyacrylamidomethylbenzylidene camphor under the name "Mexoryl SW" from the company. Chimex.

Phenylbenzimidazole derivatives: phenylbenzimidazolesulfonic acid, e.g. B.

sold under the name "Eusolex 232" by the company Merck, disodium phenyl dibenzimidazole tetrasulfonate, z. B. marketed under the name "Neo Heliopan AP" by Fa. Symrise.

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

Triazine derivatives: ethylhexyltriazone, e.g. B. sold under the name "Uvinul T150" from the company. BASF, Diethylhexylbutamidotriazone, z. B.

marketed under the name "Uvasorb HEB" by the company Sigma 3V.

Further triazine derivatives are exemplarily 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- {1,3,3,3-tetramethyl-1 - [(trimethylsilyl) oxy] disiloxanyl} propyl) amino] -1, 3,5-triazin-2-yl) amino) benzoate, sold under the name Mexoryl SBS. Structure of

Mexoryl SBS:

and bis-ethylhexyloxyphenol methoxyphenyl triazines, e.g. sold under the name Tinosorb S by BASF.

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

Imidazole derivatives: ethylhexyldimethoxybenzylidenedioxoimidazoline propionate.

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

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

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

or the UV filters of the following structures

Preference can also be given to combining with UV filters based on polysiloxane copolymers having a statistical distribution according to the following formula, where, for example, a = 1, 2; b = 58 and c = 2.8 are:

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

Suitable organic UV-protective substances are preferably to be selected from the following list: ethylhexyl salicylate,

Phenylbenzimidazolesulfonic acid, benzophenone-3, benzophenone-4, benzophenone-5, n-hexyl 2- (4-diethylamino-2-hydroxybenzoyl) benzoate, 4-methylbenzylidenecamphor, terephthalylidenedicamphorsulfonic acid, disodium phenyldibenzimidazoletetrasulfonate,

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

These organic UV filters are incorporated usually in an amount of 0.01 percent by weight to 20 percent by weight, preferably 1 wt .-% - 10 wt .-%, in the emulsion.

All mentioned UV filters can also be used in encapsulated form. In particular, it is beneficial to use organic UV filters in to use encapsulated form. Therefore, it may be preferred if one or more of the above-mentioned UV filters are present in encapsulated form. It is advantageous if the capsules are so small that they can not be observed with the naked eye. To achieve the above

Effects it is still necessary that the capsules are sufficiently stable and donate the encapsulated active ingredient (UV filter) not or only to a small extent to the environment.

Preferred emulsions may also contain at least one other

contain cosmetic active ingredient, for example selected from

Antioxidants, anti-aging ingredients, anti-cellulite ingredients,

Self-tanning substances, skin lightening agents or vitamins.

Furthermore, the compounds of the formula (I) can be combined in the emulsions according to the invention with all active substances and auxiliaries, as are systematically listed in WO2009 / 098139 from page 27, line 4 to page 64, line 20. 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

"Agents for stimulating fibroblast or keratinocyte proliferation and / or keratinocyte differentiation", "Agents for promoting the maturation of the horny envelope", "NO synthase inhibitors", "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 "," slimming agents "," agents for promoting the cutaneous microcirculation "," calmatives or anti-irritants " , "Sebo-regulating or anti-seborrhoic agents", "Astringents", "Cicatrizing agents", "Anti-inflammatory agents", "Anti-acne agents". Further additional active ingredients which are in the inventive

Sunscreen formulation may be included from the

Category "Agents for Protection of Sensitive Skin". Examples of this group of

Compounds are, for example, urea, ectoin or the compounds offered by Merck RonaCare AP and RonaCare

Cyclopeptides-fifth

The protective effect of the emulsions according to the invention against oxidative stress or against the action of free radicals can

can be improved if the emulsion contains one or more antioxidants, wherein the skilled person no difficulty in selecting suitable fast or delayed-acting antioxidants.

There are many known and proven substances in the literature that can be used as antioxidants, e.g. Amino acids (e.g.

Glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazoles, (eg urocaninic acid) and their derivatives, peptides such as D, L-carnosine, D-carnosine, L-carnosine and their derivatives (eg anserine), carotenoids, carotenes (eg α-carotene, β-carotene, lycopene) and their derivatives, chlorogenic acid and its derivatives, lipoic acid and its derivatives (eg dihydrolipoic acid), aurothioglucose, propylthiouracil and other thiols (eg thioredoxin, glutathione, cysteine, cystine, cystamine and their glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl, γ-linoleyl, cholesteryl and glyceryl esters) and salts thereof,

Dilauryl thiodipropionate, distearyl thiodipropionate, thiodipropionic acid and its derivatives (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) as well as sulfoximine compounds (for example buthionine sulfoximines,

Homocysteinsulfoximin, Buthioninsulfone, penta-, hexa-, heptathionine sulfoximine) in very low tolerated dosages (eg pmol to μΐτΊθΙ / kg), further (metal) chelators, (eg α-hydroxy fatty acids, Palmi tainic acid, phytic acid, lactoferrin), α-hydroxy acids (eg citric acid, lactic acid, malic acid), humic acid, bile acid, bile extracts, bilirubin, biliverdin, EDTA, EGTA and their derivatives, unsaturated fatty acids and their derivatives, vitamin C and derivatives (eg ascorbyl palmitate,

Magnesium ascorbyl phosphate, ascorbyl acetate), tocopherols and derivatives (eg, vitamin E acetate), vitamin A and derivatives (eg, vitamin A palmitate), as well as benzoic acid coniferyl benzoate, rutinic acid and derivatives thereof, α-glycosyl rutin, ferulic acid, furfurylidene glucitol, carnosine .

Butylhydroxytoluene, butylhydroxyanisole, nordohydroguajaretic acid, trihydroxybutyrophenone, quercitin, uric acid and its derivatives, mannose and its derivatives, zinc and its derivatives (eg ZnO, ZnS0), selenium and its derivatives (eg selenium methionine), silibens and their derivatives (eg stilbene oxide, trans-stilbene oxide).

Suitable antioxidants are also compounds of the formulas A 'or B'

wherein for the compounds of the formulas A 'and B'

R ¹ from the group -C (0) CH ₃ , -C0 ₂ R ³ , -C (0) NH ₂ and -C (O) N (R ⁴ ) ₂

can be selected

X is O or NH,

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

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

R ^{4 are} each independently H or linear or branched

Alkyl having 1 to 8 C atoms,

R ^{5 is} H or linear or branched alkyl having 1 to 8 C atoms or linear or branched alkoxy having 1 to 8 C atoms and

R ⁶ denotes linear or branched alkyl having 1 to 8 C atoms, preferably derivatives of 2- (4-hydroxy-3,5-dimethoxybenzylidene) malonic acid and / or 2- (4-hydroxy-3,5-dimethoxybenzyl) -malonic acid, more preferably 2- (4-hydroxy-3,5- dimethoxybenzylidene) malonic acid bis- (2-ethylhexyl) ester (for example Oxynex ^® ST Liquid) and / or 2- (4-hydroxy-3,5-dimethoxybenzyl) -malonic acid-bis- (2-ethylhexyl) ester (example RonaCare ^® AP).

Furthermore, the combination with 2- (4-hydroxy-3-methoxybenzylidene) malonic acid bis-isopropyl ester or 2- (4-hydroxy-3-methoxybenzyl) malonic acid bis-isopropyl ester (hydrogenated diisopropyl vanilidene malonate) is preferred. The same applies to corresponding bis-ethyl ester.

Mixtures of antioxidants are also suitable for use in the cosmetic preparations according to the invention. Known and commercially available mixtures are, for example, mixtures containing as active ingredients lecithin, L - (+) - ascorbyl palmitate and citric acid, natural tocopherols, L - (+) - ascorbyl palmitate, L - (+) - ascorbic acid and

Citric acid (for example Oxynex ^® K LIQUID), tocopherol extracts from

natural sources, L - (+) - ascorbyl palmitate, L - (+) - ascorbic acid and citric acid (for example Oxynex ^® L LIQUID), DL-a-tocopherol, L - (+) - ascorbyl palmitate, citric acid and lecithin (for example Oxynex ^® LM ) or butylhydroxytoluene (BHT), L - (+) - ascorbyl palmitate and citric acid (eg Oxynex ^® 2004). Such antioxidants are with the

Compounds of the invention in such compositions usually in weight percent ratios ranging from 1000: 1 to 1: 1000, preferably used in weight percent ratios of 100: 1 to 1: 100.

Among the phenols that can be used, the partially occurring as natural substances polyphenols are particularly interesting.

For example, the flavonoids or bioflavonoids, which are mainly known as plant dyes, frequently have an antioxidant potential. Quercetin (cyanidanol, cyanidolone 1522, meietin,

Sophoretine, ericin, 3,3 ', 4', 5,7-pentahydroxyflavone) as a particularly effective antioxidant. Suitable anti-aging agents, especially for skin care

Emulsions are preferably so-called compatible solutes. These are substances that are involved in the osmoregulation of plants or microorganisms and can be isolated from these organisms. Under the generic term compatible solutes also the described in the German patent application DE-A-10133202 osmolytes are taken. Suitable osmolytes are, for example, the polyols, methylamine compounds and amino acids and in each case their precursors. Within the meaning of the German patent application DE-A-10133202, osmolytes are understood as meaning, in particular, substances from the group of polyols, such as, for example, myo-inositol, mannitol or sorbitol and / or one or more of the osmolytically active substances mentioned below: taurine, choline, betaine, phosphorylcholine,

Glycerophosphorylcholines, glutamine, glycine, α-alanine, glutamate, aspartate, proline, and taurine. Precursors of these substances are, for example, glucose, glucose polymers, phosphatidylcholine, phosphatidylinositol, inorganic phosphates, proteins, peptides and polyamic acids. Precursors are z. B. Compounds that are converted to osmolytes by metabolic steps. Preferably according to the invention as compatible solute substances selected from the group consisting of Pyrimidincarbonsäuren (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) , ß-

Mannosylglyceramide (Firoin-A) or / and di-mannosyl-di-inositol phosphate (DMIP) or an optical isomer, derivative, for example an acid, a salt or ester of these compounds or combinations thereof.

In particular, ectoine ((S) -1,5,6-tetrahydro-2-methyl-4-pyrimidinecarboxylic acid) and hydroxyectoine ((S, S) -1,4,5,6-tetrahydro-5 are among the pyrimidinecarboxylic acids hydroxy-2-methyl-4-pyrimidinecarboxylic acid) and their derivatives.

Additional can be used as anti-aging agents Merck products such. 5,7-dihydroxy-2-methyl-chromone, marketed under the

Trade names RonaCare®Luremine or the commercial products

RonaCare®lsoquercetin, RonaCare®Tiliroside or

RonaCare® cyclopeptides 5 are used. Furthermore, the emulsions according to the invention may contain at least one self-tanner as further ingredient.

Advantageous self-tanning agents which can be used include: 1,3-dihydroxyacetone, glycerolaldehyde, hydroxymethylglyoxal, γ-dialdehyde, erythrulose, 6-aldo-D-fructose, ninhydrin, 5-hydroxy-1,4-naphthoquinone (juglone) or 2- Hydroxy-1, 4-naphthoquinone (Lawson). Very particular preference is the 1, 3-dihydroxyacetone, erythrulose or their

Combination.

Further, the emulsions of the present invention may contain at least one self-tanner as an additional ingredient that stimulates the melanogenesis of 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. The emulsions may also contain one or more other skin lightening agents or synonym depigmenting agents.

Skin lightening agents can in principle all known to those skilled Be active ingredients. Examples of compounds with skin-lightening activity are hydroquinone, kojic acid, arbutin, aloesin, niacinamide, azelaic acid, elagic acid, tranexamic acid, potassium 4-methoxysalicylate,

Mulberry extract, magnesium ascorbyl phosphate,

Licorice root extract, Emblica, ascorbic acid or rucinol as well

Substances as described in WO2007121845.

The emulsions may contain vitamins as other ingredients.

Preference is given to vitamins and vitamin derivatives selected from vitamin A, vitamin A propionate, vitamin A palmitate, vitamin A acetate, retinol, vitamin B, thiamin chloride hydrochloride (vitamin Bi), riboflavin (vitamin B ₂ ),

Nicotinic acid amide, vitamin C (ascorbic acid), vitamin D, ergocalciferol (vitamin D ₂ ), vitamin E, DL-a-tocopherol, tocopherol-E-acetate, tocopherol hydrogen succinate, vitamin Ki, esculin (vitamin P active ingredient), thiamine ( Vitamin B), nicotinic acid (niacin), pyridoxine, pyridoxal, pyridoxamine,

(Vitamin Ββ), pantothenic acid, biotin, folic acid and cobalamin (vitamin B12), particularly preferably vitamin A palmitate, vitamin C and its derivatives, DL-α-tocopherol, tocopherol E acetate, nicotinic acid,

Pantothenic acid and biotin. Vitamins are usually added to the flavonoid-containing premixes or preparations when applied cosmetically in the range of 0.01% to 5.0% by weight, based on the total weight. Nutritional physiology applications are based on the recommended vitamin requirement.

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

The said components of the emulsion can be incorporated in the usual way, by means of techniques and other excipients which are well known to the skilled person. Preferred excipients come from the group of preservatives, stabilizers, solubilizers, colorants or odor improvers.

The emulsions may contain the usual excipients such as solvents, solubilizers and other emulsifiers, e.g. Water, ethanol, isopropanol, ethyl carbonate, ethyl acetate, benzyl alcohol, benzyl benzoate, propylene glycol, 1,3-butylglycol, oils, in particular cottonseed oil, peanut oil, maize germ oil, olive oil, castor oil and sesame oil, glycerin fatty acid esters, polyethylene glycols and fatty acid esters of sorbitan or mixtures contain these substances.

The lipid phase of the emulsion according to the invention can advantageously be selected from the following substance group:

Mineral oils, mineral waxes

- Oils, such as triglycerides of capric or caprylic, also

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 in the context of the present invention is advantageously selected from the group of esters of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids having a chain length of 3 to 30 carbon atoms and saturated and / or unsaturated, branched and / or unbranched alcohols of a chain length 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. Such ester oils can then be chosen advantageously from the group isopropyl myristate, isopropyl palmitate, isopropyl stearate,

Isopropyl oleate, n-butyl stearate, n-hexyl laurate, n-decyl oleate, isooctyl stearate, isononyl stearate, isononyl isononanoate, 2-ethylhexyl palmitate,

2-ethylhexyl laurate, 2-hexadecyl stearate, 2-octyl dodecyl palmitate, oleyl oleate, oleyl erucate, erucyl oleate, erucyl erucate and synthetic, semi-synthetic and natural mixtures of such esters, e.g. B. jojoba oil.

The mixture of the invention may preferably contain excipients, 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 tartrates), or polar protic auxiliaries (for example propylene glycol, glycerol, isopropanol, ethanol) or so-called solubilizers (eg butylphthalimides, isopropylphthalimides,

Dimethylisosorbide).

Furthermore, the oil phase can be advantageously selected from the group of branched and unbranched hydrocarbons and waxes, the

Silicone oils, the dialkyl ethers, the group of saturated or unsaturated, branched or unbranched alcohols, and the fatty acid triglycerides, namely the triglycerol esters of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids having a chain length of 8 to 24, in particular 12-18 C-atoms , The fatty acid triglycerides can be selected, for example, advantageously from the group of synthetic, semi-synthetic and natural oils, for. For example, olive oil, sunflower oil, soybean oil, peanut oil, rapeseed oil, almond oil, palm oil, coconut oil, palm kernel oil and the like.

Any mixtures of such oil and wax components are also advantageous to use in the context of the present invention. It can also may be advantageous to use waxes, such as cetyl palmitate, as the sole lipid component of the oil phase.

The aqueous phase of the emulsion according to the invention contains

optionally advantageous alcohols, diols or polyols of low carbon number, 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 -monoethylether and analogous products, furthermore low C-number alcohols, e.g. As ethanol, isopropanol, 1, 2-propanediol,

Glycerol and in particular one or more thickening agents, which or which can be advantageously selected from the group

Silica, aluminum silicates, polysaccharides or their derivatives, e.g. Hyaluronic acid, xanthan gum, hydroxypropylmethylcellulose, particularly advantageous from the group of polyacrylates, preferably a polyacrylate from the group of so-called Carbopols, for example Carbopols types 980, 981, 1382, 2984, 5984, each individually or in combination.

In particular, mixtures of the abovementioned solvents are used. For alcoholic solvents, water can be another

Be part of it.

In a further embodiment, the emulsions according to the invention additionally contain hydrophilic surfactants. The hydrophilic surfactants are preferably selected from the group of alkylglucosides, acyl lactylates, betaines and cocoamphoacetates.

It is likewise advantageous to employ natural or synthetic raw materials and assistants or mixtures which are distinguished by an effective content of the active ingredients used according to the invention, for example Plantaren ^® 1200 (Henkel KGaA), Oramix NS ^® 10 (Seppic). The preparation of emulsions is well known to the person skilled in the art. The at least one compound of the formula (I), (II), (III) or (IV) as described above is used, for example, with at least one of

Emulsions suitable carrier and optionally excipients and / or fillers is mixed, in particular dispersed and / or emulsified.

The technical advantage is achieved when the particulate inorganic UV filter, as described above, is incorporated in the same phase in which the at least one compound of the formula (I) is, as described above or described as being preferred.

Another object of the invention is therefore a process for preparing an emulsion, as described above, characterized

in that the at least one compound of the formula (I) is added to one of the phases of the emulsion and then in the same phase the particulate inorganic UV filter is added.

The complete disclosures of all listed applications and publications are incorporated by reference into this application. In the description and in the examples, unless stated otherwise, percentages are by weight. The following examples further illustrate the present invention without limiting the scope of protection. Examples

Example 1: Synthesis of the compound of the formula (NM)

According to the patent application DE 10 2009 030 846 A1, the

chain-extended alcohol from the reactants 2,2,3,3,3-pentafluoropropan-1-ol (ABCR) and butylene carbonate (TCI) produced. This

Intermediate is esterified with aconitic acid (Alfa Aesar) according to the described method of synthesis and then in the last reaction step by means of an aqueous sodium hydrogen sulphite solution (Merck KGaA) sulfonated. The dynamic surface tension is after the

determined and is 28.2 mN / m (100 ms,

0.1% by weight). Example 2: Synthesis of the compound of the formula (III-2)

According to the patent application DE 10 2009 030 846 is the

chain-extended alcohol from the educts 2,2,3,3,4, 4, 4-heptafluorobutan-1-ol (ABCR) and propylene carbonate (Merck KGaA) produced. This intermediate is esterified with aconitic acid according to the described method of synthesis and then sulfonated in the last reaction step by means of an aqueous sodium hydrogen sulfite solution. The dynamic surface tension is determined by the specified method and is 66.6 mN / m (100 ms, 0.1 wt .-%). Example 3: Preparation of the emulsions and in vitro SPF determination

To study the effect of the compounds of formula (I) as described above on the properties of emulsions, only the type of titanium dioxide and the concentration of surfactants in the phases of the emulsion were varied. Emulsions without a compound of the formula (I) or the comparative surfactant sodium dodecylpoly (oxyethylene) sulfate (SLES, sodium laureth sulfate).

To prepare the W / O emulsions, the oil phase with the

Emulsifiers heated to 80 ° C and the titanium dioxide with a propeller stirrer predispersed therein. In the direct connection becomes with a

High-performance dispersing device (Ultra Turrax T-25, IKA) at defined intensity and duration again dispersed.

The likewise heated to 80 ° C water phase is slowly emulsified into the oil phase, with constant stirring. At about 70 ° C, the emulsion is homogenized with the Ultra Turrax T-25 and cooled to 40 ° C with stirring and homogenized again. In the case of an O / W emulsion, the pH is additionally adjusted to 4.5 to 5.5.

Example 3.1. : Water-in-oil emulsions

The following Table 1 gives the composition of the water-in-oil basic emulsion:

Table 1 :

The properties of the emulsion with respect to in vitro SPF elevation using the titanium dioxides Eusolex T-Pro, Eusolex TS, Eusolex T-2000 are investigated. The titanium dioxides are commercially available from Merck. For each base formulation with a corresponding titanium dioxide, 6 emulsions are prepared, containing the emulsifiers used in different amounts and / or in different phases. A) Using Eusolex T-Pro

Emulsion 1: Basic emulsion with Eusolex T-Pro

Emulsion 2: base emulsion with Eusolex T-Pro and 0.1% of the compound of formula (III-1) in the oil phase

Emulsion 3: Basic emulsion with Eusolex T-Pro and 0.5% of the compound of formula (III-1) in the oil phase

Emulsion 4: basic emulsion with Eusolex T-Pro and 0.1% of the compound of formula (III-1) in the water phase

Emulsion 5: Basic emulsion with Eusolex T-Pro and 0.5% of the compound of formula (III-1) in the water phase

Emulsion 6: Basic emulsion with Eusolex T-Pro and 0, 1% SLES in the

water phase

Emulsion 7: Basic emulsion with Eusolex T-Pro and 0.5% SLES in the

water phase

Preparation: At the beginning, the respective surfactant (the compound of the formula (II 1-1) or SLES) is dissolved in the stated phase. The oil phase and the water phase are then heated separately to 80 ° C. while stirring with a propeller stirrer.

After reaching the temperature, Eusolex T-Pro is first predispersed in the oil phase with the propeller stirrer for five minutes at approx. 500 rpm and then with the high-performance disperser Ultra-Turrax T-25 at 8000 rpm for 30 minutes Seconds dispersed. in the

Following the hot water phase is emulsified with a propeller stirrer at a speed of 1200 rev / min in the oil phase for 30 seconds. After emulsification, the emulsion is allowed to stand for 30 seconds The Ultra Turrax T-25 homogenized at 8500 rpm. The emulsion is stirred until reaching 40 ° C and then homogenized again for 30 seconds at 8500 U / min with the Ultra Turrax T-25. After this

The emulsion is homogenized with constant stirring

Cooled room temperature and then filled into 100mL glass bottles.

The in vitro SPF determination takes place one week after preparation of the emulsions.

Measurement:

To determine the sun protection factor, a sample of the emulsion, as described above, on a UV-permeable PMMA plate with unilaterally defined roughening and an area of 25 cm ² distributed (Heliplate HD Helio Screen labs Laboratories). The samples are dried in the dark for 30 minutes to achieve the formation of a stabilized product film. Thereafter, the plates are irradiated, measuring the transmission of the sample in steps of 1 nm for each wavelength from 290 nm to 400 nm. The transmittance of the formulation is detected with the UV spectrophotometer UV-2000S (transmission analyzer from Labsphere). Measured in each case on 5 measuring points of the plate. The calculation of in vitro SPF is done with the integrated

Software of the spectrophotometer. There are three plates for each emulsion as previously described

prepared. This gives 15 readings for each emulsion. The

Measurement results of the SPF determination are listed in Table 2 below: Table 2:

* Stability measured during storage in the changeover temperature test 40 ° C / -5 ° C in a 24 h time cycle over a period of 8 weeks, the assessment is inhomogeneous via observation in a light microscope

It can be seen from the results that the highest SPF values for the compound of formula (III-1) are obtained when it is in the oil phase, ie in the same phase as Eusolex T-Pro. B) Analogous to A), emulsions are prepared with the titanium dioxide Eusolex TS:

Emulsion 8: basic emulsion with Eusolex T-S

Emulsion 9: Eusolex T-S base emulsion and 0.1% of the compound of formula (III-1) in the oil phase

Emulsion 10: Basic emulsion with Eusolex T-S and 0.5% of the compound of formula (III-1) in the oil phase

Emulsion 11: Basic emulsion with Eusolex T-S and 0.1% of the compound of formula (III-1) in the water phase

Emulsion 12: Eusolex T-S base emulsion and 0.5% of the compound of formula (III-1) in the water phase

Emulsion 13: Basic emulsion with Eusolex T-S and 0.1% SLES in the

water phase

Emulsion 14: Basic emulsion with Eusolex T-S and 0.5% SLES in the

water phase

Table 3 summarizes the in vitro SPF values:

Emulsion SPF stability in weeks *

8 15,8 8 - homogeneous

9 16.3 8 - homogeneous

10 19.1 1 - homogeneous

1-4 - looks inhomogeneous, but no deposition

4-8 - light

phase separation

11 16.6 8 - homogeneous

12 16.5 8 - homogeneous

13 16.8 8 - homogeneous

14 16.9 2 - homogeneous

2-4 - looks inhomogeneous, but no deposition

4-8 - light

phase separation

^* Stability measured during storage in the changeover temperature test 40 ° C / -5 ° C in a 24 h time cycle over a period of 8 weeks, the assessment is inhomogeneous via observation in a light microscope

It can be seen from the results that for this titanium dioxide, the highest SPF value is achieved when using 0.5% by weight of the compound of the formula (III-1).

C) Analogous to A), emulsions are prepared with the titanium dioxide Eusolex T-2000:

Emulsion 15: basic emulsion with Eusolex T-2000

Emulsion 16: Eusolex T-2000 base emulsion and 0.1% of the compound of formula (III-1) in the oil phase

Emulsion 17: base emulsion with Eusolex T-2000 and 0.5% of the compound of formula (III-1) in the oil phase

Emulsion 18: basic emulsion with Eusolex T-2000 and 0.1% of the compound of formula (III-1) in the water phase

Emulsion 19: Eusolex T-2000 base emulsion and 0.5% of the compound of formula (III-1) in the water phase

Emulsion 20: Basic emulsion with Eusolex T-2000 and 0.1% SLES in the

water phase

Emulsion 21: basic emulsion with Eusolex T-2000 and 0.5% SLES in the

water phase

Table 3 summarizes the in vitro SPF values: Emulsion SPF stability in weeks ^*

15 9,5 8 - homogeneous

16 10,1 8 - homogeneous

17 12,1 4-8 - seems inhomogeneous, but none

deposition

18 9.8 8 - homogeneous

19 10,1 8 - homogeneous

20 10.0 8 - homogeneous

21 10,1 4-8 - looks inhomogeneous, but none

deposition

It can be seen from the results that for this titanium dioxide, the highest SPF value is achieved when using 0.5 wt .-% of the compound of formula (III-1) with an increase of 27%.

Example 3.2 .: Oil-in-water emulsions

The following Table 4 indicates the composition of the oil-in-water base emulsion:

Table 4:

Ingredient Function% by weight

Oil phase

Glyceryl Stearate, O / W Emulsifier 8.0

PEG-100 stearates

Glyceryl stearate coemulsifier, 2.0

bodying Cetearyl alcohol coemulsifier, 1, 0

bodying

Isopropyl palmitate oil 10.0

Propylparaben preservative 0.05

Water phase

UV filter UV filter 7.0

Water 56.8

Glycerin moisturizer 5.0

Methylparaben preservative 0.15

The properties of the emulsion with respect to the in vitro SPF increase using the titanium dioxides Eusolex T-Pro and Eusolex T-Avo in the water phase are investigated. Eusolex T-2000 was, however, due to the high hydrophobic properties with 7 wt .-% in the oil phase

incorporated. The titanium dioxides are commercially available from Merck.

For each base formulation with a corresponding titanium dioxide, 6 emulsions are prepared, containing the emulsifiers used in different amounts and / or in different phases. The

Production method of O W emulsions differs only in the phase addition and the duration of homogenization of the W / O

Emulsions of Example 3.1. In O / W emulsions, the hot oil phase is emulsified into the water phase and homogenized for a longer time.

The pre-dispersion of the water phase of 80 ° C is carried out at 500 rev / min for 5 min. The dispersion takes place in the Ultra-Turrax T-25 at 8000 rpm for 30 seconds. The emulsification with the oil phase (80 ° C) is carried out with the

Propeller stirrer at 600 rpm for 30 seconds. The homogenization is carried out at a temperature of 70 ° C in Ultra-Turrax T-25 at 8500 / min for 120 seconds. The cooling to 40 ° C is achieved at 500 U / min. The Homogenization at 40 ° C was performed in the Ultra-Turrax T-25 at 8500 rpm for 60 seconds.

After the preparation of the O / W emulsions, the pH is further adjusted with citric acid between 4.5 and 5.5.

D) Use of Eusolex T-Pro Emulsion 22: Basic emulsion with Eusolex T-Pro

Emulsion 23: base emulsion with Eusolex T-Pro and 0.1% of the compound of formula (III-1) in the oil phase

Emulsion 24: base emulsion with Eusolex T-Pro and 0.5% of the compound of formula (III-1) in the oil phase

Emulsion 25: basic emulsion with Eusolex T-Pro and 0.1% of the compound of formula (III-1) in the water phase

Emulsion 26: basic emulsion with Eusolex T-Pro and 0.5% of the compound of formula (III-1) in the water phase

Emulsion 27: Basic emulsion with Eusolex T-Pro and 0.1% SLES in the

water phase

Emulsion 28: base emulsion with Eusolex T-Pro and 0.5% SLES in the

water phase

The in vitro SPF determination takes place one week after preparation of the emulsions. The measurement is carried out according to the description of Example 3.1.

The measurement results of the SPF determination are listed in the following Table 5:

Table 5: Emulsion SPF stability in weeks ^*

22 17,7 8 - homogeneous

23 17.5 8 - homogeneous

24 18,1 8 - homogeneous

25 19,1 8 - homogeneous

26 19.9 8 - homogeneous

27 17,9 8 - homogeneous

28 17,7 8 - homogeneous

It can be seen from the results that the highest SPF values for the compound of the formula (III-1) are obtained when these are used in the

Water phase is present, i. in the same phase as Eusolex T-Pro.

E) Analogous to D), emulsions are prepared with the titanium dioxide Eusolex T-Avo:

Emulsion 29: Basic Emulsion with Eusolex T-Avo

Emulsion 30: base emulsion with Eusolex T-Avo and 0.1% of the compound of formula (III-1) in the oil phase

Emulsion 31: Eusolex T-Avo base emulsion and 0.5% of the compound of formula (III-1) in the oil phase

Emulsion 32: basic emulsion with Eusolex T-Avo and 0.1% of the compound of formula (III-1) in the water phase

Emulsion 33: Eusolex T-Avo base emulsion and 0.5% of the compound of formula (III-1) in the water phase

Emulsion 34: Basic emulsion with Eusolex T-Avo and 0.1% SLES in the

water phase Emulsion 35: basic emulsion with Eusolex T-Avo and 0.5% SLES in the water phase

Table 6 summarizes the in vitro SPF values:

It can be seen from the results that for this titanium dioxide, the highest SPF values are obtained when using 0.5% by weight of the compound of the formula (II 1-1) both in the water phase and in the oil phase, compared to the Emulsifier SLES or compared to the

Base Emulsion The use of the compound of the formula (III-1) generally leads to an improvement of the SPF for titanium dioxide with silicon dioxide coating. In order to show the advantage according to the invention for O / W emulsions, an alternative base emulsion is suitable.

F) Analogous to D), emulsions are prepared with the titanium dioxide Eusolex T-2000 in the oil phase:

Emulsion 36: basic emulsion with Eusolex T-2000

Emulsion 37: base emulsion with Eusolex T-2000 and 0.1% of the compound of formula (III-1) in the oil phase Emulsion 38: base emulsion with Eusolex T-2000 and 0.5% of the compound of formula (III-1) in the oil phase

Emulsion 39: basic emulsion with Eusolex T-2000 and 0.1% of the compound of formula (III-1) in the water phase

Emulsion 40: basic emulsion with Eusolex T-2000 and 0.5% of the compound of formula (111-1) in the water phase

Emulsion 41: basic emulsion with Eusolex T-2000 and 0.1% SLES in the

water phase

Emulsion 42: Basic emulsion with Eusolex T-2000 and 0.5% SLES in the

water phase

Table 7 summarizes the in vitro SPF values:

It can be seen from the results that for this titanium dioxide in this emulsion type of the base emulsion, the compound of the formula (III-1) is an alternative emulsifier.

Claims

claims

1. Emulsion comprising at least one compound of the formula (I)

in which

X is a hydrophilic group,

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, NC (O) -N, SiR ' ₂ -, SiR' ₂ Is -Ο, O-SO2 or SO ₂ -0, where R '= linear or branched alkyl,

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

-CH ₂ -COY ³ -L ³ - (A ³⁾ _n3 are

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

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

Alkylene, 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 ) _mi Rf ⁱ , where i = 1, 2 or 3,

Z 'is O, S or N and is attached to a C atom of L' or is a single bond,

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

Are alkyl group, Rf is a fluorine-containing radical,

n1, n2 and n3 are independently 1-6,

m1, m2 and m3 are independently 0-5,

and the compounds of formula (I) contain at least one Rf 'group, and at least one particulate inorganic UV filter, wherein both the compound of formula (I) and the particulate inorganic UV filter are in substantially the same phase of Emulsion are located.

Emulsion according to Claim 1, characterized in that the emulsion is an oil-in-water emulsion or a water-in-oil emulsion.

Emulsion according to Claim 1 or 2, characterized in that the emulsion is a water-in-oil emulsion.

Emulsion according to one or more of Claims 1 to 3, characterized in that the compounds of the formula (I) used are compounds of the formulas (II), (III) and / or (IV),

(IV)

in which

X represents -SO ₃ ^" , -OSO ₃ ^" , -PO ₃ ^{2 "} or OPO ₃ ^ ^~ ,

Y ¹ , Y ² , Y ³ , z Z ² and Z ^{3 are} O,

Rf ¹ , 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 1, 2, 3 or 4,

L ¹ , L ² and L ^{3 represent} a linear or branched C ₃ - C 6 -alkylene and

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

5. Emulsion according to one or more of claims 1 to 4, characterized in that as compounds of formula (I)

6. Emulsion according to one or more of claims 1 to 5, characterized in that a particulate metal oxide is contained as a particulate inorganic UV filter, which can carry at least one coating.

7. Emulsion according to one or more of claims 1 to 6, characterized in that at least one particulate metal oxide from the group of titanium dioxide, iron oxides, zinc oxide or Cerium oxide is contained as a particulate inorganic UV filter, which may be doped.

8. Emulsion according to one or more of claims 1 to 7,

characterized in that at least one particulate

Titanium dioxide is contained as a particulate inorganic UV filter, which may be doped and which at least one

Coating carries.

9. Emulsion according to one or more of claims 1 to 8,

characterized in that the compounds of the formula (I) are contained in 0.01 to 2 weight percent, based on the total amount of the emulsion.

10. A process for the preparation of an emulsion according to one or

more of claims 1 to 9, characterized in that the compounds of formula (I) are added to one of the phases of the emulsion and then added in the same phase of the particulate inorganic UV filter.

11.Use of compounds of the formula (I)

(I)

in which

X is a hydrophilic group,

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, NC (O) -N, SiR ' ₂ -, SiR' ₂ -Ο , O-SO ₂ or SO ₂ -O, where R '= linear or branched alkyl,

R and R ^{2 are} independently hydrogen or

-CH ₂ -COY ³ -L ³ - (A ³⁾ _n3 are

Y, 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 structure

where i is 1, 2 or 3,

Z 'is O, S or N and is attached to a C atom of L' or is a single bond,

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

Are alkyl group,

Rf is a fluorine-containing radical,

n1, n2 and n3 are independently 1-6,

m1, m2 and m3 are independently 0-5,

and the compounds of formula (I) contain at least one Rf group in emulsions containing particulate inorganic UV filters, wherein the compound of formula (I) and the particulate inorganic UV filter are in substantially the same phase of the emulsion.

12. Use according to claim 11, characterized in that the emulsion is an oil-in-water emulsion or a water-in-oil emulsion.