GB2440638A

GB2440638A - 2-(2'-Hydroxy-4'-aminophenyl)benzotriazoles as UV protecting agents

Info

Publication number: GB2440638A
Application number: GB0714357A
Authority: GB
Inventors: Barbara Wagner
Original assignee: Ciba Spezialitaetenchemie Holding AG; Ciba SC Holding AG
Current assignee: BASF Schweiz AG; Ciba SC Holding AG
Priority date: 2007-07-24
Filing date: 2007-07-24
Publication date: 2008-02-06
Also published as: GB0714357D0

Abstract

Disclosed is the use of 2-(2'-Hydroxy-4'-aminophenyl)benzotriazole derivatives of formula (I): <EMI ID=1.1 HE=34 WI=101 LX=386 LY=813 TI=CF> <PC>Wherein; <DL TSIZE=10> <DT>R1 and R4<DD>independently of each other are hydrogen; C1-C28alkyl; C1-C28alkoxy; C2-C28alkenyl; C2-C28alkinyl; C3-C12cycloalkyl; C3-C12cycloalkenyl; C7-C28 aralkyl; C1-C20heteroalkyl; C3-C12cycloheteroalkyl; or C5-C16 heteroaralkyl; and wherein C1-C28alkyl, C1-C28alkoxy, C2-C28alkenyl and C2-C28alkinyl are unsubstituted or may be substituted by at least one C1-C5alkyl, C1-C5alkoxy or hydroxy; <DT>R2 and R3<DD>independently of each other are hydrogen; C1-C28alkyl; C2-C28alkenyl; C2-C22alkinyl; C3-C12cycloalkyl; C3-C12cycloalkenyl; C7-C28 aralkyl; C1-C20heteroalkyl; C3-C12cycloheteroalkyl; C5-C16heteroaralkyl; and wherein C1-C28alkyl, C1-C28alkoxy, C2-C28alkenyl and C2-C28alkinyl are unsubstituted or may be substituted by at least one C1-C5alkyl, C1-C5alkoxy or hydroxyl; or CO-R5; or <DT>R2 and R3<DD>together with the linking nitrogen form a 5- to 7-membered, monocyclic, carbocyclic or heterocyclic ring; <DT>R5<DD>is C1-C28alkyl; C2-C28alkenyl; C2-C28alkinyl; C3-C12cycloalkyl; C3-C12cycloalkenyl; C7-C20aralkyl; C1-C20 heteroalkyl; C3-C12 cycloheteroalkyl; C1-C5alkoxycarbonyl-C1-C5alkyl; or C5-C16heteroaralkyl; and <DT>n<DD>is 1,2, 3 or 4; for protecting human and animal hair and skin from harmful effects of UV radiation e.g. as an anti-wrinkle perception modifier. </DL> Also disclosed is a cosmetic preparation comprising at least one compound of formula (1).

Description

HU/l -23526/A/PP -*1-Aminobenzotrjazoles The present invention relates

to the use of specific benzotriazole UV absorbers for protecting human and animal hair and skin from the harmful effects of UV radiation and cosmetic compositions comprising these compounds.

Therefore, the present invention relates to the use of 2-(2'-Hydroxy-4'-aminophenyl)benzotriazole derivatives of formula

HO

>=\ R2 (1) (Rl)r_1 N-\__N,wherein R1 and R4 independently of each other are hydrogen; C1-C28alkyl; C1-C28alkoxy; C2-C28al- kenyl; C2-C28alkinyl, C3-C12cycloalkyl; C3-C12cycloalkenyl; C7-C28 aralkyl; C1-C20hetero- alkyl; C3-C12cycloheteroalkyl; or C5-C1 heteroaralkyl; and wherein C1-C28aIkyl, C1-C28al-koxy, C2-C28alkenyl and C2-C28alkinyl are unsubstituted or may be substituted by at least one C1-C5alkyl, C1-C5alkoxy or hydroxy; R2 and R3 independently of each other are hydrogen; C1-C28alkyl; C2-C28 alkenyl; C2-C22alki- nyl; C3-C12cycloalkyl; C3-C12cycloalkenyl; C7-C2 aralkyl; C1-C20 heteroalkyl; C3-C12cyclo-heteroalkyl; C5-C16heteroaralkyl; and wherein C1-C28alkyl, C1-C28alkoxy, C2-C28alkenyl and C2-C78alkinyl are unsubstituted or may be substituted by at least one C1-C5alkyl, C1-C5alkoxy or hydroxy; or CO-R5; or R2 and R3 together with the linking nitrogen form a 5-to 7-membered, monocyclic, carbo-cyclic or heterocyclic ring; R5 is C1-C28alkyl; C2-C28akenyl; C2-C28alkinyl; C3-C12cycloalkyl; C3-C12cycloalkenyl; C7-C23aralkyl; C1-C20 heteroalkyl; C3-C12 cycloheteroalkyl; C1-C5alkoxycarbonyl-C1-C5alkyl; or C5-C16heteroaralkyl; and n isl,2,3or4; for protecting human and animal hair and skin from harmful effects of UV radiation.

Alkyl, cycloalkyl, alkenyl or cycloalkenyl radicals can be straight-chain or branched or also monocyclic or poycyclic.

Alkyl can be for example straight-chain 01-028 alkyl or preferably branched C3-C12 alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, isobutyl, tert.-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl, n-hexyl, n-octyl, 1,1,3,3-tetramethylbutyl, 2-ethylhexyl, nonyl, decyl, n-octadecyl, eicosyl, or dodecyl C3-C12cycloalkyl is for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, trimethylcyclohexyl, menthyl, thujyl, bornyl, 1-adamantyl or 2-adamantyl.

Alkenyl can be e.g. straight-chain C2-C28alkenyl or preferably branched C3-C12alkenyl.

C2-C28alkenyl or C3-C12cycloalkenyl refers to unsaturated hydrocarbon residues containing one or multiple double bonds such vinyl, allyl, 2-propen-2-yl, 2-buten-1-yl, 3-buten-1-yl, 1,3-butadien-2-yl, 2-cyclobuten-1 -yl, 2-penten-i -yl, 3-penten-2-yl, 2-methyl-i -buten-3-yl, 2-methyl-3-buten-2-yl, 3-methyl-2-buten-1 -yl, 1,4-pentadien-3-yl, 2-cyclopenten-i -yl, 2-cyclohexen-i -yl, 3-cyclohexen-i -yl, 2,4-cyclohexadien-i -yl, 1 -p-menthen-8-yl, 4(10)-thujen-10-yl, 2-norbornen-1-yl, 2,5-norbornadien-1-yl, 7,7-dimethyl-2,4-norcaradien-3yl or signifies different isomers of hexenyl, octenyl, nonenyl, decenyl or dodecenyl.

C7-C28 aralkyl is for example benzyl, 2-benzyl-2-propyl, i-phenyl-ethyl, 9-fluorenyl, cx,a-d imethylbenzyl, w-phenyl-butyl, o-phenyl-octyl, o-phenyl-dodecyl oder 3-methyl-5- (1', 1,3',3'-tetramethyl-butyl)-benzyl.

07-028 aralkyl can be unsubstituted or substituted at the alkyl-as well at the aryl-moiety of the aralkyl-group, but is preferably substituted at the aryl-moiety.

C5-C16heteroaralkyl isfor example a C1-C8 alkyl moiety which is substituted with a C4-C8heteroaryl group Preferably in formula (1) R1 is hydrogen; C1-C28alkyl; or C1-C28alkoxy, more preferably hydrogen; C1-C5alkyl; or C-C5alkoxy; most preferably hydrogen; methyl, tert. butyl; or methoxy; Preferably in formula (1) R4 is hydrogen; or C1-C5alkyl; more preferably hydrogen.

Preferably in formula (1), R7 is hydrogen; C1-C28alkyl; C2-C28 alkenyl; and wherein C1-C28alkyl and 02-C28alkenyl are unsubstituted or may be substituted by at least one C1-C5alkyl, C1-C5alkoxy or hydroxy; or CO-R5; and R5 is C1-C28aIkyI; C1-C5alkoxycarbonyl-C1-C5alkyI; or C3-Ci2cycloalkyl Preferably, R2 is hydrogen; C1-C1oalkyl; 02-010 alkenyl; and wherein C2-C10aikenyl is unsubstituted or may be substituted by C1-C5alkoxy; CO-R5; R5 is C1-C10alkyl; C1-C5alkoxycarbonyl-C1-C5alkyl; or C3-C12cycloalkyl.

More preferably, R2 is hydrogen; C1-C5alkyl, or CO-R5; and R5 is C1-C10alkyl; -CH2-CH2(CO)-O-07H5; or cyclohexyl; most preferably R5 is isooctyl.

Preferably in formula (1), R3 is hydrogen; or *-(CO)-CH3.

Preferred are also compounds of formula (1), wherein R2 and R3 have the same meaning; more preferably, wherein R2 and R3 are C1-C5alkyl.

Preferred are also compounds of formula (1), wherein R2 and R: together with the linking nitrogen form the heterocyclic ring radical of formula (la)

I

Preferred compounds of formula (1) are those, wherein R1 is hydrogen; C1-Calkyl; or C1-C5alkoxy; R4 is hydrogen; or 01-C5alkyl; R7 is hydrogen; C1-C10alkyl; C2-C10 alkenyl; and wherein C2-C1oalkenyl is unsubstituted or may be substituted by C1-C5alkoxy; or CO-R5; R5 is Ci-C10alkyI; C1-C5alkoxycarbonyl-C1-C5alkyI; or C3-C17cycloalkyl; R3 is hydrogen; or *-(CQ)0H3; and more preferably those, wherein R is hydrogen; or C1-Calkyl; R2 is CO-R5; R3 is hydrogen; R5 is isooctyl; and R4 is hydrogen.

Examples of preferred aminobenzotriazols of the present invention are listed in Table 1: Table 1: Aminobenzotriazoles of the present invention BT-01 HO BT-02 HO 0 > , )== -\ BT-03 HO BT-04 HO >:= >=\ -N -%j---NH2))N -K\>--NH2 BT-05 HO 0 BT-06 HO 0 BT-07 HO 0 BT-08 HO 0 BT-09 HO BT-10 HO

I N

-%j--N 0-N -j--N BT-11 HO 0 BT-12 HO 0

N-J-N

Table 1: Aminobenzotriazoles of the present invention BT-13 HO 0 BT-14

HO O

N /=

BT-15 HO 0 BT-16 HO 0

N /)=O

BT-17 HO BT-18 HO 0 BT-19 HO 0 BT-20 HO 0

N NN

BT-21 HO 0 BT-22 HO 0

N

IN

BT-23 HO 0 BT-24 HO 0 BT-25 BT-26 HO 0 HO 0 BT-27 BT-28 HO 0

HO

Table 1: Aminobenzotriazoles of the present invention BT-29 HO BT-30 HO BT-31 HO BT-32 HO The benzotriazole derivatives of formula (1) may be prepared starting from a 2-nitroaniline derivative which is then diazotized. The resulting diazonium intermediate reacts with 3-amino-or 3-amino alkyl-substituted phenols to the corresponding azo dye which is reduced to the desired benzotriazole derivative.

OH

::: H2Oi NR X= OH, NH NEt.

R1NNR2R3 1) 2)H R1NNR2R Another method for the preparation of N-alkylated benzotriazole UV absorbers according to the present invention is to alkylate a R1-/R-substituted 2-(2'-hydroxy-4'-aminophenyl benzo-triazole at the amino group. The alkylation can be achieved by conventional alkylfion me-thods. One method may be to use alkylhalogenides like alkylbromides or alkyl chlorides as alkylating reagent and sodium hydride or another deprotonating reagent. The reaction is then carried out in a suitable solvent like toluene, pyridine or polar aprotic solvents such as e.g. 1-methyl-2-pyrrolidone, dimethylformamide, dimethylsulfoxide, dioxane, tetrahydrofuran, acetonitrile and the hke. The alkylation can be carried out once resulting in the corresponding 4-monoalkylamino benzotriazole derivatives or can be carried out twice resulting in the corresponding 4'-dialkylamino benzotriazole compounds.

HO HO

7'-N R2Br >=\ 71 R1-$J,N__<\.)__NH2 NaH, DMF R1_I N N:ftDMF According to the above mentioned method the R1-/R4-su bstituted 2-(2'-hydroxy-4'-am mo-phenyl) benzotriazole may also be acylated at the amino group by using known acylating methods. A convenient method is using acyl halides as acylating reagents in a suitable sol-vent like toluene or pyridine in the presence of an acid acceptor, such as a mild base. In the case pyridine is used as a solvent, it can also serve as an acid acceptor.

R1_-:N_--NH2 CiR2 R4 Py,8OC,2h The monoacylated benzotriazoles may subsequently be acylated to the corresponding N,N- diacylated benzotriazole derivatives or may also be alkylated in another step to the corres-ponding N-alkylated benzotriazolylphenyl amide compounds.

The compounds of the formula (1) according to the present invention are particularly suitable as UV filters, i.e. for protecting ultraviolet-sensitive organic materials, in particular the skin and hair of humans and animals, from the harmful effects of UV radiation. These compounds are therefore suitable as sunscreens in cosmetic, pharmaceutical and veterinary medical preparations. These compounds can be used both in dissolved form and in the micronized state.

The UV absorbers of formula (1) according to the present invention can be used either in the dissolved state (soluble organic filters, solubelized organic filters) or in the micronised state (nanoscalar organic filters, particulate organic filters, UV-absorber pigments).

Any known process suitable for the preparation of microparticles can be used for the pre-paration of the micronised UV absorbers, for example -wet-milling (low viscous micronisation process for pumpable dispersions), with a hard grinding medium, for example zirconium silicate balls in a ball mill and a protective surfactant or a protective polymer in water or in a suitable organic solvent; -wet-kneading (high viscous micronisation process non pump-able pastes) using a continuous or discontinuous (batch) kneader. For a wet-kneading process a solvent (water or cosmetically acceptable oils), a grinding-aid (surfactant, emulsifier) and a polymeric grinding aid may be used.

-spray-drying from a suitable solvent, for example aqueous suspensions or suspensions containing organic solvents, or true solutions in water, ethanol, dichloroethane, toluene or N-methylpyrrolidone etc..

-by the expansion according to the RESS process (Rapid Expansion of Supercritical Solutions) of supercritical fluids (e.g. C02) in which the UV filter or filters is/are dissolved, or the expansion of fluid carbon dioxide together with a solution of one or more UV filters in a suitable organic solvent; -by reprecipitation from suitable solvents, including supercritical fluids (GASR process = Gas Anti-Solvent Recrystallisation I PCA process = Precipitation with Compressed Anti-solvents).

As milling apparatus for the preparation of the micronised organic UV absorbers there may be used, for example, a jet mill, ball mill, vibratory mill or hammer mill, preferably a high-speed mixing mill. Even more preferablyused are modern ball mills; manufactures of these mill-types are for example Netzsch (LMZ-mill), Drais (DCP-viscoflow or cosmo), Bühler AG (centrifugal mills) or Bachhofer. The grinding is preferably carried out with a grinding aid.

As kneading apparatus for the preparation of the micronised organic UV absorbers examples are typically sigma-hook batch kneaders but also serial batch kneaders (IKA-Werke) or continuous kneaders (Contiuna from Werner und Pfleiderer).

Useful low molecular weight grinding aids for all the above micronizing processes are sur-factants and emulsifies as disclosed below in the chapters "emulsifiers" and "surfactants" and "fatty alcohols" Useful polymeric grinding aids for water dispersion are cosmetically acceptable water soluble polymers with Mn > 500 g/mol for example acrylates (Salcare types), modified or non-modi- fied polysaccharides, polyglucosides or xanthan gum. Furthermore an alkylated vinylpyrroli- done polymer, a vinylpyrrolidone/vinyl acetate copolymer, an acyl glutamate, an alkyl poly- glucoside, ceteareth-25 or a phospholipid may be used. Oil dispersions may contain cos-meticcally acceptable waxy polymers or natural waxes as polymeric grinding aid in order to adjust viscosity during and after processing. Examples of other useful polymeric grinding aids are dieclosed below in the chapter "polymers".

Useful solvents for the grinding process are water, brine, (poly-)ethylenglycol, glycerine or cosmetically acceptable oils. Other useful sovents are disclosed below in the chapters "esters of fatty acids", "natural and synthetic triglycerides including glyceryl esters and derivatives", "perlescent waxes", "hydrocarbon oils" and "silicones or siloxanes".

The micronised UV absorbers so obtained usually have an average particle size from 0.02 to 2, preferably from 0.03 to 1.5, and more especially from 0.05 to 1.0 micrometer.

The UV absorbers according to the present invention can also be used as dry substrates in powder form. For that purpose the UV absorbers are subjected to known grinding methods, such as vacuum atomization, countercurrent spray-drying etc.. Such powders have a particle size from 0 1 micrometer to 2 micrometer. In order to avoid the occurrence of agglomeration, the UV absorbers may be coated with a surface-active compound prior to the pulverization process, for example with an anionic, non-ionic or amphoteric surfactant, e.g. a phospholipid or a known polymer, such as PVP, an acryiate etc..

The UV absorbers according to the present invention can also be used in specific carriers for cosmetics, for example in solid lipid nanoparticles (SLN) or in inert sol-gel microcapsufes wherein the UV absorbers are encapsulated (Pharmazie, 2001 (), p. 783-786).

Lipid nanoparticles (CLN, = Crystalline Lipid Nanoparticles) as described in Internat.

J. Pharmaceutics, 2002, 242, P 373-375 can be used as active carrier for UV filter according to the invention.

The cosmetic formulations or pharmaceutical compositions according to the present inven-tion may additionally contain one or more than one further UV filter as listed in Tables 1-3.

The cosmetic or pharmaceutical preparations can be prepared by physically mixing the UV absorber(s) with the adjuvant using customary methods, for example by simply stirring to-gether the individual components, especially by making use of the dissolution properties of already known cosmetic UV absorbers, like octyl methoxy cinnamate, salicylic acid isooctyl ester, etc.. The UV absorber can be used, for example, without further treatment, or in the micronised state, or in the form of a powder.

Cosmetic or pharmaceutical preparations contain from 0.05-40% by weight, based on the total weight of the composition, of one UV absorber or UV absorber mixtures.

Preference is given to the use of mixing ratios of the UV absorber of formula (1) according to the present invention and optionally further light-protective agents (as described in Ta-bles 1-3) from 1:99 to 99:1, preferably from 1:95 to 95:1 and most preferably from 10:90 to 90:10, based on weight. Of special interest are mixing ratios of from 20:80 to 80:20, preferably from 40:60 to 60:40 and most preferably approximately 50:50. Such mixtures can be used, inter a/ia, to improve the solubility or to increase UV absorption The UV absorbers of formula (1) according to the present invention or combinations of UV filters are useful to protect skin, hair and/or natural or artificial hair color.

Table 2: Suitable UV filter substances which can be additionally used with the UV absorbers accordina to the present invention p-aminobenzoic acid derivatives, for example 4-dimethylaminobenzoic acid 2-ethylhexyl ester; salicylic acid derivatives, for example salicylic acid 2-ethylhexyl ester; benzophenone derivatives, for example 2-hydroxy-4-methoxybenzophenone and its 5-sulfonic acid derivative; dibenzoylmethane derivatives, for example 1-(4-tert-butylphenyl)-3-(4-methoxyphenyl)-Table 2: Suitable UV filter substances which can be additionally used with the UV absorbers according to the present invention propane-i,3-dione; diphenylacrylates, for example 2-ethylhexyl 2-cyano-3,3-diphenylacrylate, and 3-(benzo-furanyl) 2-cyanoacrylate; 3-imidazol-4-ylacrylic acid and esters; benzofuran derivatives, especially 2-(p-aminophenyl)benzofuran derivatives, described in EP-A-582 189, US-A-5 338 539, US-A-5 518 713 and EP-A-613 893; polymeric UV absorbers, for example the benzylidene malonate derivatives described in EP-A-709 080; cinnamic acid derivatives, for example the 4-methoxycinnamic acid 2-ethylhexyl ester and isoamyl ester or cinnamic acid derivatives described in US-A-5 601 811 and WO 97/00851; camphor derivatives, for example 3-(4'-methyl)benzylidene-bornan-2-one, 3-benzylidene- bornan-2-one, N-[2(and 4)-2-oxyborn-3-ylidene-methyl)-benzyl]acrylamide polymer, 3-(4'-trimethylammonium)-benzylidene-bornan-2-one methyl sulfate, 3,3'-(l,4-phenylenedi-methine)-bis(7,7-dimethyl-2-oxo-bicyclo[2.2.1] heptane-1-methanesulfonic acid) and salts, 3-(4'-sulfo)benzylidene-bornan-2-one and salts; camphorbenzalkonium methosulfate; hyd roxyphenyltriazine compounds, for example 2-(4'-methoxyphenyl)-4,6-bis(2'-hydroxy-4'-n-octyloxyphenyl)-1,3, 5-triazine; 2,4-bis{[4-(3-(2-propyloxy)-2-hydroxy-propyloxy)-2-hy- d roxy]-phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine; 2,4-bis{[4-(2-ethyl-hexyloxy)-2-hydroxy]- phenyl}-6-[4-(2-methoxyethyl-ca rboxyl)-phenylami no]-1,3,5-triazine; 2,4-bis{[4-(tris- (tn methylsilyloxy-silylpropyloxy)-2-hyd roxy]-phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine; 2,4-bis{[4-(2"-methylpropenyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl) -1,3,5-triazine; 2,4-bis{[4-( 1', 1,l,3',5',5', 5'-heptamethyltrisilyl-2"-methyl-propyloxy)-2-hydroxy]-phenyl}-6(4-methoxyphenyl)-1,3,5-triazine; 2,4-bis{[4-(3-(2-propyloxy)-2-hydroxy-propyloxy)-2-hydroxy]-phenyl}-6[4-ethylcarboxy)-phenylamino]-1,3,5-triazine; benzotriazole compounds, for example 2,2'-methylene-bis(6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl) -phenol; trianilino-s-triazine derivatives, for example 2,4,6-trianiline-(p-carbo-2'-ethyl-l'-oxy)-l,3,5-triazine and the UV absorbers disclosed in US-A-5 332 568, EP-A-517 104, EP-A-507 691, 2-phenylbenzimidazole-5-sulfonic acid and salts thereof, menthyl o-aminobenzoates; physical sunscreens coated or not as titanium dioxide, zinc oxide, iron oxides, mica, MnO, Fe203, Ce203, A1203, Zr02. (surface coatings: polymethylmethacrylate, methicone (methy!hydrogenpolysloxane as described in CAS 9004 73-3), dimcthicone, isopropyl titanium triisostearate (as described in CAS 61417-49-0), metal soaps as magnesium stearate (as described in CAS 4086-70-8), perfluoroalcohol phosphate as C9-15 fluoroalcohol phosphate (as described in CAS 74499-44-8; JP 5-86984, JP 4-330007)).

The primary particle size is an average of l5nm-35nm and the particle size in dispersion is in the range of lOOnm -300nm.

aminohydroxy-benzophenone derivatives disclosed in DE 10011317, EP 1133980 and EP -12-Table 2: Suitable UV filter substances which can be additionally used with the UV absorbers according to the present invention phenyl-benzimidazole derivatives as disclosed in EP 1167358 the UV absorbers described in "Sunscreens", Eds. N.J. Lowe, N A.Shaath, Marcel Dekker, Inc., New York and Basle or in Cosmetics & Toiletries (107), 50ff (1992) also can be used as additional UV protective substances.

Table 3. Suitable UV filter substances which can be additionally used with the UV absorbers according to the present invention (Abbreviations T table, R row, Comp compound, Ex compound(s) of patent example, p page), the generic scope of the UV absorbers is described in the left-hand column, specific compounds are indicated in the right-hand column DE 100331804 Tab 1 p4, tab 2 + 3 p5 EP 613893 Ex 1-5 + 15, T 1, pp 6-8 EP1000950 Comp. in table 1, pp 18-21 EP1005855 T3,p13 EP1008586 Ex 1-3, pp 13-15 EP 1008593 Ex 1-8, pp 4-5 EP 1027883 Compound VII, p 3 EP 1027883 Comp 1-VI, p 3 EP 1028120 Ex 1-5, pp 5-13 EP1059082 Exl;T1,pp9-11 EP1060734 T 1-3, pp 11-14 EP1064922 Compounds 1-34, pp 6-14 EP1081140 Ex 1-9, pp 11-16 EP1103549 Compounds 1-76, pp 39-51 EP 1108712 4,5-Dimorpholino-3-hydroxypyridazine EP1123934 T3,plO EP 1129695 Ex 1-7, pp 13-14 EP1167359 Exi p11 and ex2pl2 EP1258481 Exl,pp7,8 EP 420707 Bi Ex 3, p 13 (CAS Regno 80142-49-0) EP503338 Ti, pp 9-10 EP 517103 Ex 3,4,9,10 pp 6-7 EP 517104 Ex 1, T 1, pp 4-5; Ex 8, T 2, pp 6-8 EP 626950 all compounds EP669323 Exl-3,p5 EP780382 Exl-11,pp5-7 EP 823418 Ex 1-4, pp 78 EP826361 Ti,pp5-6 EP832641 Ex5--6p7;t2,p8 EP832642 Ex22,T3pp, 10-15;T4, p16 EP852137 12, pp 41-46 EP858318 T1,p6 EP863145 Ex 1-11, pp 12-18 EP 895776 Comp. in rows 48-58, p 3; R 25+33, p 5 EP911020 T2,pll-12 EP916335 T2-4, pp 19-41 Table 3: Suitable UV filter substances which can be additionally used with the UV absorbers according to the present invention (Abbreviations I table, R row, Comp compound, Ex compound(s) of patent example, p page), the generic scope of the UV absorbers is described in the left-hand column, specific compounds are indicated in the right-hand column EP924246 T2,p9 EP 933376 Ex 1-15, pp 10-21 EP944624 Ex 1+2, ppl315 EP 945125 T 3 a+b, pp 14-15 EP 967200 Ex 2; T 3-5, pp 17-20 EP969004 Ex5,T1,pp6-8 JP 2000319629 CAS Regno. 80142-49-0, 137215-83-9, 307947-826 US 5635343 all compounds on pp 5-10 US 5338539 Ex 1-9, pp 3+4 US5346691 Ex40,p7;T5,p8 US 5801244 Ex 1-5, pp 6-7 WO 0238537 All componds p3, compounds on rows 1-10 p4 WO 9220690 Polymeric comp in examples 3-6 Table 4: Suitable UV filter substances and adjuvants which can be additionally used with the UV absorbers according to the present invention Nc Chemical Name CAS No. 1 (+/-)-1,7,7-trimethyl-3-[(4-methylphenyl)methylene]bicyclo[2.2.1] -36861-47-9 _____ heptan-2-one; p-methyl benzylidene camphor 2 1,7,7-trimethyl-3-(phenylmethylene)bicyclo[2.2. 1]heptan-2-one; 15087-248 benzylidene camphor 3 (2-Hydroxy-4-methoxyphenyl)(4-methyphenyl)methanone 1641-17-4 4 2,4-dihydroxybenzophenone 131-56-6 2,2',4,4'-tetrahydroxybenzophenone 131-55-5 6 2-Hyd roxy-4-methoxy benzophenone 131-57-7 7 2-Hydroxy-4-methoxy benzophenone-5-sulfon ic acid 4065-45-6 8 2,2'-dihydroxy-4,4'-dimethoxybenzophenone 131 -54-4 9 2,2'-Dihydroxy-4-methoxybenzophenone 131-53-3 Alpha-(2-oxoborn-3-ylidene)toluene-4-sulphonic acid and its salts; 56039-58-8 _____ Mexoryl SL 11 1 -[4-(1, 1 -dimethylethyl)phenyl]-3-(4-methoxyphenyl)propane-1,3-70356-09-1 -14Table 4: Suitable UV filter substances and adiuvants which can be additionally used with the UV absorbers according to the present invention Nc Chemical Name CAS No. dione; avobenzone 12 Methyl N,N,N-trlmethyl-4-[(4,7,7-trimethyl-3-oxobjcyclo[22 1]hept-2-52793-97-2 _____ ylidene)methyl]anilinium sulphate; Mexoryl SO 22 3,3, 5-Trimethyl cyclohexyl-2-hyd roxy benzoate; homosalate 118-56-9 23 Isopentyl p-methoxycinnamate; isoamyl methoxy cinnamate 71617-10-2 27 Menthyl-o-aminobenzoate 134-09-8 28 Menthyl salicylate 89-46-3 29 2-Ethylhexyl 2-cyano,3,3-diphenylacrylate; Octocrylene 6197-30-4 2-ethylhexyl 4-(dimethylamino)benzoate 21245-02-3 31 2-ethylhexyl 4-methoxycinnamate; octyl methoxy cinnamate 5466-77-3 32 2-ethylhexyl salicylate 118-60-5 33 Benzoic acid, 4,4', 4"-(1, 3, 5-triazine-2, 4, 6-triyltriimino)tris-, 88122-99-0 tris(2-ethylhexyl)ester, 2,4,6-Trian ilino-(p-carbo-2'-ethylhexyl-l -oxi)- 1,3,5-triazine; octyl triazone 34 4-aminobenzoic acid 150-13-0 Benzoic acid, 4-amino-, ethyl ester, polymer with oxirane 113010-52-9 38 2-phenyl-1 H-benzimidazole-5-sulphonic acid; 27503-81-7 phenylbenzimidazolsu Ifonic acid 39 2-Propenamide, N-[4-[(4,7,7-trimethyl-3-oxobicyclo[2.2. 1]hept-2-147897-12-9 _____ ylidene)methyl]phenylJmethyl]-, homopolymer Triethanolamine salicylate 2 174-16-5 41 3, 3'-(l,4-phenyleriedimethylene)bis[7, 7-dimethyl-2-oxo-90457-82-2 _____ bicyclo[2.2.1]heptane-1 methanesulfonic acid]; Cibafast H 42 Titanium dioxide 13463-67-7 44 Zinc oxide 1314-13-2 2,2'-Methylene-bis-[6-(2 H-benzotriazol-2-yl)-4-( 1,1, 3,3-tetramethyl-103597-45-1 ______ butyl)-phenol], Tinosorb M 46 2,4-bis{[4-(2-ernylliexyloxy)-2-nydroxyj-phenyl}-6-(4-187393-00-6 _____ methoxyphenyi)-(1,3,5)-triazine; Tinosorb S 47 1 H-Benzimidazole-4,6-disulfonic acid, 2,2'-(l,4-phenylene)bis-, 180898-377 disodium salt 48 Benzoic acid, 4,4'-[6-[4-[( 1,1 -dimethylethyl)amino]carbonyl]phenyl]-154702-15-5 aminoji,3,5-triazine-2,4-diylJdiimino]bis-, bis(2-ethylhexyl)ester; di-_____ ethylhexyl butamido triazone; Uvasorb HEB 49 Phenol, 2-(2 H-benzotriazol-2-yl)-4-methyl-6-[2-methyl-3-[1,3,3,3-155633-54-8 Table 4: Suitable UV filter substances and adjuvants which can be additionally used with the UV absorbers according to the present invention Nc Chemical Name CAS No. tetra methyl-i -[(trimethylsilyl)oxy]disiloxanyl]propyl]-, drometrizole trisiloxane; Mexoryl XL Dimethicodiethylbenzalmalonate; Polysilicone 15; Parsol SLX 207574-74-i 51 Benzenesu Ifon ic acid, 3-(2 H-benzotriazol-2-yl)-4-hydroxy-5-( 1-92484-48-5 _____ methylpropyl)-, monosodium salt; Tinogard HS 52 Benzoic acid, 2-[4-(diethylamino)-2-hydroxybenzoyl]-, hexyl ester; 302776-68-7 Uvinul a plus _____________ 53 1 -Dodecanaminium, N-[3-[4-(dimethylamino)benzoyl]amino]propyl]-156679-41-3 N,N-dimethyl-, salt with 4-methylbenzenesulfonic acid (1:1); Escalol H P6 10 54 1 -Propanamin ium, N, N, N-trimethyl-3-[( 1 -oxo-3-phenyl-2-propenyl)-177190-98-6 amino]-, chloride 1 H-Benzimidazole-4,6-disulfonic acid, 2,2'-(i,4-phenylene)bis-170864-82-1 56 1,3,5-Triazine, 2,4,6-tris(4-methoxyphenyl)-7753-12-0 57 1,3,5-Triazine, 2,4,6-tris[4-[(2-ethylhexyl)oxy]phenyl]-208114-14-i 58 1 -Propan am iniu m, 3-[3-[3-(2 H-benzotriazol-2-yl)-5-( 1,1-340964-15-0 dimethylethyl)-4-hyd roxyphenyl]-1 -oxopropyl]am ino]-N, N-diethyl-N_____ methyl-, methyl sulfate (salt) 59 2-Propenoic acid, 3-(1 H-imidazol-4-yl)-104-98-3 Benzoi c acid, 2-hydroxy-, [4-( 1 -methylethyl)phenyl]methyl ester 94134-93-7 61 1,2,3-Propanetriol, 1 -(4-aminobenzoate); glyceryl PABA 136-44-7 62 Benzeneacetic acid, 3,4-d imethoxy-a-oxo-4732-70-1 63 2-Propenoic acid, 2-cyano-3,3-diphenyl-, ethyl ester 5232-99-5 64 Anthralinic acid, p-menth-3-yl ester 134-09-8 2,2'-bis(l,4-phenylene)-1 H-benzimidazole-4,6-disulphonic acid mo-349580-12-7, no sodium salt or Disodium phenyl dibenzimidazole tetrasulfonate or _____ Neoheliopan AP 66 1,3,5-Triazine-2,4,6-triamine, N,N'-bis[4-[5-(1, 1 -dimethylpropyl)-2-288254-16-0 benzoxazolyl]phenyl]-N"-(2-ethylhexyl)-or Uvasorb K2A 67 Merocyanine derivatives as described in WO 2004006878 and in I PC0M000022279D Table 4: Suitable UV filter substances and adluvants which can be additionally used with the UV absorbers according to the present invention No Chemical Name CAS No. N-C=C-C-< /

H H H CN

68 sterols (cholesterol, lanosterol, phytosterols), as described in 69 mycosporines and/or mycosporine-like amino acids as described in W02002039974, e.g. Helioguard 365 from Milbelle AG, isolated mycosporine like amino acids from the red alga porphyra umbilicalis _____ (INCI. Porphyra Umbilicalis) that are encapsulated into liposomes,) ______________ alpha-lipoic-acid as described in DE 10229995 71 synthetic organic polymers as described in EP 1371358, [0033]- _____ [004 1] 72 phyllosilicates as described in EP 1371357 [0034]-[0037] ____________ 73 silica compounds as described in EP1371356, [0033]-[0041] 74 inorganic particles as described in DE10138496 [0043]-[0055] latex particles as described in DE1O1 38496 [0027]-[0040] 76 1 H-Benzimidazole-4,6disulfonic acid, 2,2'-(l,4-phenylene)bis-, 180898-37-7 disodium salt Bisimidazylate; Neo Heliopan APC Preferred cosmetic and/or dermatological compositions according to the present invention are: 1 a. Cosmetic and/or dermatological compositions for the protection from UV radiation comprising a compound of formula (1) and powders having a core of at least one siloxane elastomer coated with trimethylsiloxylate and/or its derivatives as described in D 101 57 439 from page 2, line 46 to page 4, line 6 dud pdge 4, line 49 -54.

1 b. Cosmetic and/or dermatological compositions for the protection from UV radiation comprising a compound of formula (1) and powders having a core of at least one siloxane elastomer coated with trimethylsiloxylate and/or its derivatives and a further UV filter selected from the group of triazines, benzotriazoles, UV filters being liquid at room temperature, sulfonated, water soluble UV filters, oil soluble UV broadband filters and organic and/or anorganic pigments, which are preferably suface-coated asdescribed in DE 101 57 489, ≈[051] -[0079].

2. Self-tanning composition comprising a cosmetic acceptable carrier: (a) at least a self tanning agent; and (b) at least a compound of formula (1) as described in EP-A-1,317,920.

3. Cosmetic and/or dermatological composition for topical use comprising in a cosmetic

acceptable medium

(a) 0.1 -15% b.w. of 1.4-di(3-methylidene-10-comphosulfonic) benzoic acid; and (b) 0.1 -15% b.w. of a compound of formula (1).

As described in EP-A-1,317,919.

4. Cosmetic and/or dermatological composition for topical use, preferably for the photoprotection of the skin and/or hair comprising in a cosmetic acceptable medium (a) at least an insoluble organic UV filter having a particle size from 10 nm to 5 jim as first filter as desribed, for example in EP-A-1,317,918 ≈[0025]-[0050]; and (b) as second filter at least one compound of formula (1).

Cosmetic and/or dermatological composition for the protection against UV radiation with UV filters selected from a compound of formula (1), anorganic micro pigments and at least one siloxane elastomer selected from the group existing of siloxane elastomers ob- tainable either by the reaction of vinyl-terminal polymethylsiloxane and methylhydrodi-menthylsiloxane or by reaction of hydroxy-terminal dimethylpolysiloxane and trimethyl-siloxy-terminal methylpolysioxane in form of spheric powder or in form of gels as described in DE 101 55 865, ≈[0009] -[0013], [0020] -[0021] and [0045] -[0050].

6. Cosmetic and/or dermatological compositions for the protection against UV radiation comprising (a) at least one compoL!nd 0f formula (1); (b) at least one triazine-or benzotriazole derivative as described in WO 03/039507, pages5-16;and optionally further cosmetic actives, adjuvants and additives as described in 7a. Cosmetic and/or dermatological compositions comprising (a) at least one compound of formula (1); (b) at least one dialkylnaphthalate of formula wherein R1 and R2 independently from each other are branched or unbranched C6C24aIkyls as described in WO 03/039,506.

7b. Cosmetic and/or dermatological compositions comprising (a) at least one compound of formula (1); (b) at least a dialkylnaphthalate of formula wherein R1 and R2 independently from each other are branched or unbranched C6-C24alkyls; and (c) a further UV filter selected from the group of triazines, benzotriazoles, liquid UV filters and organic and/or inorganic pigments as described in WO 03/039506, page 17, line 20 and page 18-20.

8a. Cosmetic and/or dermatological composition comprising (a) a compound of formula (1) and (b) 8-hexadecene-1.16-dicarboxylic acid; as described in WO 03/039,502.

8b. Cosmetic and/or dermatologicat composition comprising (a) a compound ottormula (1); (b) 8-hexadecene-1.1 6-dicarboxylic acid; and (c) a further UV-A filter and/or broadband filter selected from the group of dibenzoyl- methane derivatives, preferably 4-(tert. butyl)-4 -methoxydibenzoylmethane, pheny-Iene-1,4-bis-(2-benzimidazyl)-3,3'-5,5'-tetrasulfonic-bissodium salt, 1,4-di(2-oxol0- su lfo-3-bornylidenemethyl)-benzene and the salts thereof and 2,4-bis-{4-(2-ethyl-hexyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-1,3, 5-triazine, wherein the fil- ters may be present as single substances or in any combination of each sub-stance.

9 Self-foaming, foaming, after-foaming or foamable cosmetic and/or dermatological compositions comprising I. an emulsifier system as described for example in WO 03/039493, pages 6-19, consisting of A. at least one emulsifier A selected from the group of totally partially or not neutralized, branched and/or unbranched, saturated and/or unsaturated C10-C40fatty acids; B at least one emulsifier B selected from the group of polyethoxylated C10-C4ofatty acid esters having an ethoxylation degree of 5 -50; C at least one co-emulsifier C selected from the group of saturated and/or unsaturated branched and/or unbranched C10-C40fatty alcohols; and II. until 30 % b.w., based on the overall weight of the composition,of a lipid phase comprising (a) one or more lipids selected from silicon oils and silicon waxes; and (b) one or more lipids selected from inpolar lipids having a polarity = 30 mM/m wherein the ratio (a) : (b) is in the range of 1:3 -3:1, and (c) 0.5-10, preferably 0.5 -10 % b.w. of at least one compound of formula (1).

10. Cosmetic and/or dermatological compositions for the protection against UV radiation comprising (a) at least one compound of formula (1); and (b) potassium-ethylenediaminetetramethlenephosphonate as described in PP-_1 Un 7'Q E 1flfl771 -Ifl 9Rl -,-- LJ 11. Cosmetic and/or dermatological compositions for the protection against UV radiation comprising (a) at least one compound of formula (1); and -20 - (b) at least an acrylamide polymer, acrylamide copolymer, and derivatives thereof and/or an acrylamide polymer, acrylamide copolymer and derivatives thereof; as described in EP-A-1,310,239 12. Cosmetic and/or dermatological compositions for the protection from UV radiation comprising (a) at least one compound of formula (1); and (b) imidosuccinic acid and/or derivatives thereof as described for example in EP-A-1,310,236 ≈[0028] -[0030].

13. Pickering emulsions comprising fine disperse systems of WI0 or 01W type comprising (1) an oil phase (2) an aqueous phase, (3) at least one type of a micronised particle, which (a) have a mean particle size of < 200 nm and which (b) have hydrophilic and lipophilic properties which have also amphiphilic character and are dispersible in water and in oil and which have (4) at least one compound of formula (1) as described in EP-A-1,310,235.

14. Cosmetic and/or dermatological compositions for the protection against UV radiation producing a permanent and non-covering colaration on the skin natural bronzing comprising in a cosmetical acceptable medium at least a susceptible pigment obtained from the extraction with an organic or hydroorganic solvent in a medium of myromydete culture of the type monascus; and at least one compound of formula (1): as described in EP-A-1,302,199.

15. Cosmetic and/or dermatological composition in form of an 0/W emulsion comprising at least one compound of formula (1). -21 -

The basic compontents of the O/W emulsion are disclosed in EP-A-1 291,012, ≈[0049] -[0277].

16. Cosmetic and/or dermatological composition in form of an W/O emulsion comprising at least one compound of formula (1).

The basic compontents of the W/O emulsion are disclosed in EP-A-1,291,009, ≈[0047] -[0245].

1 7. Cosmetic and/or dermatological composition representing finedisperse systems of O/W type comprising (a) an oil phase, (b) an aqueous phase, (c) one or more stabilzers as disclosed in EP-A-1,291,007 ≈[0022] -[0080].

(d) at most 2.00 % b.w. of oner or more emulsifiers, and (e) at least one compound of formula (1).

Further basic components of this cosmetic or dermatological composition are disclosed in EP-A-1,291,007.

18. Cosmetics sticks comprising a) a lipid phase comprising at least an oil component and/or at least a wax component as described in EPA-i,290,999 ≈[0031] -[0058] and b) at least one compound of formula (1).

19. UV filter combination, comprising (a) a compound which absorbs essentially in he UVA range, and (b) further compounds which absorb in the UV-A-, UV-B-range and in the UV-A-and UV-B-range, wherein the moiety is in the UV-A-range (a) an effective amount of t iest one compound of formula

H Rh.)

wherein R1, R2 and R3 independently from each other are Ci-C8alkyl; and (b) an effective amount of one or more compounds selected from -22 -ba) at least one compound of formula (1); bb) a compound of formula

OR COGV U'

wherein R7 and R8 independently from each other are C1-C12alkyl or CrCiocycloalkyl; bc) the compound of formula

K H

-* Wy)4yM _ (t_0 ( bd) the compound of formula !=OK be) the compound of formula

HO HO

> !=Lk bf) the compound of formula CR OS(CH3)3 CHHCH2SiCH3 (VII) HO Ac3 bg) the compound of formula C.H. [Ck * rc 1 C Lcw Lv1 Jci wherein V' is the group of formula V1 is methyl or V1' is group of formula oi r I () VILIb, C13 (c 1. v Je-.

wherein V2' is a group of formula Ca2" C'-"CH2-'O--"-( s-=c V2 is methyl or V'2; or mixtures of the compounds VIlla and VIlIb, wherein t is a number up to 100 and u is a avalue up to 20 with the proviso that u is = 0, when V1 = V1' and/or V2 = V2', and u has a value from I -20, when V1 is CH3 and/or V3 isCH3; bh) a compound of formula -24 -

U

H

W--e' (..

bi) a compound of formula bj) a compound of formula XcsNSOX XL wherein X is hydrogen, sodium, potassium, ammonium or tnethanolammonium; bk) a compound of formula

OH OH Is

II I Ii Hcr" as photostable UV filter formulation for the protection of the human skin and hair from Uv radiation, optionally together with further known cosmetic UV filters.

21. Cosmetic and/or dermatological composition for the protection of the human epidermis or hair from UV radiation in the range of 280 -400 nm, comprising in a cosmetic or pharmaceutical suitable carrier an effective amount of UV filter combinations as photostable UV filters, wherein the effective component of the absorbing part in the UV- A range consists of a) an effective amount of a compound of formula

L

and component b) comprises an effective amount of one or more compounds selected from ba) the compound of formula U, bb)the compound of formula H. H ( NN _(%.s.m%tt 0 NH III, bc) the compound of formula NyN S -t bd) the compound of formula !=N ir' y' L)k. !=k1c -26 -be) CH OSi(CH CI2CHCH2ICH3 HOJ OSi(CH)3 bf) an organosiloxanebenzalmalonate of formula [cH L u-S-)-!-t L'3 L1 J wherein V1' is the group of formula c c:_ c. o-- C V1 is methyl or V1' is group of formula rc i*ci.

I I1b

I E

I I

LC3 J. Li' wherein V2' is a group of formula -C o} OC C CH"O" V2 is methyl or V'2; or mixtures of compounds VIla and Vllb, wherein t is a number upt o 100 and u is a avalue up to 20 with the proviso that u is = 0, when V1 = V1' and/or V2 = V2' and u has a value from I -20, when V1 is CH3 and/or V3 is CH3; bg) the compound of formula fOCr''N bh) the compound of formula bi) the compound of formula t. ç J[ 0 bj) a compound of formula XOJ t4%rfl /\_/YrtN1_' $O3> xorn>' N'sox wherein X is hydrogen, sodium, potassium, ammonium or triethanolammonium; bk)the compound of formula bj) the compound of formula (1) bm) the compound of formula C).

bn) the compound of formula OH C) CH rLT)Lr bo) the compound of formula and bp) tin oxide and/or titanium dioxide, optionally together with further known cosmetic UV filters.

22. Cosmetic and/or dermatological composition for topical use, preferably for the photoprotection of the skin and/or hair comprising in a cosmetic acceptable medium (a) at least one dibenzoyl methane deivative as described in EP-A-1,323,413 ≈[0027 -0030] (b) at least one I,3,5triazine derivative as described in EP-A-1,323,413 ≈[0019- 0027] being photosensitive in the presence of the dibenzoylmethane derivative; (c) at least one compound of formula (1) 23. Cosmetic and/or dermatological composition for topical use, preferably for the photoprotection of the skin and/or hair comprising in a cosmetic acceptable medium (a) at least one dibenzoyl methane derivative as described in EP-A-1,323,412 ≈[0040 -0042]; (b) at least one compound of formula (1).

-29 - 24. Cosmetic and/or dermatological composition for topical use, preferably for the photoprotection of the skin and/or hair comprising in a cosmetic acceptable medium (a) at least one si/ide derivative benzotriazole (first filter) as described in EP-A- 1,323,411 ≈[0021 -0036] (b) at least one dibenzoyl methane deivative (c) at least one compound of formula (1) (= third filter) 25. Cosmetic and/or dermatological composition comprising one or more lecithins for increasing the light protection factor and/or UVA protection as described in EP-A-1,166,759; and at least one compound of formula (1).

26 Cosmetic and/or dermatological composition comprising (a) triglyceride waxes as decribed in EP-A-1,000,611 to increase the UVA protection factor of cosmetic or dermatological compositions containing conventional UV-A-filters; and/or (b) at least one compound of formula (1) that also provide protection against UV radiation with a wavelength above 355 nm.

27. Cosmetic and/or dermatological composition comprising (a) ethylhexyl 2-cyano-3,3-diphenylacrylate (octocrylene) as described in EP A-i,034,778; and (b) at least one compound of formula (i) for solubilizing and for increasing the light protection factor and/or the UV-A protection performance of the compound of formula (1).

28. Oil-free cosmetic or dermatoiogicai composition comprising (a) at least one compound of formula (i) and (b) at least one UV filter liquid at room temperature as described in EP-A-i,074,24i 29. 01W emulsion, preferably OIW-microemulsion or OIW/O-emulsions or OIWIO'-emulsions comprising -30 - (a) water phase (b) optionally usual water soluble or dispersible substances, (c) an oil phase, wherein at least one cosmetic or dermatologic UV filter substance selected from at least one compound of formula (1)is present in suspended form, (d) at least one emulsifier (A) selected from emulsifiers with the following properties -the lipophilic property is either dependent on the pH inasmuch rising or lowering the pH the lipophilic property will increase or decrease being insubstantial which of both alternatives of changing the lipophilic properties by rising or lowering the pH is effected and/or - the lipophilic property is dependent on the temperature, inasmuch the lipophilic properties will increase with rising temperature and the hydrophilic properties will increase with rising temperature, (e) and further substances which are optionally soluble or dispersible in the oil phase, preferably those substances which are outside the definition of emulsifier (A), preferably those substances which predominantly act as W/O emulsifiers.

30. Cosmetic light protection formulation comprising (a) one or more amide oils as described in DE-A-1 9942714; and (b) at least one compound of formula (1) The cosmetic or pharmaceutical preparations may be, for example, creams, gels, lotions, al-coholic and aqueous/alcoholic solutions, emulsions, wax/fat compositions, stick preparations, powders or ointments. In addition to the above-mentioned UV filters, the cosmetic or pharma-ceutical preparations may contain further adjuvants as described below.

As water-and oil-containing emulsions (e.g. WIO, 01W, 0/WIO and W/OIW emulsions or mi-croemulsions) the preparations contain, for example, from 0.1 to 30 % by weight, preferably from 0.1 to 15 % by weight and especially from 0.5 to 10 % by weight, based on the total weight of the composition, of one or more UV absorbers, from 1 to 60 % by weight, espec-ially from 5 to 50 % by weight and preferably from 10 to 35 % by weight, based on the total weight of the composition, of at least one oil component, from 0 to 30 % by weight, especially from 1 to 30 % by weight und preferably from 4 to 20 % by weight, based on the total weight of the composition, of at least one emulsifier, from 10 to 90 % by weight, especially from 30 -31 -to 90 % by weight, based on the total weight of the composition, of water, and from 0 to 88.9 % by weight, especially from ito 50 % by weight, of further cosmetically acceptable adju-va rits.

The compounds of formula (i) may also be used as as an anti-wrinkle perception modifier Preferably, the following combinations comprising UV absorbers are of special interest: N A CASNo.ofA B UV absorber selected from the formulas _____ ________________________________ ___________ (101)and (102) Comb (4-I-)-1,7,7-trimethyl-3-[(4-methytphe-36861-47-9 001 nyl)methylene}bicyclo[2.2. 1]heptan-2-X _____ one; p-methyl benzylidene camphor ____________ ______________________ Comb 1,7,7-trimethyl-3-(phenylmethyllene)-15087-24-8 002 bicyclo[2.2.i}heptan-2-one; benzylidene X _____ camphor _____________ _______________________ Comb (2-Hyd roxy-4-methoxyphenyl)(4-methyl-1641-17-4 003 phenyl)methanone ____________ X Comb 2,4-dihydroxybenzophenone 131-56-6 X 004 _____________________________________ _____________ ________________________ Comb 2,2',4,4'-tetrahydroxybenzophenone 131-55-5 X

____________________________________ _____________ ________________________

Comb 2-Hyd roxy-4-methoxy benzophenone; 131-57-7 X 006 ____________________________________ _____________ ________________________ Comb 2-Hyd roxy-4-methoxy benzophenone-5-4065-45-6 X 007 sulfonic acid _____________ ________________________ Comb 2,2'-dihydroxy-4,4'-dimethoxybenzophe-131 -54-4 X 008 none _____________ _______________________ Comb 2,2'-Dihydroxy-4-methoxybenzophenone 13 1-53-3 X 009 ____________________________________ _____________ ________________________ Comb AIpha-(2-oxoborn-3-yidene)toI uene-4-56039-58-8 X sulphonic acid and its sa'ts; Mexoryl SL ____________ ______________________ Comb 1 -[4-(1, 1 -dimethylethyl)phenyl]-3-(4-70356-09-i X 011 methoxyphenyl)propane-1,3-dione; _____ avobenzone Comb Methyl N,N,N-trimethyl-4-[(4,7,7-52793-97-2 X fl') +rI rfh,i Q,, l1h,r+') .1 I C_ LI I I .' I 1)1 .' LI L/IJI ., y La.. I J IL. JL ..

ylidene)methyl]anilinium sulphate; ____ Mexoryl SO __________ ___________________ Comb 3,3,5-Trimethyl cyclohexyl-2-hydroxy 118-56-9 X 013 benzoate; homosalate ___________ Comb Isopentyl p-methoxycinnamate; isoamyl 71617-10-2 X 014 methoxy cinnamate ____________ _____________________ Comb Menthyl-o-aminobenzoate 134-09-8 X

_________________________________ ____________ _____________________

-32 -N A CASNo.ofA B UV absorber selected from the formulas _____ ________________________________ ____________ (101)and (102) Comb Menthyl salicylate 89-46-3 X 016 _________________________________ Comb 2-Ethylhexyl 2-cyano,3,3-6197-30-4 X 017 diphenylacrylate; octocrylene ____________ ______________________ Comb 2-ethylhexyl 4-(dimethylamino)benzoate 21245-02-3 X 018 ________________________________ Comb 2-ethylhexyl 4-methoxycinnamate; octyl 5466-77-3 X 019 methoxy cinnamate ____________ Comb 2-ethylhexyl salicylate 118-60-5 X

____________________________________

Comb Benzoic acid,4,4',4"-(1, 3, 5-triazine-88122-99-0 X 021 2,4,6-triyltriimino)tris-,tris(2-ethylhexyl)- ester; 2,4,6-Trianilino-(p-carbo-2'-ethyl-hexyl-1 -oxi)-l,3,5-triazine; Octyl _____ Triazone Comb 4-aminobenzoic acid 150-13-0 X 022 ____________________________________ Comb Benzoic acid, 4-amino-, ethyl ester, poly-113010-52-9 X 023 mer with oxirane Comb 2-phenyl-1 H-benzimidazole-5-sulphonic 27503-81-7 X 024 acid; phenylbenzimidazolsulfonic acid _____________ ________________________ Comb 2-Propenamide, N-[4-[(4,7,7-trimethyl-3-147897-12-9 X oxobicyclo[2.2.1]hept-2-ylidene)methyl]- _____ phenyl]methyl]-, homopolymer ____________ ______________________ Comb Triethanolamine salicylate 2174-16-5 X 026 __________________________________ Comb 3, 3'-(l, 4-phenylenedimethylene)bis-90457-82-2 X 027 [7,7-dimethyl-2-oxobicyclo[2.2.1]hep- _____ tane-1 methanesulfonic acid]; Cibafast H _____________ Comb Titanium dioxide 13463-67-7 X 028 ___________________________________ Comb Zinc oxide 1314-13-2 x 029 ___________________________________ Comb 2,2'-Methylene-bis-[6-(2 H-benzotriazol-2-103597-45-1 X yl)-4-(1, 1,3,3-tetramethylbutyl)-phenol]; _____ Tinosorb M ____________ Comb 2,4-bis{[4-(2-ethylhexyloxy)-2-hydroxy]-1 87393-00-6 X 031 phenyl}-6-(4-methoxyphenyl)-(1,3,5)- _____ triazine; Tinosorb S Comb 1 H-Benzimidazole-4,6-disulfonic acid, 180898-37-7 X 032 2,2'-(l,4-phenylene)bis-, disodium salt Comb Benzoic acid, 4,4'-[6-[4-[(1, 1 -dimethyl-154702-15-5 X 033 ethyl)amlno}carbonyl]phenyl]amino]1,3,5-triazine-2,4-diyl]diimino]bis-, bis(2-ethyl- _____ hexyl)ester; diethyihexyl butamido tria ______________ -33 -A CASNo.ofA B UV absorber selected from the formulas _____ ________________________________ ___________ (101)and (102) _____ zone; Uvasorb HEB ____________ ______________________ Comb Phenol, 2-(2H-benzotriazol-2-yl)-4-me-155633-54-8 X 034 thyl-6-[2-methyl-3-[1,3, 3,3-tetramethyl-1 - [(trimethylsilyl)oxy]disiloxanyl]propyl]-; _____ drometrizole trisiloxane; Mexoryl XL ____________ Comb Dimethicodiethylbenzalmalonate; 207574-74-1 X Polysilicone 15; Parsol SLX ____________ ______________________ Comb Benzenesu Ifon ic acid, 3-(2 H-benzotri-92484-48-5 X 036 azol-2-yl)-4-hydroxy-5-( 1 -methylpropyl)-, _____ monosodium salt; Tinogard HS _____________ Comb Benzoic acid, 2-[4-(diethylamino)-2-hy-302776-68-7 X 037 droxybenzoyl]-, hexyl ester, Uvinul a plus _____________ ________________________ Comb 1 -Dodecanaminium, N-[3-[4-(dimethyl-156679-41-3 X 038 amino)benzoyl]amino]propyl]N,N- dimethyl-, salt with 4-methylbenzene_____ sulfonic acid (1:1); Escalol HP61O ____________ ______________________ Comb 1 -Propanaminium, N,N,N-trimethyl-3-[(1 -177190-98-6 X 039 oxo-3-phenyl-2-propenyl)amino]-, _____ chloride _____________ _________________________ Comb 1 H-Benzimidazole-4,6-disulfonic acid, 170864-82-1 X 2,2'-(l,4-phenylene)bis-____________ _______________________ Comb 1,3,5-Triazine, 2,4,6-tris(4-methoxy-7753-12-0 X 041 phenyl) _____________ ________________________ Comb 1 3,5-Triazine, 2,4,6-tris[4-[(2-ethyl-208114-14-1 X 042 hexyl)oxy]phenyl]-(Rinosorb S) ____________ ______________________ Comb 1-Propanaminium, 3-[3-[3-(2H-benzo-340964-15-0 X 043 triazol-2-yl)-5-( 1, 1 -dimethylethyl)-4- hydroxyphenyl]-1 -oxopropyl]amino]-N, N- _____ diethyl-N-methyl-, methyl sulfate (salt) _____________ ________________________ Comb 2-Propenoic acid, 3-(1 H-imidazol-4-yl)-104-98-3 X 044 ____________________________________ _____________ ________________________ Comb Benzoic acid, 2-hydroxy-, [4-(1-methyl-94134-93-7 X ethyl)phenyl]methyl ester ______________ _________________________ Comb 1,2,3-Propanetriol, 1 -(4-aminobenzoate); 136-44-7 X 046 glyceryl PABA _____________ _______________________ Comb Benzeneacetic acid, 3,4-dimethoxy-a-4732-70-1 X 047 oxo _____________ _______________________ Comb 2-Propenoic acid, 2-cyano-3,3-diphenyl-, 5232-99-5 X 048 ethyl ester _____________ ________________________ Comb Anthralinic acid, p-menth-3-yl ester 134-09-8 X 049 ___________________________________ _____________ _______________________ Comb 2,2'-bis(l,4-phenylene)-1 H-benzimida-349580-12-7, X zole-4,6-disulphonic acid mono sodium salt or Disodium phenyl dibenzimidazole _____ tetrasulfonate (Neoheliopan AP) _____________ ________________________ Comb 1,3,5-Triazine-2,4,6-triamine, N,N'-bis[4-288254-16-0 X -34 -Nc A CASNo.ofA B UV absorber selected from the formulas ____ _______________________________ ___________ (101)and (102) 051 [5-( 1,1 -d imethylpropyl)-2-benzoxazolyl]- _____ phenyl]-N "-(2-ethylhexyl)-(Uvasorb K2A) _____________ ________________________ Comb Merocyanine derivatives as described in X 052 WO 2004006878 and in _____ I PC0M000022279D ____________ ______________________ Comb X K-0 = c-c

H H H CN

Comb sterols (cholesterol, lanosterol, phyto-X 054 sterols), as described in W0034 1675 ___________ _____________________ Comb mycosporines and/or mycosporine-like X amino acids as described in from Milbelle AG, isolated mycosporine like amino acids from the red alga porphyra umbilicalis (INCI: Porphyra Umbilicalis) that are encapsulated into _____ liposomes,) _____________ _______________________ Comb alpha-lipoic-acid as described in DE X 056 10229995 ____________ _____________________ Comb synthetic organic polymers as described X 057 in EP 1371358, [0033]-[0041] ____________ ___________________ Comb phyllosilicates as described in EP X 058 1371357 [0034]-[0037] ___________ _____________________ Comb silica compounds as described in X 059 EP1371356, [0033J-[0041] ___________ _____________________ Comb inorganic particles as described in X DE10138496 [0043]-[0055] ___________ _____________________ Comb latex particles as described in X 061 DE10138496 [0027]-[0040] ____________ _____________________ Furthermore, the following specific UV filter combinations are of specific interest: No. A CAS No. of A UV absorber selected from the formulas _____ ___________________________________ __________ (101)and (102) Comb (+/-)-1,7,7-trimethyl-3-[(4-methylphenyl)-3686 1-47-9 X 062 methylene]bicyclo[2.2.1]heptan-2-one; p-methyl benzylidene camphor -35 -A CAS No. of A UV absorber selected from the formulas ___________________________________ __________ (1O1)and (102) Comb 1,7,7-trimethyl-3-(phenylmethylene)bi-15087-24-8 X 063 cyclo[2.2.1]heptan-2-one; benzylidene camphor Comb (2-Hydroxy-4-methoxyphenyl)(4-1641-17-4 X 064 methylphenyl)methanone Comb 2,4-dihydroxybenzophenone 131-56-6 X

________________________________________

Comb 2,2',4,4'-tetrahydroxybenzophenone 131-55-5 X Comb 2-Hydroxy-4-methoxy benzophenone; 131-57-7 X Comb 2-Hydroxy-4-methoxy benzophenone-5-4065-45-6 X 068 sulfonic acid Comb 2,2'-dihydroxy-4,4'-dimethoxybenzophenone 131 -54-4 X Comb 2,2'-Dihydroxy-4-methoxybenzophenone 131-53-3 X Comb Alpha-(2-oxoborn-3-ylidene)tol uene-4-sul-56039-58-8 X 071 phonic acid and its salts; Mexoryl SL Comb 1 -[4-(1, 1 -dimethylethyl)phenyl]-3-(4-methoxy-70356-09-1 X 072 phenyl)propane-1,3-dione; avobenzone Comb Methyl N, N, N-trimethyl-4-[(4, 7, 7-trimethy!-3-52793-97-2 X 073 oxobicyclo[2,2,1]hept-2-ylidene)methyl]-anilinium sulphate; Mexoryl SO Comb 3,3,5-Trimethyl cyclohexyl-2-hydroxy 118-56-9 X 074 benzoate; homosalate Comb Isopentyl p-methoxycinnamate, isoamyl 71617-10-2 X methoxy cinnamate Comb Menthyl-o-aminobenzoate 134-09-8 X 076 ________________________________________ ___________ Comb Menthyl salicylate 89-46-3 X 077 ________________________________________ ___________ Comb 2-Ethylhexyl 2-cyano,3,3-diphenylacrylate; 6 197-30-4 X 078 octocrylene Comb 2-ethylhexy! 4-(dimethylamino)benzoate 21245-02-3 X Comb 2-ethylhexyl 4-methoxycinnamate; octyl 5466-77-3 X methoxy cinnamate Comb 2-ethylhexyl salicylate 118-60-5 X Comb Benzoic acid,4,4',4"-(1, 3, 5-triazine-2,4,6-88122-99-0 X 082 triyltriimino)tris-,tris(2-ethylhexyl)ester;2,4,6-____________ _______________________ -36 - 1 =1Q. A CAS No. of A UV absorber selected from the formulas _____ ___________________________________ __________ (101)and (102) Trianilino-(p-carbo-2'-ethy!hexyl-l -oxi)-l,3,5-triazine; octyl triazone Comb 4-aminobenzoic acid 150-13-0 X 083 ________________________________________ ___________ ______________________ Comb Benzoic acid, 4-amino-ethyl ester, polymer 113010-52-9 X 084 with oxirane Comb 2-phenyl-1 H-benzimidazo!e-5sulphonic acid; 27503-81-7 X phenylbenzimidazolsulfonic acid Comb 2-Propenamide, N-[4-[(4,7,7-trimethyl-3-oxo-147897-12-9 X 086 bicyclo[2.2.1]hept-2-ylidene)methyl]phenyl]- _____ methyl]-, homopolymer ___________ _____________________ Comb Triethanolamine salicylate 2174-16-5 X 087 __________________________________________ ____________ _______________________ Comb 3, 3'-(l, 4-phenylenedimethylene)bis[7,7-90457-82-2 X 088 dimethyl-2-oxo-bicyclo[2.2.1]heptane-1 -methanesulfonic acid]; Cibafast H Comb Titanium dioxide 13463-67-7 X 089 ________________________________________ ___________ _____________________ Comb Zinc oxide 1314-13-2 X

__________________________________________ ____________ ______________________

Comb 2,2'-Methylene-bis-[6-(2 H-benzotriazol-2-yl)-103597-45-1 X 091 4-(1, 1,3,3-tetramethylbutyl)-phenol]; Tinosorb

M

Comb 2,4-bis{[4-(2-ethylhexyloxy)-2-hydroxy]-187393-00-6 X 092 phenyl}-6-(4-methoxyphenyl)-(1,3,5)-triazine; Tinosorb S Comb 1H-Benzimidazole-4,6-disulfonic acid, 2,2'-180898-37-7 X 093 (1,4-phenylene)bis-, disodium salt Comb Benzoic acid, 4,4'-[6-[4-[( 1,1 -dimethylethyl)-154702-15-5 X 094 amino]carbonyl]phenyl]amino]1,3,5-triazine- 2,4-diyl]diimino]bis-,bis(2-ethylhexyl)ester; _____ diethylhexyl butamido triazone; Uvasorb HEB Comb Phenol, 2-(2H-benzotriazol-2-yl)-4-methyl-6-155633-54-8 X [2-methyl-3-[1,3,3,3-tetramethyl-1-[(trime-thylsilyl)oxy]d isiloxanyl]propyl]-; drometrizole trisiloxane; Mexoryl XL Comb Dimethicodiethylbenzalmalonate; Polysilicone 207574-74-1 X 096 15; Parsol SLX Comb Benzenesulfon ic acid, 3-(2 H-benzotriazol-2-92484-48-5 X 097 yl)-4-hydroxy-5-( 1 -methylpropyl)-, monosodium salt; Tinogard HS -37 -Nc A CAS No. of A UV absorber selected from the formulas _____ ___________________________________ __________ (1O1)and (102) Comb Benzoic acid, 2-[4-(diethylamino)-2-hydroxy-302776-68-7 X 098 benzoyl]-, hexyl ester, Uvinul a plus Comb 1-Dodecanaminium, N-[3-[4-(dimethylami-156679-41-3 X 099 no)benzoyl]aminojpropyl]N,N-thmethy!-, salt with 4-methylbenzenesulfonic acid (1:1) _____ (Escalol HP61O) ___________ Comb 1-Propanaminium, N,N,N-trimethyl-3-[(1-oxo-177190-98-6 X 3-phenyl-2-propenyl)amino]-, chloride Comb 1 H-Benzjmjdazole-4,6-disulfonic acid, 2,2'-170864-82-1 X 101 (1,4-pheny!ene)bis-Comb 1,3,5-Triazine, 2,4,6-tris(4-methoxyphenyl)-7753-12-0 X Comb 1,3,5-Triazine, 2,4,6-tris[4-[(2-ethylhexyl)oxy]-208114-14-1 X 103 phenyl]-(Tinosorb S) __________ Comb 1 -Propanaminium, 3-[3-[3-(2H-benzotriazol-340964-15-0 X 104 2-yl)-5-(1, 1 -dimethylethyl)-4-hydroxyphenyl]- 1 -oxopropyl]am ino]-N, N-diethyl-N-methyl-, _____ methyl sulfate (salt) Comb 2-Propenoic acid, 3-(1 H-imidazol-4-yl)-104-98-3 X Comb Benzoic acid, 2-hydroxy-, [4-(1-methylethyl)-94 134-93-7 X 106 phenyl]methyl ester Comb 1,2,3-Propanetriol, 1-(4-aminobenzoate); 136-44-7 X 107 glyceryl PABA Comb Benzeneacetic acid, 3,4-dimethoxy-a-oxo-4732-70-1 X 108 ________________________________________ ___________ _____________________ Comb 2-Propenoic acid, 2-cyano-3,3-diphenyl-, 5232-99-5 X 109 ethyl ester Comb Anthralinic acid, p-menth-3-yl ester 134-09-8 X

__________________________________ _________

Comb 2,2'-bis(l,4-phenylene)-1 H-benzimidazole-349580-12-7, X 111 4,6-disulphonic acid mono sodium salt or Disodium phenyl dibenzimidazole tetrasulfonate or Neohelopan AP Comb 1,3,5-Triazine-2,4,6-triamine, N,N'-bis[4-[5-288254-16-0 X 112 (1,1 -dimethylpropyl)-2-benzoxazolyl]phenyl]- _____ N"-(2-ethylhexyl)-(Uvasorb K2A) ____________ Comb Merocyanine derivatives as described in X 113 W02004006878 and 1PC0M000022279D -38 -Nc A CAS No. of A UV absorber selected from the formulas _____ ___________________________________ __________ (101)and (102) Comb x c -c

H H H CN

Comb sterols (cholesterol, lanosterol, phytosterols), X as described in W00341675 Comb mycosporines and/or mycosporine-like amino X 116 acids as described in W02002039974, e.g. Helioguard 365 from Milbelle AG, isolated mycosporine like amino acids from the red alga porphyra umbilicalis (INCI: Porphyra Umbilicalis) that are encapsulated into _____ liposomes,) Comb alpha-lipoic-acid as described in DE X 117 10229995 Comb synthetic organic polymers as described in X 118 EP 1371358, [0033]-[0041] Comb phyllosilicates as described in EP 1371357 X 119 [0034]-[0037] Comb silica compounds as described in X EP1371356, [0033]-[0041] __________ Comb inorganic particles as described in X 121 DE10138496 [0043]-[0055] __________ Comb latex particles as described in DE10138496 X 122 [0027]-{0040] Furthermore, the following specific UV filter combinations are of specific interest No. UV filter (A) UV filter (B) 1 UV filter (C) Comb 2-ethylhexyl 4-methoxy-micron ized UV absorber of UV absorber selected 124 cinnamate; octyl methoxy formula (103) from the formulas cinnamate (101)and (102) Comb 2-ethylhexyl 4-Benzoic acid, 2-[4-(diethyl-UV absorber selected methoxycinnamate; octyl amino)-2-hydroxybenzoyl}-, from the formulas ____ methoxy cinnamate hexyl ester; Uvinul a plus (101)and (102) Comb 2-ethylhexyl 4-methoxy-Benzoic acid, 2-[4-(diethyl-UV absorber selected _____ cinnamate; octyl methoxy amino)-2-hydroxybenzoyl]-, from the formulas -39 -No. UV filter (A) UV filter (B) UV filter (C) 126 cinnamate hexyl ester; Uvinul a plus (101) and (102) Comb 2-ethylhexyl 4-methoxy-Benzoic acid, 4,4'-[6-[4-[(1,1-UV absorber selected 127 cinnamate, octyl methoxy dimethylethyl)amino}carbo-from the formulas cinnamate nyl]phenyl]amino]1,3,5-triazine-(101) and (102) 2,4-diyl]diimino]bis-, bis(2-ethylhexyl)ester; diethylhexyl butamido triazone (Uvasorb ____ __________________ HEB) Comb 2-ethylhexyl 4-methoxy-2,2'-bis(l,4-phenylene)-1 H-Uv absorber selected 128 cinnamate; octyl methoxy benzimidazole-4,6-disulphonic from the formulas cinnamate acid mono sodium salt or Di-(101) and (102) sodium phenyl dibenzimidazole tetrasulfonate (Neohelio- _____ ______________________ pan AP) Comb 2-ethylhexyl 4-methoxy-2-Ethyihexyl 2-cyano,3,3-UV absorber selected 129 cinnamate; octyl methoxy diphenylacrylate; octocrylene from the formulas cinnamate (101)and (102) Comb 2-ethylhexyl 4-methoxy-Benzoic acid, 4, 4', 4u(1, 3, 5 UV absorber selected cinnamate; octyl methoxy triazine-2,4,6-triyltriimino)tr-is-, from the formulas cinnamate tris(2-ethylhexyl)ester; 2,4,6-(101) and (102) Trian ilino-(p-carbo-2'-ethyl-hexyl-1'-oxi)-l,3,5-triazine; _____ ________________________ octyl triazone Comb 2-ethylhexyl 4-methoxy-2-phenyl-1 H-benzimidazole-5-UV absorber selected 131 cinnamate; octyl methoxy sulphonic acid; phenylbenz-from the formulas cinnamate imidazolsulfonic acid (101) and (102) Comb 2-ethylhexyl 4-methoxy-1 -[4-( 1,1 -dimethylethyl)phenyl]-UV absorber selected 132 cinnamate; octyl methoxy 3-(4-methoxyphenyl)propane-from the formulas cinnamate 1,3-dione; avobenzone (101) and (102) Comb 2-ethylhexyl 4-methoxy-Phenol, 2-(2H-benzotriazol-2-UV absorber selected 133 cinnamate; octyl methoxy yl)-4-methyl-6-{2-methyl-3-from the formulas cinnamate [1,3,3,3-tetramethyl-1 -[(tn-(101) and (102) methylsilyl)oxy]disiloxanyl]prop yl]-; drometrizole trisiloxane; _____ ______________________ Mexoryl XL Comb 2-ethylhexyl 4-methox-Dimethicodiethylbenzalmalonat UV absorber selected 134 ycinnamate; octyl methoxy e; Polysilicone 15; Parsol SLX from the formulas cinnamate (101)and (102) Comb 2-ethylhexyl 4-methoxy-2,2'-Methylene-bis-[6-(2 H-ben-UV absorber selected cinnamate; octyl methoxy zotriazol-2-yl)-4-(1,1,3,3-tetra-from the formulas cinnamate methylbutyl)-phenol]; Tinosorb (101) and (102)

M

Comb 2-ethylhexyl 4-methoxy-2,4-bis{[4-(2-ethylhexyloxy)-2-UV absorber selected 136 cinnamate; octyl methoxy hydroxy]-phenyl}-6-(4-me-from the formulas -40 -No. UV filter (A) UV filter (B) UV filter (C) cinnamate thoxyphenyl)-(1,3,5)-triazine; (101) -(105) Tinosorb S Comb 2,4-bis{[4-(2-ethylhexyl-2,2'-Methylene-bis-[6-(2H-UV absorber selected 137 oxy)2-hydroxy]-phenyl}-6-benzotriazol-2-yl)-4-(1,1,3,3-from the formulas (4-methoxyphenyl)-(1,3,5)-tetramethylbutyl)-phenol]; (101) and (102) triazine; Tinosorb S Tinosorb M Comb Benzoic acid, 2-[4-(diethyl-1-[4-(1,1-dimethylethyl)phenyl]-UV absorber selected 138 amino)-2-hydroxybenzoyl]-3-(4-methoxyphenyl)propane-from the formulas _____ hexyl ester; Uvinul a plus 1,3-dione; avobenzone (101)-(105) Comb 2,4-bis{[4-(2-ethylhexyl-1 -[4-( 1,1 -d imethylethyl)phenyl]-UV absorber selected 139 oxy)-2-hydroxy]-phenyl}-6-3-(4-methoxypheny)propane-from the formulas (4-methoxyphenyl)-(1,3,5)-1,3-dione; avobenzone (101) and (102) triazine; Tinosorb S Comb 1 -[4-(1, 1 -dimethylethyl)-2,2'-bis(l,4-phenylene)-1 H-Uv absorber selected phenyl]-3-(4-methoxy-benzimidazole-4,6-disulphonic from the formulas phenyl)propane-1,3-dione; acid mono sodium salt or Di-(101) and (102) avobenzone sodium phenyl dibenzimidazole tetrasulfonate or Neoheliopan

AP

The cosmetic or pharmaceutical preparations may be, for example, creams, gels, lotions, alcoholic and aqueous/alcoholic solutions, emulsions, wax/fat compositions, stick prepa-rations, powders or ointments. In addition to the above mentioned UV filters, the cosmetic or pharmaceutical preparations may contain further adjuvants as described below.

As water-and oil-containing emulsions (e.g. W/O, O/W, O/W/O and W/O/W emulsions or microemulsions) the preparations contain, for example, from 0.1 to 30 % by weight, pre-ferably from 0.1 to 15 % by weight and especially from 0.5 to 10 % by weight, based on the total weight of the composition, of one or more UV absorbers, from 1 to 60 % by weight, especially from 5 to 50 % by weight and preferably from 10 to 35 % by weight, based on the total weight of the composition, of at least one oil component, from 0 to 30 % by weight, especially from 1 to 30 % by weight tind preferably from 4 to 20 % by weight, based on the total weight of the composition, of at least one emulsifier, from 10 to 90 % by weight, especially from 30 to 90 % by weight, based on the total weight of the composition, of water, and from 0 to 88.9 % by weight, especially from 1 to 50 % by weight, of further cosmetically acceptable adjuvants. -41 -

The cosmetic or pharmaceutical compositions/preparations according to the invention may also contain one or one more additional compounds as described below.

Fatty alcohols Guerbet alcohols based on fatty alcohols having from 6 to 18, preferably from 8 to 10 carbon atoms including cetyl alcohol, stearyl alcohol, cetearyl alcohol, oleyl alcohol, octyldodecanol, benzoate of C12-C15 alcohols, acetylated lanolin alcohol, etc..

Esters of fatty acids Esters of linear C6-C74 fatty acids with linear C3-C24 alcohols, esters of branched C6-C13car-boxylic acids with linear C-C24 fatty alcohols, esters of linear C6-C24 fatty acids with branched alcohols, especially 2-ethylhexanol, esters of hydroxycarboxylic acids with linear or branched C6-C22 fatty alcohols, especially dioctyl malates, esters of linear and/or branched fatty acids with polyhydric alcohols (for example propylene glycol, dimer diol or trimer triol) and/or Guerbet alcohols, for example caproic acid, caprylic acid, 2- ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeo-stearic acid, arachidic acid, gadoleic acid, behenic acid and erucic acid and technical-grade mixtures thereof (obtained, for example, in the pressure removal of natural fats and oils, in the reduction of aldehydes from Roelen's oxosynthesis or in the dimerisation of unsaturated fatty acids) with alcohols, for example, isopropyl alcohol, caproic alcohol, capryl alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linoyl alcohol, linolenyl alcohol, elaeostearyl alcohol, arachidyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and technical-grade mixtures thereof (obtained, for example, in the high-pressure hydrogenation of technical-grade methyl esters based on fats and oils or aldehydes from Roelen's oxosynthesis and as monomer fractions in the dimerisation of unsaturated fatty alcohols).

Examples of such ester oils are isopropylmyristate, isopropylpalmitate, isopropylstearate, so- propyl isostearate, isopropyl oleate, n-butylstearate, n-hexyllaurate, n-decyloleate, isooctyl- stearate, iso-nonylstearate, isononyf isononanoate, 2-ethylhexylpalmitate, 2-hexyllaurate, 2- hexyldecylstearate, 2-octyldodecylpalmitate, oleyloleate, oleylerucate, erucyloleate, erucyl-erucate, cetearyl octanoate, cetyl palmitate, cetyl stearate, cetyl oleate, cetyl behenate, cetyl -42 - acetate, myristyl myristate, myristyl behenate, myristyl oleate, mynstyl stearate, myristyl pal-mitate, myristyl lactate, propylene glycol dicaprylate/caprate, stearyl heptanoate, diisostearyl malate, octyl hydroxystearate, etc..

Other adiuvants alpha glucosyirutin (CAS No. 130603-71-3), 2-butyloctyl o-hydroxybenzoate (CAS No. 190085-41-7), vitamin E (CAS No. 1406-18-4), , vitamin E acetate (CAS No. 58-95-7), diethylhexyl 2,6-naphthalate, di-n-butyl adipate, di(2-ethylhexyl)-adipate, di(2-ethylhexyl)-succinate and diisotridecyl acelaat, and also diol esters, such as ethylene glycol dioleate, ethylene glycol diisotridecanoate, propylene glycol di(2-ethylhexanoate), propylene glycol diisostearate, propylene glycol dipelargonate, butanediof diisostearate and neopentyl glycol dicaprylate. Esters of C6-C24 fatty alcohols and/or Guerbet alcohols with aromatic carboxylic acids, saturated and/or unsaturated, especially benzoic acid, esters of C2-C12dicarboxylic acids with linear or branched alcohols having from 1 to 22 carbon atoms or polyols having from 2 to 10 carbon atoms and from 2 to 6 hydroxy groups, or iminodisuccinic acid and imiondisuccinic acid salts [CAS 7408-20-0] or latex particles, aloe vera, chamomile, ginko biloba, ginseng, coenzyme Q10, laminaria ochroleuca extract, magnolia oborata extract, melalenca alternifolia leaf oil, rubus idaeus seed oil, vaccinium macrocarpon seed oil, pumpkin seed extract, pumpkin seed oil, grape seed extract, carnosine, alpha-arbutin, madecassoside, termino-laside, tetrahydrocurcuminoids (THC), mycosporines, mycosporine like amino acids from the red alga porphyra umbilicalis, mycosporine-like amino acids (as described in W02002039974), cis-9-octadecenedioic acid, lipoic acid,laurimino dipropiomic acid tocopheryl phosphates (LDTP), microcrystalline cellulose (MOO), polycarbonates as described in WO 0341676, sterols (cholesterol, lanosterol, phytosterols), as described in W00341675 and linear poly-aipha-glucans as described in US6616935 Natural or synthetic triglycerides including glyceryl esters and derivatives Dior tri-glycerides, based on 06-018 fatty acids, modified by reaction with other alcohols (caprylic/capric triglyceride, wheat germ giyceriaes, etc.). Fatty acid esters of polyglycerin (polyglyceryl-n such as polyglyceryl-4 caprate, polyglyceryl-2 isostea rate, etc. or castor oil, hydrogenated vegetable oil, sweet almond oil, wheat germ oil, sesame oil, hydrogenated cottonseed oil, coconut oil, avocado oil, corn oil, hydrogenated castor oil, shea butter, cocoa butter, soybean oil, mink oil, sunflower oil, safflower oil, macadamia nut oil, olive oil, hydro-genated tallow, apricot kernel oil, hazelnut oil, borago oil, etc. -43 - Waxes including esters of long-chain acids and alcohols as well as compounds having wax-like properties, e.g., carnauba wax, beeswax (white or yellow), lanolin wax, candellila wax, ozokerite, japan wax, paraffin wax, microcrystalline wax, ceresin, cetearyl esters wax, syn-thetic beeswax,etc. Also, hydrophilic waxes as Cetearyl Alcohol or partial glycerides.

Pearlescent waxes.

Ikylene glycol esters, especially ethylene glycol distearate, fatty acid alkanolamides, especially coco fatty acid diethanolamide; partial glycerides, especially stearic acid monoglyceride; esters of polyvalent, unsubstituted or hydroxy-substituted carboxylic acids with fatty alcohols having from 6 to 22 carbon atoms, especially long-chained esters of tartaric acid; fatty substances, for example fatty alcohols, fatty ketones, fatty aldehydes, fatty ethers and fatty carbonates, which in total have at least 24 carbon atoms, especially laurone and distearyl ether; fatty acids, such as stearic acid, hydroxystearic acid or behenic acid, ring-opening products of olefin epoxides having from 12 to 22 carbon atoms with fatty alcohols having from 12 to 22 carbon atoms and/or polyols having from 2 to 15 carbon atoms and from 2 to 10 hydroxy groups, and mixtures thereof.

Hydrocarbon oils: Mineral oil (light or heavy), petrolatum (yellow or white), microcrystalline wax, paraffinic and isoparaffinic compounds, hydrogenated isoparaffinic molecules as polydecenes and polybu-tene, hydrogenated polyisobutene, squalane, isohexadecane, isododecane and others from plant and animal kingdom.

Silicones or siloxanes (organosubstituted polysiloxanes) Dimethylpolysiloxanes, methylphenylpolysiloxanes, cyclic silicones, and also amino-, fatty acid-, alcohol-, polyether-, epoxy-, fluorine-, glycoside-and/or alkyl-modified silicone com- pounds, which at room temperature may be in either liquid or resinous form. Linear poly-siioxanes, dimeihicone (Dow Corning 200 fluid, Rhodia Mirasil DM), dimethiconol, cyclic silicone fluids, cyclopentasiloxanes volatiles (Dow Corning 345 fluid), phenyltrimethicone (Dow Corning 556 fluid). Also suitable are simethicones, which are mixtures of dimethicones having an average chain length of from 200 to 300 dimethylsiloxane units with hydrogenated silicates. A detailed survey by Todd et a!. of suitable volatile silicones may in addition be found in Cosm. Toil. 91, 27(1976) -44 -Fluorinated or erfluorinated oils Perfluorhexane, d irnethylcyclohexane, ethylcyclopenta ne, polyperfluoromethylisopropyl ether.

Emulsifiers Any conventionally usable emulsifier can be used for the compositions. Emulsifier systems may comprise for example. carboxylic acids and their salts: alkaline soap of sodium, potassium and ammoniurn, metallic soap of calcium or magnesium, organic basis soap such as Lauric, palmitic, stearic and oleic acid etc... Alkyl phosphates or phosphoric acid esters, acid phosphate, diethanolamine phosphate, potassium cetyl phosphate. Ethoxylated carboxylic acids or polyethyleneglycol esters, PEG-n acylates. Linear fatty alcohols having from 8 to 22 carbon atoms, branched from 2 to 30 mol of ethylene oxide and/or from 0 to 5 mol propylene oxide with with fatty acids having from 12 to 22 carbon atoms and with alkylphenols having from 8 to 15 carbon atoms in the alkyl group. Fatty alcohol polyglycol-ether such as laureth-n, ceteareth-n, steareth-n, oleth-n. Fatty acid polyglycolether such as PEG-n stearate, PEG-n oleate, PEG-n cocoate. Monoglycerides and polyol esters. C 12-022 fatty acid mono-and di-esters of addition products of from 1 to 30 mol of ethylene oxide with polyols. Fatty acid and polyglycerol ester such as monostearate glycerol, diisostearoyl polyglyceryl-3-diisostearates, polyglyceryl-3-di isostearates, triglyceryl d iisostearates, polyglyceryl-2-sesqu iisostearates or polyglyceryl d irnerates. Mixtures of corn pounds from a plurality of those substance classes are also suitable. Fatty acid polyglycolesters such as rnonostearate diethylene glycol, fatty acid and polyethylene glycol esters, fatty acid and saccharose esters such as sucro esters, glycerol and saccharose esters such as sucro glycerides. Sorbitol and sorbitan, sorbitan mono-and di-esters of saturated and unsaturated fatty acids having from 6 to 22 carbon atoms and ethylene oxide addition products. Polysor- bate-n series, sorbitan esters such as sesquiisostearate, sorbitan, PEG-(6)-isostearate sor-bitan, PEG-(i0)-sorbitan laurate, PEG-i 7-dioleate sorbitan. Glucose derivatives, 08-022 alkyl-mono and oligo-glycosides and ethoxylated analogues with glucose being preferred as the sugar component. 01W emulsifiers such as methyl gluceth-20 sesquistearate, sorbitan stearate/sucrose cocoate, methyl glucose sesq uistearate, cetearyl alcohol/cetearyl gluco-side. WI0 emulsifiers such as methyl glucose dioleate/ methyl glucose isostearate. Sulfates and sulfonated derivatives, dialkylsulfosuccinates, dioctyl succinate, alkyl lauryl sulfonate, linear sulfonated parafins, sulfonated tetraproplyne sulfonate, sodium lauryl sulfates, amo- -45 - nium and ethanolamine lauryl sulfates, lauyl ether sulfates, sodium laureth sulfates, sulfosuc- cinates, aceyl isothionates, alkanolamide sulfates, taurines, methyl taurines, imidazole sul- fates. Amine derivatives, amine salts, ethoxylated amines, oxide amine with chains contain-fling an heterocycle such as alkyl imidazolines, pyridine derivatives, isoquinoteines, cetyl pyridinium chlorure, cetyl pyridinium bromide, quaternary ammonium such as cetyltrimethyl-broide amonium broide (CTBA), stearylalkonium. Amide derivatives, alkanolamides such as acylamide DEA, ethoxylated amides such as PEG-n acylamide, oxydeamide; polysiloxane/-polyalkyl/polyether copolymers and derivatives, dimethicone, copolyols, silicone polyethylene oxide copolymer, silicone glycol copolymer; propoxylated or POE-n ethers (Meroxapols); polaxamers or poly(oxyethylene)mblockpoly(oxypropylene)nblock(oxyethylene). zwitter-ionic surfactants that carry at least one quaternary ammonium group and at least one car-boxylate and/or sulfonate group in the molecule. Zwitterionic surfactants that are especially suitable are betaines, such as N-alkyl-N,N-dimethylammonium glycinates, cocoalkyldimethyl- ammonium glycinate, N-acylaminopropyl-N,N-dimethylammonium glycinates, cocoacyl-aminopropyldimethylammonjum glycinate and 2-alkyl-3-carboxyn-iethyI3hydroxyethyp imidazolines each having from 8 to 18 carbon atoms in the alkyl or acyl group and also coco-acylaminoethylhydroxyethylcarboxymethylglycinate N-alkylbetaine, N-alkylaminobetaines.

alkylimidazolines, alkylopeptides, lipoaminoacides, self emulsifying bases and the com-pounds as described in K.F.DePolo, A short textbook of cosmetology, Chapter 8, Table 8-7, p250-251.

Non ionic emulsifiers such as PEG-6 beeswax (and) PEG-6 stearate (and) polyglyceryl - 2-isostearate [Apifac], glyceryl stearate (and) PEG-i00 stearate. [Arlacel 165], PEG-5 glyceryl stearate [arlatone 983 S], sorbitan oleate (and) polyglyceryl-3 ricinoleate.[Arlacel 1689], sorbitan stearate and sucrose cocoate [arlatone 2121], glyceryl stearate and laureth- 23 [Cerasynth 945], cetearyl alcohol and ceteth-20 [Cetomacrogol Wax], cetearyl alcohol and colysorbate 60 and PEG-i 50 and stearate-20[Polawax GP 200, Polawax NF], cetearyl alcohol and cetearyl polyglucoside [Emulgade PL 1618], cetearyl alcohol and ceteareth-20 [Emu!gade I000N, Cosmowax], cetedryl dicohol and PEG-40 castor oil [mulgade F Special], cetearyl alcohol and PEG-40 castor oil and sodium cetearyl sulfate [Emulgade F], stearyl alcohol and steareth-7 and steareth-lO [Emulgator E 2155], cetearyl alcohol and szeareth-7 and steareth-lO [Emulsifying wax U.S.N.F], glyceryl stearate and PEG-75 stearate [Getot 64], propylene glycol ceteth-3 acetate.[Hetester PCS], propylene glycol isoceth-3 acetate [Hetester PHA], cetearyl alcohol and ceteth-i2 and oleth-i2 [Lanbritol Wax -46 -N 21], PEG -6 stearate and PEG-32 stearate [Tefose 1500], PEG-6 stearate and ceteth-20 and steareth-20 [Tefose 2000], PEG-6 stearate and ceteth-20 and glyceryl stearate and steareth-20 [Tefose 2561], glyceryl stearate and ceteareth20 [Teginacid H, C, XI.

Anionic emulsifiers such as PEG-2 stearate SE, glyceryl stearate SE [Morielgine, Cutina KD], propylene glycol stearate [Tegin P], cetearyl Alcohol and Sodium cetearyl sulfate [Lanette N, Cutina LE, Crodacol GP], cetearyl alcohol and sodium lauryl sulfate [Lanette W], trilaneth-4 phopshate and glycol stearate and PEG-2 stearate [Sedefos 75], glyceryl stearate and sodium lauryl Sulfate [Teginacid Special]. Cationic acid bases such as cetearyl alcohol and cetrimonium bromide.

The emulsifiers may be used in an amount of, for example, from 1 to 30 % by weight, especially from 4 to 20 % by weight and preferably from 5 to 10 % by weight, based on the total weight of the composition.

When formulated in 0/W emulsions, the preferably amount of such emulsifier system could represent 5% to 20% of the oil phase.

juvants and additives The cosmetic / pharmaceutical preparations, for example creams, gels, lotions, alcoholic and aqueous/alcoholic solutions, emulsions, wax/fat compositions, stick preparations, powders or ointments, may in addition contain, as further adjuvants and additives, mild surfactants, su-per-fatting agents, consistency regulators, thickeners, polymers, stabilisers, biogenic active ingredients, deodorising active ingredients, anti-dandruff agents, film formers, swelling agents, further UV light-protective factors, antioxidants, hydrotropic agents, preservatives, insect repellents, self-tanning agents, solubilisers, perfume oils, colourants, bacteria-inhibiting agents and the like.

Super fottinQ oqents Substances suitable for use as super-fatting agents are, for example, lanolin and lecithin and also polyethoxylated or acrylated lanolin and lecithin derivatives, polyol fatty acid esters, monoglycerides and fatty acid alkanolamides, the latter simultaneously acting as foam stabilisers.

-47 -S U rIactants Examples of suitable mild surtactants, that is to say surfactants especially well tolerated by the skin, include fatty alcohol polyglycol ether sulfates, monoglyceride sulfates, mono-and/or di-alkyl sulfosuccinates, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, fatty acid glutamates, (x-olefin sulfonates, ethercarboxylic acids, alkyl oligoglucosides, fatty acid glucamides, alkylamidobetaines and/or protein fatty acid condensation products, the latter preferably being based on wheat proteins.

Consistency regulators/thickeners and rheology modifiers Silicium dioxide, magnesium silicates, aluminium silicates, polysaccharides or derivatives thereof for example hyaluronic acid, xanthan gum, guar-guar, agar-agar, alginates, carra- ghenan, gellan, pectines, or modified cellulose such as hydroxycellulose, hydroxypropyl-methylcellulose. In addition polyacrylates or homopolymer of reticulated acrylic acids and polyacrylamides, carbomer (carbopol types 980, 981, 1382, ETD 2001, ETD2O2O, Ultrez 10) or Salcare range such as Salcare SC8O(steareth-1 0 allyl ether/acrylates copolymer), Salcare SC81(acrylates copolymer), Salcare SC91 and Salcare AST(sodium acrylates copoly-mer/PPG-1 trideceth-6), sepigel 3OS(polyacrylamide/laureth7) Simulgel NS and Simulgel EG (hydroxyethyl acrylate / sodium acryloyldimethyl taurate copolymer), Stabilen 30 (acrylates / vinyl isodecanoate crosspolymer), Pemulen TR-1(acrylates / Cl 0-30 alkyl acrylate crosspolymer-), Luvigel EM (sodium acrylates copolymer), Aculyn 28 (acrylates/beheneth-25 methacrylate copolymer), etc. Polymers Suitable cationic polymers are, for example, cationic cellulose derivatives, for example a qua-ternised hydroxymethyl cellulose obtainable under the name Polymer JR 400 from Amerchol, cationic starches, copolymers of diallylammonium salts and acrylamides, quarternised vinyl-pyrrolidone/vinyl imidazole polymers, for example Luviquat (BASF), condensation products of polyglycols and amines, quaternised collagen polypeptides, for example lauryldimonium hydroxypropyl hyaroiyzed collagen (Lamequat L/Grünau), quaternised wheat polypeptides, polyethyleneimine, cationic silicone polymers, for example amidomethicones, copolymers of adipic acid and dimethylaminohydroxypropyldiethylenefrij (Cartaretin/Sandoz), copoly- mers of acrylic acid with dimethyldiallylammonium chloride (Merquat 550 / Chemviron), poly- aminopolyamides, as described, for example, in FR-A-2 252 840, and the crosslinked water-soluble polymers thereof, cationic chitin derivatives, for example of quaternised chitosan, -48 -optionally distributed as microcrystals; condensation products of dihaloalkyls, for example dibromobutane, with bisdialkylamines, for example bisdimethylamino-i,3-propane, cationic guar gum, for example Jaguar c-i 7, Jaguar 0-16 from Celanese, quaternised ammonium salt polymers, for example Mirapol A-i 5, Mirapol AD-i, Mirapol AZ-i from Miranol. As an-ionic, zwitterionjc, amphoteric and non-ionic polymers there come into consideration, for example, vinyl acetate I crotonic acid copolymers, vinylpyrrolidone I vinyl acrylate copoly-mers, vinyl acetate / butyl maleate I isobornyl acrylate copolymers, methyl vinyl ether / maleic anhydride copolymers and esters thereof, uncrosslinked polyacrylic acids and polyacrylic acids crosslinked with polyols, acrylamidopropyltrimethyJamrnonim chloride /acrylate copolymers, octyl acrylamidelmethyl methacrylatetertbutylaminoethyl methacrylate!2-hydroxypropy: methacrylate copolymers, polyvinylpyrrolidone, vinylpyrrolidone/vinyl acetate copolymers, vinyl pyrrolidone/d imethylami noethyl methacrylate/vinyl caprolactam terpolymers and also optionally derivatised cellulose ethers and silicones. Furthermore the polymers as described in EP i093796 (pages 3-8, paragraphs 17-68) may be used.

Biogenic active ingredients Biogenic active ingredients are to beunderstood as meaning, for example, tocopherol, toco-pherol acetate, tocopherol palmitate, ascorbic acid, deoxyribonucleic acid, retinol, bisabolol, allantoin, phytantriol, panthenol, AHA acids, amino acids, ceramides, pseudoceramides, essential oils, plant extracts and vitamin complexes.

Deodorising active ingredients As deodorising active ingredients there come into consideration, for example, antiperspi-rants, for example aluminium chlorohydrates (see J. Soc. Cosm. Chem. 24, 28i (1973)).

Under the trade mark Locron of Hoechst AG, Frankfurt (FRG), there is available corner-cially, for example, an aluminium chlorohydrate corresponding to formula Al2(OH)Cl x 2.5 H20, the use of which is especially preferred (see J. Pharm. Pharmacol. 26, 53i (i 975)) Besides the chlorohydrates, it is also possible to use aluminium hydroxyacetates and acidic aiuminium!zirconiurn sails. Esterase inhibitors may be added as further deodorising active ingredients. Such inhibitors are preferably trialkyl citrates, such as trimethyl citrate, tripropyl citrate, triisopropyl citrate, tributyl citrate and especially triethyl citrate (Hydagen CAT, Hen-kel), which inhibit enzyme activity and hence reduce odour formation. Further substances that come into consideration as esterase inhibitors are sterol sulfates or phosphates, for example lanosterol, cholesterol, campesterol, stigmasterol and sitosterol sulfate or phos- -49 - phate, dicarboxylic acids and esters thereof, for example glutaric acid, glutaric acid mono-ethyl ester, glutaric acid diethyl ester, adipic acid, adipic acid monoethyl ester, adipic acid diethyl ester, malonic acid and malonic acid diethyl ester and hydroxycarboxylic acids and esters thereof, for example citric acid, malic acid, tartaric acid or tartaric acid diethyl ester.

Antibacterial active ingredients that influence the germ flora and kill or inhibit the growth of sweat-decomposing bacteria can likewise be present in the preparations (especially in stick preparations) Examples include chitosan, phenoxyethanol and chlorhexidine gluconate. 5-chloro-2-(2,4-dlchlorophenoxy)phenol (Triclosan, Irgasan, Ciba Specialty Chemicals Inc.) has also proved especially effective.

Anti-dandruff aQents As anti-dandruff agents there may be used, for example, climbazole, octopirox and zinc pyri- thione. Customary film formers include, for example, chitosan, microcrystalline chitosan, qua-ternised chitosan, polyvinylpyrrolidone, vinylpyrrolidorie/vinyl acetate copolymers, polymers of quaternary cellulose derivatives containing a high proportion of acrylic acid, collagen, hyaluronic acid and salts thereof and similar compounds.

Antioxidarits In addition to the primary light-protective substances it is also possible to use secondary light-protective substances of the antioxidant kind that interrupt the photochemical reaction chain triggered when UV radiation penetrates the skin or hair. Typical examples of such anti- oxidants are amino acids (e.g. glycine, histidine, tyrosine, tryptophan) and derivatives there-of, imidazoles (e.g. urocanic acid) and derivatives thereof, peptides, such as D,L-carnosine, D-carnosine, L-carnosine and derivatives thereof (e.g. anserine), carotinoids, carotenes, lycopene and derivatives thereof, chiorogenic acid and derivatives thereof, lipoic acid and derivatives thereof (e.g. dihydrolipoic acid), aurothioglycose, propyithiouracil and other thiols (e.g thioredoxin, glutnione, cysteine, cystine, cystamine and the glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl, lauryl, palmitoyl, oleyl, linoleyl, cholesteryl and glyceryl esters thereof) 3nd so Salts thereof, dauryi Uiiodipropionate, distearyl thiodipropionate, thiodi-propionic acid and derivatives thereof (esters, ethers, peptides, lipids, nucleotides, nucleo- sides and salts) and also sulfoximine compounds (e.g. buthionine sulfoximines, homo-cysteine sulfoximine, buthionine sulfones, penta-, hexa-, hepta-thionine sulfoximine), also (metal) chelating agents (e.g. hydroxy fatty acids, palmitic acid phytic acid, lactoferrin), hydroxy acids (e.g. citric acid, lactic acid, malic acid), humic acid, bile acid, bile extracts, -50 -bilirubin, biliverdin, EDTA, EDDS, EGTA and derivatives thereof, unsaturated fatty acids and derivatives thereof (e.g. linolenic acid, linoleic acid, oleic acid), folic acid and derivatives thereof, ubiquinone and ubiquinol and derivatives thereof, vitamin C and derivatives (e.g. ascorbyl palmitate, magnesium ascorbyl phosphate, ascorbyl acetate), tocopherols and derivatives (e.g. vitamin E acetate), vitamin A and derivatives (e.g. vitamin A palmitate) and also coniferyl benzoate of benzoin resin, rutinic acid and derivatives thereof, glycosyirutin, ferulic acid, furfurylidene glucitol, carnosine, butyl hydroxytoluene, butyl hydroxyanisole, nordihydroguaiaretic acid, trihydroxybutyrophenone, uric acid and derivatives thereof, mannose and derivatives thereof, superoxide dismutase, N-[3-(3,5-di-tert-butyl-4-hydroxy phenyl)propionylJsulfaniljc acid (and salts thereof, for example the disodium salts), zinc and derivatives thereof (e.g. ZnO, ZnSO4), selenium and derivatives thereof (e.g. selenium me-thionine), stilbene and derivatives thereof (e.g. stilbene oxide, trans-stilbene oxide) and the derivatives suitable according to the invention (salts, esters, ethers, sugars, nucleotides, nucleosides, peptides and lipids) of those mentioned active ingredients. HALS ("Hindered Amine Light Stabilizers") compounds may also be mentioned.

Further synthetic and natural antioxidants are listed e.g. in patent WO 0025731: Structures 1-3 (page 2), structure 4 (page 6), structures 5-6 (page 7) and compounds 7-33 (page 8-14).

The amount of antioxidants present is usually from 0.001 to 30 % by weight, preferably from 0.01 to 3 % by weight, based on the weight of the UV absorber of formula (1).

tjydrotropic agents To improve the flow behaviour it is also possible to employ hydrotropic agents, for example ethoxylated or non ethoxylated mono-alcohols, diols or polyols with a low number of carbon atoms or their ethers (e.g. ethanol, isopropanol, 1,2-dipropanediol, propyleneglycol, glyerin, ethylene glycol, ethylene glycol monoethylether, ethylene glycol monobutylether, propylene g!yco! monomcthylether, propdene glycul rriorioethyiether, propylene glycol monobutylether, diethylene glycol monomethylether; diethylene glycol monoethylether, diethylene glycol monobutylether and similar products). The polyols that come into consideration for that purpose have preferably from 2 to 15 carbon atoms and at least two hydroxy groups. The polyols may also contain further functional groups, especially amino groups, and/or may be modified with nitrogen. Typical examples are as follows: glycerol, alkylene glycols, for -51 -example ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, hexylene glycol and also polyethylene glycols having an average molecular weight of from 100 to 1000 Dalton; technical oligoglycerol mixtures having an intrinsic degree of condensation of from 1.5 to 10, for example technical diglycerol mixtures having a diglycerol content of from 40 to 50 % by weight; methylol compounds, such as, especially, trimethylolethane, trimethylol-propane, trimethylolbutane, pentaerythritol and dipentaerythritol; lower alkyl-glucosides, especially those having from 1 to 8 carbon atoms in the alkyl radical, for example methyl and butyl glucoside; sugar alcohols having from 5 to 12 carbon atoms, for example sorbitol or mannitol; sugars having from 5 to 12 carbon atoms, for example glucose or saccharose; amino sugars, for example glucamine; diatcohol amines, such as diethanolamine or 2-amino-1,3-propanediol.

Preservatives and Bacteria-inhibiting agents Suitable preservatives include, for example,Methyl-,Ethyl-, Propyl-, Butyl-parabens, Benzal-konium chloride, 2-Bromo-2-nitro-propane-1,3-diol, Dehydroacetic acid, Diazolidinyl Urea, 2- Dichloro-benzyl alcohol, DMDM hydantoin, Formaldehyde solution, Methyldibromoglu-tanitrile, Phenoxyethanol, Sodium Hydroxymethylglycinate, Imidazolidinyl Urea, Triclosan and further substance classes listed in the following reference: K.F.DePolo -A short textbook of cosmetology, Chapter 7, Table 7-2, 7-3, 7-4 and 7-5, p210-219.

Typical examples of bacteria-inhibiting agents are preservatives that have a specific action against gram-positive bacteria, such as 2,4,4'-trichloro-2'-hydroxydiphenyl ether, chlorhexi-dine (1,6-di(4-chlorophenyl-biguanido)hexane) or TCC (3,4,4'-trichlorocarbanilide). A large number of aromatic substances and ethereal oils also have antimicrobial properties. Typical examples are the active ingredients eugenol, menthol and thymol in clove oil, mint oil and thyme oil. A natural deodorising agent of interest is the terpene alcohol farnesol (3,7,11-tn-methyl-2,6,10-dodecatrien-1-ol), which is present in lime blossom oil. Glycerol monolaurate has also proved to be a bacteriostatic agent. The amount of the additional bacteria-inhibiting dgerItb present is usudiiy irorn 0.1 to 2 % by weight, basea on the so'ids content ot the preparations.

Perfume oils There may be mentioned as perfume oils mixtures of natural and/or synthetic aromatic sub-stances. Natural aromatic substances are, for example, extracts from blossom (lilies, -52 -lavender, roses, jasmine, neroli, ylang-ylang), from stems and leaves (geranium, patchouli, petitgrain), from fruit (aniseed, coriander, carraway, juniper), from fruit peel (bergamot, lemons, oranges), from roots (mace, angelica, celery, cardamom, costus, iris, calmus), from wood (pinewood, sandalwood, guaiacum wood, cedarwood, rosewood), from herbs and grasses (tarragon, lemon grass, sage, thyme), from needles and twigs (spruce, pine, Scots pine, mountain pine), from resins and balsams (galbanum, elemi, benzoin, myrrh, olibanum, opoponax) Animal raw materials also come into consideration, for example civet and castoreum. Typical synthetic aromatic substances are, for example, products of the ester, ether, aldehyde, ketone, alcohol or hydrocarbon type. Aromatic substance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethylmethylphenyl glycinate, allylcyclohexyl propionate, styrallyl propionate and benzyl salicylate. The ethers include, for example, benzyl ethyl ether; the aldehydes include, for example, the linear alkanals having from 8 to 18 hydrocarbon atoms, citral, citronellal, citronellyl oxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal; the ketones include, for example, the ionones, isomethylionone and methyl cedryl ketone; the alcohols include, for example, anethol, citronellol, eugenol, isoeugenol, geraniol, linalool, phenyl ethyl alcohol and terpinol; and the hydrocarbons include mainly the terpenes and balsams. It is preferable, however, to use mixtures of various aromatic substances that together produce an attractive scent. Ethereal oils of relatively low volatility, which are chiefly used as aroma components, are also suitable as perfume oils, e.g. sage oil, camomile oil, clove oil, melissa oil, oil of cinnamon leaves, lime blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil, labolanum oil and lavandin oil. Preference is given to the use of bergamot oil, dihydromyrcenol, lilial, lyral, citronellol, phenyl ethyl alcohol, hexyl cinnamaldehyde, geraniol, benzyl acetone, cyclamen aldehyde, linalool, boisambrene forte, ambroxari, indole, hedione, sandelice, lemon oil, tangerine oil, orange oil, allyl amyl glycolate, cyclovertal, lavandin oil, muscatel sage oil, damascone, bourbon geranium oil, cyclohexyl salicylate, vertofix coeur, iso-E-Super, Fixolide NP, evernyl, iraldein gamma, phenylacetic acid, geranyl aceidie, benzyi acetate, rose oxide, romillat, irotyl and floramat alone or in admixture with one another.

Colourants There may be used as colourants the substances that are suitable and permitted for cos-metic purposes, as compiled, for example, in the publication "Kosmetische Färbemittel" of -53 - the Farbstoffkommission der Deutschen Forschungsgemeinschaft, Verlag Chemie, Wein-heim, 1984, pages 81 to 106. The colourants are usually used in concentrations of from 0.001 to 0.1 % by weight, based on the total mixture.

Other adjuvants It is furthermore possible for the cosmetic preparations to contain, as adjuvants, anti-foams, such as silicones, structurants, such as maleic acid, solubilisers, such as ethylene glycol, propylene glycol, glycerol or diethylene glycol, opacifiers, such as latex, styrene/PVP or sty-rene/acrylamide copolymers, complexing agents, such as EDTA, NTA, alaninediacetic acid or phosphonic acids, propellants, such as propane/butane mixtures, N20, dimethyl ether, 002, N2 or air, so-called coupler and developer components as oxidation dye precursors, reducing agents, such as thioglycolic acid and derivatives thereof, thiolactc acid, cysteamine, thiomalic acid or mercaptoethanesulfopic acid, or oxidising agents, such as hydrogen peroxide, potassium bromate or sodium bromate.

Suitable insect repellents are, for example, N,N-diethyl-m-toluamide 1,2-pentanediol or in-sect repellent 3535; suitable self-tanning agents are, for example, dihydroxyacetone and/or erythrulose or dihydroxy acetone and/or dihydroxy acetone precursors as described in WO 01/85124 and/or erythrulose.

Polymeric beads or hollow spheres as SPF enhancers The combination of the UV-absorbers and UV-absorber combinations, listed above, with SPF enhancers, such as non-active ingredients like Styrene/acrylates copolymer, silica beads, spheroidal magnesium silicate, crosslinked Polymethylniethacrylates (PMMA; Micopearl M305 Seppic), can maximize better the UV protection of the sun products. Holosphere additives (Sunspheres ISP, Silica Shells Kobo.) deflect radiation and the effective path length of the photon is therefore increased.( EP08931 19). Some beads, as mentioned pre-viously, provide a soft feel during spreading. Moreover, the optical activity of such beads, e g.Micropcrl M305, cans modulate skin shine by eliminating reflection phenomena and indirectly may scatter the UV light.

-54 -Cosmetic or pharmaceutical preparations Cosmetic or pharmaceutical formulations are contained in a wide variety of cosmetic preparations. There come into consideration, for example, especially the following preparations -skin-care preparations, e.g. skin-washing and cleansing preparations in the form of tablet-form or liquid soaps, soapless detergents or washing pastes, -bath preparations, e.g. liquid (foam baths, milks, shower preparations) or solid bath preparations, e.g. bath cubes and bath salts; -skin-care preparations, e.g. skin emulsions, multi-emulsions or skin oils; -cosmetic personal care preparations, e.g. facial make-up in the form of day creams or powder creams, face powder (loose or pressed), rouge or cream make-up, eye-care preparations, e.g. eyeshadow preparations, mascara, eyeliner, eye creams or eye-fix creams; lip-care preparations, e.g. lipsticks, lip gloss, lip contour pencils, nail-care preparations, such as nail varnish, nail varnish removers, nail hardeners or cuticle removers; -foot-care preparations, e.g. foot baths, foot powders, foot creams or foot balsams, special deodorants and antiperspirants or callus-removing preparations; -light-protective preparations, such as sun milks, lotions, creams or oils, sunblocks or tropicals, pre-tanning preparations or after-sun preparations; -skin-tanning preparations, e.g. self-tanning creams; -depigmenting preparations, e.g. preparations for bleaching the skin or skin-lightening preparations; -insect-repellents, e.g. insect-repellent oils, lotions, sprays or sticks; -deodorants, such as deodorant sprays, pump-action sprays, deodorant gels, sticks or roll-ons; -antiperspirants, e.g. antiperspirant sticks, creams or roll-ons; -preparations for cleansing and canng for blemished skin, e.g. synthetic detergents (solid or iiqui, peeling or scrub preparations or peeling masks; -hair-removal preparations in chemical form (depilation), e.g. hair-removing powders, liquid hair-removing preparations, cream-or paste-form hair-removing preparations, hair-removing preparations in gel form or aerosol foams; 55 - -shaving preparations, e.g. shaving soap, foaming shaving creams, non-foaming shaving creams, foams and gels, preshave preparations for dry shaving, aftershaves or aftershave lotions; -fragrance preparations, e g. fragrances (eau de Cologne, eau de toette, eau de parfum, parfum de toilette, perfume), perfume oils or perfume creams; -cosmetic hair-treatment preparations, e.g. hair-washing preparations in the form of shampoos and conditioners, hair-care preparations, e.g. pretreatment preparations, hair tonics, styling creams, styling gels, pomades, hair rinses, treatment packs, intensive hair treatments, hair-structuring preparations, e.g hair-waving preparations for permanent waves (hot wave, mild wave, cold wave), hair-straightening preparations, liquid hair-setting preparations, hair foams, hairsprays, bleaching preparations, e.g. hydrogen per-oxide solutions, lightening shampoos, bleaching creams, bleaching powders, bleaching pastes or oils, temporary, semi-permanent or permanent hair colourarits, preparations containing seif-oxidising dyes, or natural hair colourants, such as henna or camomile.

Presentation forms The final formulations listed may exist in a wide variety of presentation forms, for example: -in the form of liquid preparations as a WIO, 01W, O/W/O, WI0/W or PIT emulsion and all kinds of microemulsions, -in the form of a gel, -in the form of an oil, a cream, milk or lotion, -in the form of a powder, a lacquer, a tablet or make-up, -in the form of a stick, -in the form of a spray (spray with propellent gas or pump-action spray) or an aerosol, -in the form of a foam, or -in the form of a paste.

Of special importance as cosmetic preparations for the skin are light-protective preparations, such as sun milks, lotions, creams, oils, sunbiocks or tropicals, pretanning preparations or after-sun preparations, also skin-tanning preparations, for example self-tanning creams. Of particular interest are sun protection creams, sun protection lotions, sun protection milk and sun protection preparations in the form of a spray.

-56 - Of special importance as cosmetic preparations for the hair are the above-mentioned prepa-rations for hair treatment, especially hair-washing preparations in the form of shampoos, hair conditioners, hair-care preparations, e.g. pretreatment preparations, hair tonics, styling creams, styling gels, pomades, hair rinses, treatment packs, intensive hair treatments, hair-straightening preparations, liquid hair-setting preparations, hair foams and hairsprays. Of special interest are hair-washing preparations in the form of shampoos.

A shampoo has, for example, the following composition. from 0.01 to 5 % by weight of a UV absorber according to the invention, 12.0 % by weight of sodium laureth-2-sulfate, 4.0 % by weight of cocamidopropyl betaine, 3.0 % by weight of sodium chloride, and water ad 100%.

For example, especially the following hair-cosmetic formulations may be used: a1) spontaneously emulsifying stock formulation, consisting of the UV absorber according to the invention, PEG-6-Ciooxoalcohol and sorbitan sesquioleate, to which water and any desired quaternary ammonium compound, for example 4 % minkamidopropyl dimethyl- 2- hydroxyethylammonium chloride or Quaternium 80 is added; a2) spontaneously emulsifying stock formulation consisting of the UV absorber according to the invention, tributyl citrate and PEG-20-sorbitan monooleate, to which water and any desired quaternary ammonium compound, for example 4 % minkamidopropyl dimethyl-2-hydroxyethylammonium chloride or Quaternium 80 is added; b) quat-doped solutions of the UV absorber according to the invention in butyl triglycol and tributyl citrate; c) mixtures or solutions of the UV absorber according to the invention with n-alkylpyrrolidone.

Other typical ingredients in such formulations are preservatives, bactericides and bacterio-static agents, perfumes, dyes, pigments, thickening agents, moisturizing agents, humectants, fats, OilS, waxes or other typical ingredients of cosmetic and personal care formulations such as alcohols, poly-alcohols, polymers, electrolytes, organic solvents, silicon derivatives, emollients, emulsifiers or emulsifying surfactants, surfactants, dispersing agents, antioxi-dants, anti-irritants and anti-inflammatory agents etc. -57 -Examples of cosmetic and pharmaceutical preparations (X = preferred combinations) 01W systems: Ingredients 7 Em u Isifiers Potassium Cetyl Phosphate 2%-5% X Cetearyl Alcohol! Dicetyl Phosphate/Ceteth-lO Phos-X phate 2%-6% SodrumStearylPhtalamatel%-2% X Cetearyl Alcohol/Behentrimonium Methosulfate 1 %-5% X Quaternium-32 1%-5% X Dimethicone copolyol! Caprylic/Capric Triglyceride (1 %-X 4%) Steareth-2 /Steareth-21 2%-5% -X - Polyglyceryl Methyl Glucose Distearate 1%-4% --Lipophilicemollient/dispersantoil 15%-20% X X X X X X X Fatty Alcohols and/or Waxes 1 %-5% X X X X X X X Thickeners (water swellable thickeners) 0.5% -1.5% X X X K X X K Preservatives 0.5% -1% X X X X X X K Chelating agents (such as EDTA) 0%-0.2% X X X K x x x Antioxidants 0.05% -0.2% X X X X X X X K Water deionized Qs 100% X X X X X K K K Perfumeoils 0.1%-Q.4% X X X XXX X L UV-absorber according to the invention 0,1% -20% X X X X X K X ( UV-absorber as described in table 2-4 0% -30% X X X X X X X ( W/O systems Ingredients 1 2 3 Emulsifiers K K X X X Polyglyceryl-2 Dipolyhydroxystearate 2%-4% K K X X X PEG-30 Dipolyhydroxystearate 2%-4% -K ---Rapeseed Oil Sorbitol Esters 1 %-5% X PEG-45/Dodecyl Glycol Copolymer 1%-5% ---X -Sorbitan Oleate I Polycerol-3 ricinoleate 1 %-5% ----X Lipophilic emollient/dispersant oil 10% -20% K K X X X Fatty Alcohols and/or Waxes 10% -15% K K X X X Electrolytes (NaCI, MgSO4) 0.5%-1% L L. .2. .2. .2.

Polyoi phase (Propylene glyco!, glycerin) 1% -8% K K X K X Preservatives 0.3% -0.8% K K K K X Perfume oils 0.1%-0.4% K K K K K Chelating agents (such as EDTA) 0% -0.2% L L 2 2. 2.

Antioxidants 0.05% -0.2% K K X X X Water deionized Qs 100% ( L 2. .2L.2.

UV-absorber according to the invention 0,1% -20%. L L. .. 2. 2L UV-absorber as described in table 2-4 0% -30%. L L. .2S.. 2L 2.

-58 - -W/Silicone systems Ingredients.1 4 Dimethicone Copolyol I Cyclomethicone 5%-10% X X Laurylmethicone Copolyol 5%-10% -. -Cyclopentasiloxane 5%-25% x Dimethicone 15%-25% X X -Dimethicone/Vinyldimethicone Crosspolymer 1%-10% X X X X Humectant/polyols (Propylene glycol, glycerin...) 2%-8% X X X X Chelating agents (such as EDTA) 0%-0.2% X X X X Antioxidants 0.05%-0.2% X X X X Preservatives 0.3%-0.8% X X X X Perfume oils 0.1%-0.4% X X X X Water deionized Qs 100% X X X X UV-absorber according to the invention 0,1% 20% X X X X UV-absorber as described in table 2-4 0%-30% X X X X Multiple emulsions Ingredients 1 2 3 4 5 6 7 8 9 10 11 i PEG-30 Dipolyhydroxystearate X X X (2%-6%) Cetyl Dimethicone Copolyol X X 1%-3% PEG-30 Dipolyhydroxystearate/ X X Steareth-21 Steareth-21 4%-6% Polyglyceryl-2 Dipolyhydroxy-X X stearate 1%-3% Polyglyceryl-6 Ricinoleate 1 %-3% X X X Oil phase 15%-30% Fatty acid esters X X X X X X X Natural and synthetic Triglycerides X X X X X X X Hydrocarbon oils X X X X X X X Silicone oils x X X X X X X Preservatives 0.3% -0.8% X X X X X X X X X X X X Water Deioniz. qs 100% X X X X X X X X X X X X Sorbitan Stearate/Sucrose Cocoate X X X 3% -7% Sucrose Ldura[e 3%-7% X -X X Poloxamer 407 3%-7% -X -X X Polyoxyethylene(20)Sorbate X X X Monoleate 3%-5% Primary emulsion WhO 50% X X X X X X X X X X X X Thickeners (water swellable X X X X X X X X X X X X polymers) 0.3%-1% --Water deionized Os 100% X X X X X X X X X X X X Perfumeoils 0.1%-0.4% X X X X X X X X X X X X -59 -Multiple emulsions Ingredients i 2 3 4 5 6 7 8 9 10 11 12 UV-absorber according to the X X X X X X X X X X X X invention 0,1%-20% UV-absorber as described in table X X X X X X X X X X X X 2-4 0%-30% O1/W/02 emulsions Ingredients.i. 4 1 Primary emulsion 011W PEG-60 Hydrogenated Castor Oil 25% X X X X Steareth-25 25% X X X X Oil phase 75% Fatty acid esters x X Natural and synthetic Triglycerides X X Hydrocarbon oils X X Silicone oils X X Preservatives 0.3% -0.8% X X X X X X X X Water deionized Qs 100% X X X X X X X X Non ionic multifunctional W/O emulsifier 2%-X X X X X X X X 5% Waxesl%-5% X X X X X X X X Oil phase 20%-30% X X X X X X X X Silicone oils PrimaryemulsionOl/W 15% X X X X X X X X Electrolytes (NaCI, Mg504) 0.1%-0.5% X X X X X X X X Water deionized Qs 100% X X X X X X X X Perfume oils 0.1%-0.4% X X X X X X X X UV-absorber according to the invention X X X X X X X X 0,1%-20% UV-absorber as described in table 2-4 X X X X X X X X 0%-30% Microemulsions Ingredients.1 4 7 PEG-8 Caprylic/Capric Glycerides 10%-25% X --X X --X X PPG-5-ceteth-20 i0%-25% X X X X X Polyglyceryl-6 Isostearate 5%-15% X X. Polyglyceryl-3 Diisostearate 5%-15% X -X ----Polyglyceryl-6 Dioleate 5%-15% X X PPG-10 Cetyl Ether 5%-15% X X Ethoxydiglycol 5%-15% X X Oilphase 10%-80% X X X X X X X X X X sostearylBenzoate... X X X X X)< X X X Isostearyl Isostearate X X X XIX X X X X X -60 -Microemulsjons Ingredients 1 2 3 4 5 6 7 8 9 10 PEG-7 Glyceryl Cocoate X X X X X X X X X X Cyclomethicone X X X X X X X X X X Polyalcohols/Humectants 1%-10% X X X X X X X X X X Preservatives 0.3 -0. 8% X X X X X X X X X X Perfumeoils0.1%-0.4% X X X X X X X X X X Water Deioniz. qs 100% X X X X X X X X X X UV-absorber according to the invention 0,1%-X X X X X X X X X X 20% UV-absorber as described in table 2-4 X X X X X X X X X X 0%-30% 01W Spray emulsions Ingredients 1 2 3 4 Alkyl Phosphates 0.1%-5% X X X Glucosidic derivatives 0.1%-5% X X Solubilisants Ethoxylated Glyceryl ethers 0.1%-1% X X Polysorbates 0.1%1% X X Ethoxylated Oleyl ethers 0.1%-1% X X PVPIVA Coplymer 1%-10% X X X PVMIMACopolymer 1%-10% X X X Oilphase 5%-20% X X X X X X Natural oils (Meadowfoam, Jojoba, Macadamia...) X X X X X X Fatty acids esters x x x x x x Mineral oils X X X X X X Silicone oils x X X X X X Alcohol 0%-50% X X X X X X Thickeners 0.1%-0.5% X X X X X X Polyacrylates X X X X X X Aluminium/Magnesium Silicates X X X X X X Gums x x x x x x Neutralizing agents 0%-1% X X X X X X Polyalcohols/Humectants 1%-5% X X X X X X Chelating agents (such as EDTA) 0%-0.2% X X X X X X Antioxidants 0.05%-0.2% X X X X X X Water Deioniz. qs 100% X X X X X X Perfume oiis 0. 1%-0.5% X X X X X X preservatives 0.4%-1% X X X X X X UV-absorber according to the invention 0,1% -20% X X X X X X UV-absorber as described in table 2-4 0% -30% X X X X X X -61 -G -Aqueous Ingredients 1 2 3 4 5 6 7 8 9 10 11 12 Thickeners Natural Thickener 1%-5% X X X ____ X Semi-synthetic Thickener 1 %-5% X X X X Synthetic Thickener 0.3% -1.3% X X X X ____ Neutralizing Agents 0.5% -1.5% X X X X X X X X X X X X Polyols -Humectants 5%-50% X X X X X X X X X X X X Polyquaternium series 1%-5% X X X X X X ____ PVM/MA Copolymer 1 %-5% X X X X X X Preservatives 0.5%-1% X X X X X X X X X X X X Chelating Agents (as EDTA) < X X X X X X X X X X X X 0.1% Water Deioniz. qs 100% X X X X X X X X X X X X Perfume oils 0.05%-0.4% X X X X X X X X X X X X Ethoxylated Glyceryl ethers X X X 0.1%-5% Polysorbates 0.1%-5% X X X Ethoxylated Oleyl ethers X X X X X X 0.1%-5% UV-absorber according to the X X X X X X X X X X X X invention 0, 1 %-20% UV-absorber as described in table X X X X X X X X X X X X 2-4 0%30% Oleoqels Ingredients 1 2 3 4 5 6 7 8 9 10 Hydrogenated Lecithin 1%-1O% X Silica Dimethyl Silylate 1%-10% X X Silica 1%-5% X X C24.28 Alkyl Dimethicone 1 %-5% X X Aluminium or Magnesium Stearate 1 %-5% X X Polyols -Humectants 5%-70% X X X X X X X X X X Oil phase 20% -90% Dicaprylyl Ether X X X Phenyl Trimethicone X X Hydrogenated PoIyisohiitne X Isopropyl Isostearate X X Oleogel basis (Mineral oil and hydrogenated X X Butylene/Ethylene or Ethylene/Propylene Styrene Copolymer) Silicone wax 1%-10% X X X X X X X X X X Dimethiconol Behenate X X X X X X X X X X Dimethiconol Stearate X X X X X X X X X X Perfume oils 0.1%-0.5% X X X X XX X X X X -62 -Oleogels Ingredients.1. . 4 Z. 1Q Antioxidants 0.05%-0.2% X X X X X X X X X X UV-absorber according to the invention 0,1%-X X X X X X X X X X 20% UV-absorber as described in table 2-4 X X X X X X X X X X 0%-30%) Light/dry cosmetic oils Ingredients.1 4 Hydrocarbon oils 30%-70% X X Fatty acid esters branched or not 10%-50% X X Silicones/Siloxanes 0% -10% X -X Perfluorinated oils and Perfluoroethers 0%-10% -X -X Viscosifying agents 0%-10% X X X X Esters of long chain acids and alcohols 0% -2% X X X X Antioxidants 0.1%-1% X X X X Solubilisants/dispersing agents 0%-5% X X X X Perfume oils 0.1%-0.5% X X X X UV-absorber according to the invention 0,1 %-20%. X X X X UV-absorber as described in table 2-4 0%-30% X X X X Foaming/mousse products Ingredients 1 SD Alcohol 40 0%-8% X Propellant 8%-15% X Nonionic Emulsifier/Surfactant 0.5% -3% X Corrosion Inhibitor 0% -1% X Per-fun-ieoils 0.1%-0.5% X Preservatives 0.1%-1% X Miscellaneous 0%-1% X UV-absorber according to the invention 0,1%-20%. X UV-absorber as described in table 2-4 0%-30% X Stick products Ingredients Vv'axes 1 5%-30% X Natural and silicone oils 20%-75% X Lanoline derivatives 5%->50% X Esters of lanolin x Acetylated lanolin x Lanolin oil x Colorants and pigments 10% -15% x Antioxidants 0.1% -0.8% X -63 -Stick products Ingredients Perfumeoils 0.1%-2% X Preservatives 0.1%-0.7% x UV-absorber according to the invention 0,1 %-20% X UV-absorber as described in table 2-4 0%-30% X Liquid and compact Ingrecflents 1 Liquid foundation Powder phase 10%-15% X ____ Oil phase 30% -40%; 75%(only for anhydrous form) X Thickener/suspending agentsl %-5% X _____ Film forming polymers 1 %-2% X _____ Antioxidants 0.1% -1% X _____ Perfumeoils 0.1%-0.5% X ____ Preservatives 0.1%-0.8% X _____ Water deionized Qs 100% X _____ Compact powder Powder phase 15%-50% ____ X Oilphase 15%-50% X Polyol phase 5% -15% ____ X Antioxidants 01%-1% X Perfume oils 0.1% -0.5% ____ X Preservatives 0.1%-0.8% X For the two product forms UV-absorber according to the invention 0,1 %-20% X X UV-absorber as described in table 2-4 0%-30% X X The cosmetic preparation according to the invention is distinguished by excellent protection of human skin against the damaging effect of sunlight.

-64 -

Examples

A. Preparation Examples Example A-i: Preparation of the compound of formula (101) 1 4.09g of 2-nitroaniline are suspended in 1 00m1 water. The suspension is treated with 25m1 of concentrated hydrochloric acid and cooled to 5-10 C. After dropwise addition of a mixture of 6.9g sodium nitrite in 1 5m1 water the resulting mixture is stirred for 2h at 0-5 C. This mixture is then dropped into a solution of i7.7g 3diethylaminophenol and 5m1 concentrated hydrochloric acid in 200m1 water at 0-3 C.

The resulting suspension is stirred at 0-i C for 1 h. The intermediate is filtered off, washed with water and suspended in 1 OOml water. At 60 C the suspension is treated with 60m1 NaOH (25 %) and i9.35g zinc dust and subsequently stirred at 80 C for 4h.

The reaction mixture is cooled down to room temperature and the byproducts are filtered off.

The resulting solution is treated with 200g ice and the pH of the resulting suspension is adjusted to 8 by the addition of concentrated hydrochloric acid.

A beige product precipitates which is isolated by filtration and purified by column chromatography (eluent: toluene/ethyl acetate: 95:5).

UV-spectrum: (ethanol) = 385 nm, F = 29591.

Example A-2: Preparation of the compound of formula (102) N-\ 2.56g of hexanoyl chloride are added dropwise to a mixture of 3.89g 5-amino-2-(2H-benzo-triazol-2-yl)-phenol (prepared as described for example in the EP 0 751 134 Al) with lOmi pyridine. The resulting reaction mixture is stirred at 100 C for 3h. After cooling down to room temperature the crude product is filtered off and washed 4x with 0.1 molar HCI solution and then 4x with water.

-65 -The resulting crystals are recrystallized 2x from isopropanol and 2x from toluene yielding pale beige crystals.

UV-spectrum X (ethanol) = 346 nm, E = 29933.

B. Application Examples Example B-i: Sun-protection cream, type 01W INCI name %wlw (as used) Part A Polyglyceryl-3 methylglucose distearate 2.0 Decyl oleate 5.7 Isopropyl palmitate 5.8 Caprylic/capric triglyceride 6.5 UV absorber according to this invention 2.0 Ethylhexyl methoxycinnamate 5.0 Cetyl alcohol 0.7 Part B Glycerol 3.0 Carbomer 0.3 Water q.s.to 100 Part C Phenoxyethanol (and) methylparaben (and) ethylparaben (and) 0.5 butylparaben (and) propylparaben (and) isobutylparaben Part D Methylene bis-benzotriazolyl tetramethylbutylphenol (and) aqua 8.0 (and) decyl glucoside (and) propylene glycol (and) xanthan gum Water 20.0 Part E Water (and) sodium hydroxide q.s.

Fragrance q.s.

Preparation procedure Part A and part B arc hctcd separately to 75 C. Part A is poured into part B while stir ring.

The mixture is homogenised with an Ultra Turrax at ii 000 rpm for 1 5sec. The mixture is cooled to 60 C and part C and part D are incorporated. The mixture is homogenised again for a short time (5 sec.Ii 1 000 rpm) and further cooled, with moderate stirring. At room temperature, the pH is adjusted with sodium hydroxide solution to between 5.5 and 6 0.

Finally, fragrance is added.

Claims

-66 -Claims 1. Use of 2-(2'-Hydroxy-4'-aminophenyl)benzotrjazole

derivatives of formula

HO R2

(1) (Rl)flt,JN_\I/__N, wherein R1 and R4 independently of each other are hydrogen; C1-C28alkyl; C1-C28alkoxy; C2-C28al- kenyl; C2-C28alkinyl; C3-C12cycloalkyl; C3-C12cycloalkenyl; C7-C28 aralkyl; C1-C20hetero- alkyl; C3-C12cycloheteroalkyl; or C5-C16heteroaralkyl; and wherein C1-C28alkyl, C1-C28al-koxy, C2-C28alkenyl and C2-C28alkinyl are unsubstituted or may be substituted by at least one C1-C5alkyl, C1-C5alkoxy or hydroxy; R2 and R3 independently of each other are hydrogen; C1-C28alkyl; C2-C28 alkenyl; C2-C22alki- nyl; C3-C12cycloalkyf; C3-C12cycloalkenyl; C7-C28 aralkyl; C1-C20 heteroalkyl; C3-C12cyclo-heteroalkyl; C5-C16heteroaralkyl; and wherein C1-C28alkyl, C1-C28alkoxy, C2-C28alkenyl and C2-C28alkinyl are unsubstituted or may be substituted by at least one C1-C5alkyl, C1-C5alkoxy or hydroxy; or CO-R5; or R2 and R3 together with the linking nitrogen form a 5-to 7-membered, monocyclic, carbo-cyclic or heterocyclic ring; R5 is C1-C28alkyl; C2-C28alkenyl; C2-C28alkinyl; C3-C12cycloalkyl; C3-C12cycloalkenyl; C7-C20aralkyl; C1-C20 heteroalkyl; C3-C12 cycloheteroa lkyl; C1-Calkoxycarbonyl-C1-C5alkyl; or C-C16heteroaralkyl; and n isl,2,3or4; for protecting human and animal hair and skin from harmful effects of UV radiation.

2. Use according to claim 1, wherein in formula (1) R1 is hydrogen; C1-C28alkyl; or C1-C28alkoxy. .1

3. Use according to claim 2, wherein in formula (1) R1 is hydrogen, C1-C5alkyl; or C1-C5alkoxy.

4. Use according to claim 2 or 3, wherein in formula (1) R1 is hydrogen; methyl, tert. butyl; or methoxy; -67 - 5. Use according to any of claims 1 to 4, wherein R4 is hydrogen.

6. Use according to any of claims 1 to 5, wherein R is hydrogen; C1-C28alkyl; C2-C28 alkenyl; and wherein C1-C28alkyl and C-C28aIkenyl are unsubstituted or may be substituted by at least one C1-C5alkyl, C1-C5alkoxy or hydroxy; or CO-R5; and R is C1-C28aIkyl; C1-C5alkoxycarbonyI-C1-CaIkyI; or C3-Ci2cycloalkyl.

7. Use according to claim 6, wherein in formula (1) R2 is hydrogen; C1-C10alkyl; C2-C10 alkenyl; and wherein C2-C1oalkenyl is unsubstituted or may be substituted by C1-C5alkoxy; or CO-R5; and R5 is C1-C10alkyI; C1-C5alkoxycarbonyl-C1-C5aIkyI; or C3-C12cycloalkyl.

8. Use according to claim 6 or 7, wherein in formula (1) R2 is hydrogen; C1-C5alkyl; *CiC4aIkyIeneHCCH..O..C1.C5aIkyI; or CO-R5; R5 is C1-C10aIkyl; -CH2-CH2(CO)-O-C2H5; or cyclohexyl.

9. Use according to any of claims 6 to 8, wherein in formula (1) R5 is isooctyl.

10. Use according to any of claims 1 to 9, wherein in formula (1) R3 is hydrogen; or *-(CO)CH3.

11. Use according to any of claims 6 to 8, wherein R2 and R3 have the same meaning.

12. Use according to claim 11, wherein R2 anci R3 are G1-C5aIKyl.

13 Use according to any of claims 1 to 5, wherein in formula (1) -68 -R2 and R3 together with the linking nitrogen form the heterocyclic ring radical of formula (la) 14. Use according to any of claims 1 to 13, wherein in formula (1) R is hydrogen; C1-C5alkyI; or C1-C5alkoxy; R4 is hydrogen; or C1-C5alkyl; R2 is hydrogen; C1-C1oalkyl; C2-C10 alkenyl; and wherein C2-C10alkenyl is unsubstituted or may be substituted by C1-C5alkoxy; or CO-R5; R5 is C1-C10alkyl; C1-C5alkoxycarbonyl-C1-C5alkyl; or C:rCi2cycloalkyl; and R3 is hydrogen; or *-(CO)-CH3; 15. Use according to claim 14, wherein R1 is hydrogen; or C1-C5alkyl; R2 is CO-R5; R3 is hydrogen; R5 is isooctyl; and R4 is hydrogen.

16. Use of the compounds of formula (1) according to any of claims 1 to 15 as an anti-wrinkle perception modifier.

17. A cosmetic preparation comprising at least one compound of formula (1) according to any of claims 1 to 15 together with cosmetically tolerable carriers or adjuvants.