WO2004085412A2

WO2004085412A2 - Symmetrical triazine derivatives

Info

Publication number: WO2004085412A2
Application number: PCT/EP2004/050331
Authority: WO
Inventors: Thomas Ehlis; Stefan Müller; Pascal Hayoz
Original assignee: Ciba Specialty Chemicals Holding Inc.
Priority date: 2003-03-24
Filing date: 2004-03-19
Publication date: 2004-10-07
Also published as: MX267068B; EP1606270A2; ES2435512T3; EP1606270B1; WO2004085412A3; US7311897B2; BRPI0408994A; TWI331997B; AU2004224086A1; AU2004224086B2; JP4764817B2; KR101187002B1; JP2006523197A; US20040191191A1; TW200503771A; KR20050114231A; BRPI0408994B1; MXPA05010167A

Abstract

Disclosed is the use of the compounds of formula wherein A is a radical of formula (1a) or (1b) R, R1 and R5 independently from each other are hydrogen; C1-C18alkyl; or C6-C12aryl; R2, R3 and R4 independently from each other are hydrogen; or a radical of formula wherein at least one of the radicals R2, R3 and R4are a radical of formula (1c); R6, R7, R8, R9 and R10 independently from each other are hydrogen; hydroxy; C1-C18alkyl; C1-C18alkoxy;C6-C12aryl; C6-C12aryloxy; C1-C18alkylthio; carboxy; -COOM; C1-C18alkylcarboxyl; aminocarbonyl; or mono- or di-C1-C18alkylamino; M is an alkali metal ion; x is 1 or 2; and y is a number from 2 to 10; for the protection of human and animal hair and skin against the damaging effect of UV radiation. The compounds of formula (1) are high effective UV absorbers for cosmetic formulations aund can - depending on their physical properties - be used in micronized or soluble form.

Description

Symmetrical Triazine derivatives

The present invention relates to the use of specific symmetrical triazine derivatives for the protection of human and animal hair and skin against the damaging effect of UV radiation, cosmetic compositions comprising these triazine derivatives and process for preparation of these compounds.

Triazines which are symmetrically substituted by biphenyl or naphthyl are known, for example from US-A-6,225,467. They are used as for electroluminescent devices.

Surprisingly it has been found that these compounds can be used as highly effective UV absorbers for cosmetic applications.

Therefore, the present invention refers to the non-therapeutic use of the compounds of formula

(1) . wherein

A is a radical of formula (1a) λ— ; or (1b)

Ri and R₅ independently from each other are hydrogen; Cι-C₁₈alkyl; or C_β-Cι₂aryl; R₂, R₃ and R independently from each other are hydrogen; or a radical of formula

(1c) , , wherein at least one of the radicals R₂, R₃ and R, are a radical of

formula (1c); Re, Rτι Re, R₉ and R1₀ independently from each other are hydrogen; hydroxy; halogen; d-

C-|₈alkyl; Cι-Cιaalkoxy; C_β-Cι₂aryl; biphenylyl; C₆-C₁₂aryloxy; Cι-Cι_βalkylthio; carboxy;

-COOM; CrCiβ-alkylcarboxyl; amiπocarbonyi; or mono- or di-CrCiβalkylamino; Cr

Cι₀acylamino; -COOH; M is an alkali metal ion; x is 1 or 2; and

y is a number from 2 to 10; for the protection of human and animal hair and skin against the damaging effect of UV radiation.

CrCι_βalkyl according to the definition for the radicals of the compound of formula (1) are straight-chain or branched alkyl radicals like methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.butyl, tert.butyl, amyi, isoamyl αrtert.amyl, hexyl, 2-ethylhexyl, heptyl, octyl, isooc yl, nonyl, decyl, undecyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl or octadecyl.

Cι-Cιsalkyl according to the definition for the radicals of the compound of formula (1) may be substituted by methoxyethyl, ethoxypropyl, 2-ethylhexyl, hydroxyethyl, chloropropyl, N,N-di- ethylaminopropyl, cyanoethyl, phenethyl, benzyl, p-tert-butylphenethyi, p-tert-octylphenoxy- ethyl, 3-(2,4-di-tert-amylphenoxy)-propyI, ethoxycarbonylmethyl-2-(2-hydroxyethoxy)ethyl, or 2-furylethyl.

C Cieaikyl according to the definition for the radicals of the compound of formula (1) are for example methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec.butoxy, tert.butoxy, amyloxy, isoamyloxy or tert.amyloxy, hexyloxy, heptyloxy, octyloxy, isooctyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tetradecyloxy, pentadecyloxy, hexadecyloxy, heptadecyloxy or octa- decyloxy.

according to the definition for the radicals of the compound of formula (1) is for example naphthyl und preferably phenyl.

Preferably compounds of formula

are used, wherein

Ri, R5, e, R7 und R₈ are defined as in formula (1).

In formula (2) Riand R₅ are preferably hydrogen.

Most preferably compounds of formula (1) or (2) are used wherein R₆ and Re are hydrogen.

Compounds of formula (1) of preferred interest are those, wherein

R₇ is hydrogen; hydroxy; C C₅alkyl; Cι-C₅alkoxy; -COOM; -COOH; or COOR₁₀;

M is an alkali metal ion; and

R₁₀ is d-Csalkyl.

Furthermore compounds of formula

are preferably used, wherein

R11 R2, R3, Rg and R_i0 are defined as in formula (1). Preferably compounds of formula (3) are used, wherein

Ri, R∑, Re, R9 and R10 are hydrogen; or, independently from each other, C Cιβalkyl.

Examples of triazine derivatives, which are preferably used in the present invention, are the compounds of formula

(9) ; or

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 according to the present invention - depending on the substituents of the triazine aryl groups Ri, R₂ R₅, Rs, ? , Re. Rs and ι₀ in formulae (1a), 1(b) or (1c) - can be used either in the dissolved state (soluble organic filters, soiubelized organic filters) or in the micronised state (nanoscalar organic filters, particulate organic filters, UV-absorber pigments).

The triazine derivatives of formula (1) which have no alkyl substituents or only lower-alkyl substituents are characterized by a poor oil-solubility and a high melting point. They are therefore suitable in particular as UV absorbers in the micronized state.

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.

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 microcapsules wherein the UV absorbers are encapsulated (Pharmazie, 2001 (56), 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 (for example the compound of formula 6).

The cosmetic formulations or pharmaceutical compositions according to the present invention 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 together 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.

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 1. Suitable UV filter substances which can be additionally used with the UV absorbers according 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)- propane-1,3-dione; diphenylacrylates, for example 2-ethylhexyl 2-cyano-3,3-diphenylacrylate, and 3-(benzofura- nyl) 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-613893; polymeric UV absorbers, for example the benzylidene malonate derivatives described in EP-A-709080; 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)beπzylidene-boman-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'-(1 ,4- phenylenedimethine)-bis(7,7-dimethyl-2-oxo-bicyclo[2.2.1 ]heptane-1 -methanesulfonic acid) and salts, 3-(4'-suIfo)benzylidene-bornan-2-one and salts; camphorbenzalkonium methosulfate; hydroxyphenyltriaziπe 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- hydroxy]-phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine; 2,4-bis{[4-(2-ethyl-hexyloxy)-2- hydroxy]-phenyl}-6-[4-(2-methoxyethyl-carboxy])-phenylamino]-1,3,5-triazine; 2,4-bis{[4-

(tris(trimethylsilyloxy-siIylpropyloxy)-2-hydroxy]-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',1',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- Table 1. Suitable UV filter substances which can be additionally used with the UV absorbers accordino to the present invention

(1 ,1 ,3,3-tetramethylbutyl)-phenol; trianilino-s-triazine derivatives, for example 2,4,6-trianiline-(p-carbo-2'-ethyl-1 '-oxy)-1 ,3,5- triazine and the UV absorbers disclosed in US-A-5 332568, EP-A-517 104, EP-A-507691, WO 93/17002 and EP-A-570 838;

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, AI₂θ₃, Zr0₂. (surface coatings: polymethylmethacrylate, methicoπe (methylhydrogenpolysiloxane as described in CAS 9004-73-3), dimethicone, 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 15nm-35nm and the particle size in dispersion is in the range of 100nm - 300nm. aminohydroxy-benzophenone derivatives disclosed in DE 10011317, EP 1133980 and EP 1046391 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.

Preferably, the following UV filter combinations are of special interest:

- UV-fϊlter combinations (A) comprising

(ai) at least one symmetrical triazine derivatives of formula (1) and

(a₂) at least one aminobenzophenone derivative of formula

wherein

Ri and R₂ independently from each other are; Ci-Czoalkyl; C₂-C2oalkenyl; C₃-

Ciocycloalkyl; C -C₁₀cycloalkenyl; or Ri and R₂ together with the linking nitrogen atom form a 5- or 6-membered heterocyclic ring; ni is a number from 1 to 4; when n_! = 1 ,

R₃ is a saturated or unsaturated heterocyclic radical; hydroxy-d-Cβalkyl; cyclohexyl, M optionally substituted with one or more d-Csalkyl; phenyl optionally substituted with a heterocyclic radical, aminαcarbαnyl or d-Csalkylcarboxy;

R₃ is an alkylene-, cycloalkylene, alkenylene or phenylene radical which is optionally substituted by a carbonyl- or carboxy group; a radical of formula — CH_J-C≡C-CHJ— « or R₃ together with A forms a bivalent radical of the

formula (1a) — A ^ J — ; wherein

n₂ is a number from 1 to 3;

R₃ is an alkanetriyl radical; wenn n^ is 4,

R₃ is an alkanetetrayl radical;

A is -0-; or-N(R₅)-; and

R₅ is hydrogen; d-Csalkyl; or hydroxy-Ci-Csalkyl.

Most preferred are UV-filter combinations (A1) comprising (a₃) at least one compound of formula (6) and/or (9); and

(a₄) the compound of formula

- UV-filter combinations (B) comprising

(bi) at least one symmetrical triazine derivatives of formula (1); and

(b₂) at least one aminobenzophenone derivative of the formula

wherein

R¹and R² independently from each other is hydrogen, d-doalkyl; C₂-C₂₀alkenyl; C₃-

Ciocycloalkenyl; wherein R and R² may form a five- or six-membered ring; R³ and R⁴ independently from each other is d-doalkyl; C₂-C₂₀alkenyl; C₃-

Ciocycloalkenyl, d-doalkoxy, CrC₂₀alkoxycarbonyl, d-Czoalkylamino, di(C

C₂₀alkyl)amino, optionally substituted aryi or Heteroaryl; X is hydrogen; COOR⁵; or CONR^eR^7: R⁶, R^β, R⁷ independently from each other are hydrogen, Cι-C₂₀alkyl; C₂-C₂₀alkenyl; C₃-

Ciocycloalkyl; C₃-Cι₀cycloalkenyl; (Y-0)_q-Z; optionally substituted aryl; Y is -(CH₂)₂-; -(CH₂)₃-; -(CH₂)₄-; -CH(CH₃)-CH₂-; 2. is -CH₂-CH₃; -CH -CH -Cri₃; -CH₂-CH -CH₂-Cπ₃; CH(CH₃)-Cπ₃; m is O; 1; 2; or 3; n is 0; 1; 2; 3; or 4; and q is a number from 1 to 20.

Most preferred are UV-filter combinations (B1) comprising (b₃) the compound of formula (6) and/or (9); and

(b ) the compound of formula

- UV-filter combinations (C) comprising

(ci) at least one symmetrical triazine derivatives of formula (1); and

(c₂) at least one benzotriazole derivative of formula

T₂ is Cι-Cιoalkyl or phenyl-substituted d-dalkyl;

Most preferred are UV-filter combinations (C1) comprising (c₃) the compound of formula (6) and/or (9); and

(c ) the micronized compound of formula

- UV-filter combinations (D) comprising

(di) at least one symmetrical triazine derivatives of formula (1); and

(d₂) at least one compound of formula

in which

Ri and R₂, independently of one another, are C₃-C₁₈alkyl; C₂-C₁₈alkenyl; a radical of the formula -CH₂-CH(-OH)-CH₂-0-T₁ ; or

Ri and R₂ are a radical of the formula (4a) — ijj-Si— o- -Si-R,,

R<,

Rι₂ is a direct bond; a straight-chain or branched Cι-C₄alkylene radical or a radical of the formula -C H- or -c_m H— o- ;

Ri3, Ri4 and R15, independently of one another, are d-Cι₈alkyl; Cι-Cι₈alkoxy or a radical

of the formula — O-Si — R« ;

R_1β is d-C₆alkyl; mi and m₃, independently of one another, are 1 to 4;

Pi is 0; or a number from 1 to 5;

Ai is a radical of the formula

(1b)

\ N (1d)

R₃ is hydrogen; d-d₀alkyl, -(CH₂CHR₅-θ) -R₄ ; or a radical of the formula ⁿ1

-CH₂-CH(-OH)-CH₂-0-T₁ ; Rt is hydrogen; M; d-Csalkyl; or a radical of the formula -(CH₂)_m-0-T₁ ;

R₅ is hydrogen; or methyl;

T1 is hydrogen; or d-C₈alkyl;

Q1 Cι-Cι₈alkyl;

M is a metal cation; m₂ is 1 to 4; and

Most preferred are UV-filter combinations (D1) comprising (d₃) the compound of formula (6) and/or (9); and (d₄) the compound of

formula

- UV-filter combinations (E) comprising

(ei) at least one symmetrical triazine derivatives of formula (1) and

(e₂) at least one hydroxyphenyltriazine compound of formula

R-i, R₂ and R₃ are each independently of the others Cι-Cι₈alkyl; d-doalkenyl; or phenyl- Cι-C₄alkyl; and R₄ is hydrogen; or d-Csalkyl.

Most preferred are UV-filter combinations (E1) comprising (e₃) the compound of formula (6) and/or (9); and

(e₄) the compound of formula

- UV-filter combinations (F) comprising

( ) at least one symmetrical triazine derivatives of formula (1); and

(f₂) at least one dibenzoylmethane derivative of

formula

Most preferred are UV-filter combinations (F1) comprising

(f₃) the compound of formula (6) and/or (9); and

(f ) 1-[4-(1,1-dimethyiethyl)phenyl]-3-(4-methoxyphenyl)propane-1,3-dione (Avobenzone);

- UV-filter combinations (G) comprising

(gi) at least one symmetrical triazine derivative of formula (1), preferably the compound of formula (6) and/or (9); and (g₂) disodium phenyl dibenzimidazole tetrasulfonate (Heliopan AP).

• UV-filter combinations (H) comprising (hi) at least one symmetrical triazine derivatives of formula (1); and (h₂) benzoxazole-substituted triazines of formula

Ri, R₂ and R₃ independently from each other are branched or unbranched d-Csalkyl.

Most preferred are UV-filter combinations comprising (h₃) the compound of formula (6) and/or (9); and

(h₄) 1 ,3,5-triazine-2,4,6-triamine, N,N'-bis[4-[5-(1,1-dimethylpropyl)-2-benzoxazolyl]phenyl]- N"-(2-ethylhexyi); (CAS No. 288254-16-0).

Furthermore, UV filter combination (H2) comprising (h₅) the compound of formula (6) or (9); and (h_β) at least one of the compound of formula (h₂1), wherein (h_β1) Ri and R₂ are tertamyl; and R₃ is tert.butyl; or wherein (h^) Ri and R₂ are tert.butyl and R₃ is tert.octyl; or wherein (he₃) Ri and R₂ are tert.butyl; and R₃ is 2-ethylhexyl; or wherein (h_M) Ri and R₂ are tert.amyl; and R₃ is 2-ethylhexyl; are of preferred interest.

- UV-filter combinations (I) comprising

(ii) at least one symmetrical triazine derivatives of formula (1 ), preferably the compound of formula (6) and/or (9); and (i₂) 2-(2H-benzotriazol-2-yl)-4-methyI-6-[2-methyI-3-[1 ,3,3,3-tetramethyM -[(trimethyl- silyl)oxy]disiloxanyl]propyI]-; (CAS-No. 155633-54-8; Drometrizole Trisiloxaπe;

Mexoryl XL);

- UV-filter combinations (K) comprising

(ki) at least one symmetrical triazine derivatives of formula (1), preferably the compound of formula (6) and/or (9); and (k₂) siloxanes and silicones, di-Me, 1-[[4-[3-ethoxy-2-(ethoxycarbonyl)-3-oxo-1-propenyl]p- henoxy]methyl]ethenyl Me, 3-[4-[3-ethoxy-2-(ethoxycarbonyl)-3-oxo-1 -propenyl]-

phenoxy]-1-propenyl Me, Me hydrogen (Dimethicodiethylbenzalmalonate ; CAS-No. 207574-74-1);

- UV-filter combinations (L) comprising

(I-i) at least one symmetrical triazine derivatives of formula (1), preferably the compound of formula (6) and/or (9); and (l₂) (+/-)-1 ,7,7-trimethyl-3-[(4-methylphenyl)methylene]bicyclo[2.2.1 ]heptan-2-one; p-methyl benzylidene camphor;

- UV-filter combinations (M) comprising

(mι)at least one symmetrical triazine derivatives of formula (1), preferably the compound of formula (6) and/or (9); and (m₂)α-(2-oxoborn-3-ylidene)toluene-4-sulphonic acid and its salts (Mexoryl SL);

- UV-filter combinations (N) comprising

(ni) at least one symmetrical triazine derivatives of formula (1), preferably the compound of formula (6) and/or (9); and (n₂) methyl N,N,N-trimethyl-4-[(4,7,7-trimethyl-3-oxobicyclo[2,2,1]hept-2-ylidene)methyl]- anilinium sulphate (Mexoryl SO);

- UV-filter combinations (O) comprising

(o^ at least one symmetrical triazine derivatives of fonnula (1), preferably the compound of formula (6) and/or (9); and (o₂) 2-ethylhexyl 2-cyano,3,3-diphenylacrylate (Octocrylene);

- UV-filter combinations (P) comprising

(pi) at least one symmetrical triazine derivatives of formula (1), preferably the micronized compound of formula (6) and/or (9); and (p₂) 2- ethylhexyl 4-methoxycinnamate (octyl methoxy cinnamate);

- UV-filter combinations (Q) comprising

(qi) at least one symmetrical triazine derivative of formula (1), preferably the compound of formula (6) and/or (9); and (q₂) benzoic acid, 4,4',4"-(1,3,5-triazine-2,4,6-triyltriimino)tris-,tris(2-ethylhexyl)ester; 2,4,6- TrianiIino-(p-carbo-2'-ethylhexyl-1 '-oxi)-1 ,3,5-triazine (Octyl Triazone);

- UV-filter combinations (R) comprising

(r-i) at least one symmetrical triazine derivative of formula (1), preferably the compound of formula (6) and/or (9); and (r₂) 2-phenyI-1 H- benzimidazole-5-sulphonic acid (Phenylbenzimidazolsulfonic Acid);

- UV-filter combinations (S) comprising

(si) at least one symmetrical triazine derivative of formula (1), preferably the compound of formula (6) and/or (9); and (s₂) benzoic acid,4,4'-[[6-[[4-[[(1,1-dimethylethyl)amino]carbonyl]phenyl]amino]1 ,3,5-triazine-

2,4-diyl]diimino]bis-,bis(2-ethylhexyl)ester; diethylhexyl butamido triazone

(Uvasorb HEB).

In the compositions (A) - (S) the compound of formula (1), (6) and (9) respectively are preferably present in the composition in micronized form.

The compounds of formula (1) may also be used as as an anti-wrinkle perception modifier (see Example 29). This is a futher object of the present invention.

The compounds of formula (1) can be prepared according to known methods as described for example in US-A-6,225,467.

Furthermore, the compounds of formula (1) may be obtained in a Grignard reaction starting from the corresponding halogen aromatic compounds and a trihalogen triazine.

The cyclotrimerisation of aromatc nitrilic compounds is a further well method for the preparation of symmetrical triazine derivatives of formula (1) achieving minor yields.

Surprisingly a simple method for the preparation of the compounds of formula (1) was found. The reaction of trihalogen-1 ,3,5-triazines with aromatic compounds in a Friedel-Crafts- reaction delivers high yields of symmetrical triazine derivatives. Suitable aromatic compounds are:

wherein R₁-R₁₀ are defined as in formula (1)

According to this method the compound of formula (101) can be prepared according to the following reaction scheme

Cyanuπc chloride is preferably used as trιhalogen-1 ,3,5-tπazιne

The reaction temperature is from -10 to 250°C, preferably from 5-150°C, most preferably from 70-130°C

Classes of compounds that can be used as catalyst are listed in the table below

Preferred catalysts are (as single compounds or in combination AICI₃, AIBr₃, BF₃, BCl₃, BBr₃, BeCI₂, CdCI₂, ZnCI₂, GaCI₃, GaBr₃, FeCI₃, SbCI₃, BιCI₃, TιCI₄, ZrCI₄, SnCI₄, UCI₄ and SbCI₅

Advantageously the compounds listed in the table above are used in stoichlometric amounts or in excess.

As co-catalysts are used: alcohols, water, HCl, HF, H₂S0₄ , H₃P0₄ , RCOOH (organic acids), sulfonic acids like for example p-toluene sulfonic acid.

The co-catalysts can also be used in stoichiometric amounts or in excess.

Preferably gaseus HCl is used as co-catalyst.

As catalysts, co-catalysts or promotors compounds or classes of compounds are used: Cations forming compounds: preferred are alkyl- and acyl-halogenides as well as compounds comprising oxygen-, sulfur-, or halogen-donor atoms.

- Adducts: ZnCI₂-AICI₃ , SnCI₄ , AICI₃ -ketones, AICI₃-Pyridine, AICI₃-RN0₂ , AIBr₃-RN0₂ , GaCI₃-RN0₂ , SbF₆, BF₃-0Et₂, BF₃-C₆H₅OH; AICI₃-Sulfolane. (R-N0₂: nitroaliphatic and nitroaromatic compounds).

Suitable solvents are: aliphatic hydrocarbons, aromatic hydrocarbons, sulfur-hydrocarbons, halogenaromatic compounds, halogenaliphatic compounds, alyl-aryl ethers, alkyl-alkyl ethers, sulfolane, nitroaromatic compounds and nitroaliphatic compounds.

Mostly preferred are: chlorbenzene, 1 ,2-dichlorbenzene, 1 ,4-dichlorbenzene, nitrobenzene, nitromethane, tetrachlormethane.

Furthermore, the reaction can be carried out in ionic fluids like for example 1-butylpyri- diniume chloride - aluminum(lll) chloride and 1 -butyl-3-methylimidazolium chloride - alu- minum(lll) chloride (s. 1-ethyl-3-methylimidazolium halogenoaluminate ionic liquids as solvents for Friedel-Crafts acylation reactions of ferrocene. Journal of the Chemical Society, Dalton Transactions: Inorganic Chemistry 1999 (1), 63). Surprisingly it was found that the reaction can be carried out in absence of a solvent like 1 ,2- dichlorobenzene. The reaction runs particularly well when gaseous HCl is discharged into the reaction mixture.

This preparation process has specific significance since the use of halogenated aromatic solvents causes residues of solvents which are only difficult to remove in the end product. These kinds of solvents are inappropriate for cosmetic applications.

The cosmetic or pharmaceutical preparations may be, for example, creams, gels, lotions, alcoholic and aqueous/alcoholic solutions, emulsions, wax/fat compositions, stick preparations, 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, 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, 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 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 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.

The cosmetic or pharmaceutical compositions/preparations according to the invention may also contain one or one more additional compounds like fatty alcohols esters of fatty acids, natural or synthetic triglycerides including glyceryl esters and derivatives, pearlescent waxes: hydrocarbon oils, silicones or siloxanes (organosubstituted polysiloxanes) fluorinated or per- fluorinated oilsemuisifiers, super-fatting agents, surfactants, consistency regulators/thickeners and rheology modifiers, polymers, biogenic active ingredients, deodorising active ingredients anti-dandruff agents, antioxidants, hydrotropic agents, preservatives and bacteria-inhibiting agents, perfume oils, colourants, polymeric beads or hollow spheres as SPF enhancers.

Cosmetic or pharmaceutical formulations are contained in a wide variety of cosmetic preparations. There come into consideration, for βssample, especially the following preparations like skin-care preparations, bath preparations, cosmetic personal care preparations, foot-care preparations,; light-protective preparations, skin-tanning preparations, depigmenting preparations, insect-repellents, deodorants, antiperspirants, preparations for cleansing and caring for blemished skin, hair-removal preparations in chemical form (depilation), shaving preparations, fragrance preparations or cosmetic hair-treatment preparations.

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

Of special importance as cosmetic preparations for the skin are light-protective preparations, such as sun milks, lotions, creams, oils, sunblocks 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.

Of special importance as cosmetic preparations for the hair are the above-mentioned preparations 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.

The cosmetic preparation according to the invention is distinguished by excellent protection of human skin against the damaging effect of sunlight. Examples

Preparation of UV absorbers

Example 1: Preparation of the compound of formula (101)

Cyanuric chloride (36.9 g, 0.20 mol) is dissolved in 1 ,2-dichlorobenzene (500 ml). Aluminum chloride (96.0 g, 0.72 mol) is added and the reaction mixture is heated up to 140°C. Biphenyl (111.0 g, 0.72 mol), dissolved in 200 ml 1 ,2-dichlorobenzene, is added slowly dropwise and the temperature is maintained at 140-145°C for 1 to 4 hours.

The reaction mixture is cooled down to about 60°C and added to a mixture of 150ml cone. HCl and 350g ice. After phase separation at about 110°C the dichloro benzene phase is removed, stirred with Na₂C0₃ and filtered hot at 100 - 110°C. The desired compound recrystallizes from the filtrate.

For purification the compound is recrystallized from dichiorobenzene and dioxane.

¹³C NMR (90 MHz, CDCI₃, TMS):

Example 2:

Biphenyl (200.0 g, 1.28 mol) is submitted and melted at 70-75°C. Cyanuric chloride (9.2 g, 0.05 mol) is added and hydrogen chloride is discharged for 10 minutes. Aluminum chloride (20.0 g, 0.15 mol) is added within 40 minutes in 5 equal portions, whereby hydrogen chloride is discharged again after the first two additions. After termination of the reaction 95 per cent ethanol (200 ml) is added dropwise slowly. The reaction mixture is heated up for 1h under reflux. Finally, acetone (400 ml) is added and agitated for 1h, cooled down to room temperature and the failed product is filterd under suction.

Yield of tris(biphenyl)-1 ,3,5-triazin (formula 101): approx. 65%

Example 3: Preparation of the compound of formula (102)

According to the procedure described in Example 1 the compound of formula (102) is obtained, if naphthalene is used instead of biphenyl.

Example 4: Preparation of the compound of formula (103)

Reaction Scheme:

Example 4a:

0.5g 2,4,6-Tris-(4-Bromophenyl)-1,3,5-triazin (CAS Nr. 30363-03-2) and 0.816g of 4-bi- phenylboronic acid are added to 10ml of toluene under argon. 2.238g of Cesium carbonate are dissolved in 3.5ml water and added to the reaction mixture. After the addition of 0.03 equivalents of a palladium(ll) catalyst, the reaction mixture is heated under reflux for 4h. The reaction mixture is cooled down to room temperature and then filtered. The filter cake is dissolved in hot DMF, filtered and under cooling the desired product crystallized out. The white fine needles have a melting point of 360°C and the ¹H-NM confirmed the structure.

NMR-Data: 1H-NMR (340 MHz, CDCI3): δ= 8.83 (d, 6H), 7.82 (d, 6H), 7.75 (d, 6H), 7.67 (d, 6H), 7.62-7.60 (m, 6H), 7.44-7.40 (m, 6H), 7.34-7.30 ppm (m, 3H). Instead of the bromide, also the chloride, iodide or tosylate might be used as starting material. Bromide is preferred.

Example 4b:

The compound of formula (103) can be synthesized alternatively via the following pathway:

X = Cl, Br, I, O-Tosyl (X = preferably Br)

Example 4c:

Another pathway for the preparation of the compound of formula (103) is as follows:

Example 4d:

According to the procedure described in Example 1 the compound of formula (103) is obtained, if p-terphenyl is used instead of biphenyl.

Example 5: Preparation of the compound of formula (104)

According to the procedure described in Example 1 the compound of formula (104) is obtained, if p,p-quarterphenyl is used instead of biphenyl as starting compound.

Example 6: Preparation of a micronized UV absorber

100 parts of the compound of formula (101), (102), (103) or (104) respectively are milled together with zirconium silicate bells (diameter: 0,1 to 4 mm) as grinding aids, a dispersing agent (15 parts of C₈-C₁₆polyglucoside) and water (85 parts) in a ball mill to a mean particle size of d₅o = 130nm.

With this method a micropigment dispersion of a UV absorber is obtained.

Example 7: Preparation of a micronized UV absorber

100 parts of the compound of formula (101), (102), (103) or (104) respectively are milled together with zirconium silicate bells (diameter: 0,1 to 4 mm) as grinding aids, a dispersing agent (15 parts Cι₂gyceride-PEG10) and water (85 parts) in a ball mill to a mean particle size ofdso ³ 130nm.

With this method a micropigment dispersion of a UV absorber is obtained. Application Examples

Manufacturing instruction for Examples 8a-8d:

Part A and part B are heated separately to 75°C. Part A is poured into part B under continuous stirring. Immediately after the emulsification, cyclopentasiloxane and PEG-12 Di-

methicone from part D are incorporated into the mixture. Afterwards the mixture is homogenized with an Ultra Turrax at 11 000 rpm for 30 sec. After cooling down to 65°C Sodium Acrylates Copolymer (and) Paraffinium Liquidum (and) PPG-1 Trideceth-6 are incorporated. Part C is added at a temperature < 50°C. At a temperature < 35°C Tocopheryl Acetate is incorporated and subsequently the pH is adjusted with Water (and) Citric Acid. At room temperature part E is added.

Manufacturing instruction:

Part A by is prepared by incorporating all ingredients, then stirred under moderate speed and heated to 75"C. Part B s prepared and heated to 75°C. At this temperature part B is poured into part A under progressive stirring speed. Then the mixture is homogenized (30sec, 15000 rpm ) . At a temperature < 55°C the ingredients of part C are incorporated. The mixture is cooled down under moderate stirring, then the pH is checked and adjusted with triethanolamine.

Example 10: Sun Protection Emulsion

Manufacturing instruction:

Part A is prepared by incorporating all ingredients, then stirred under moderate speed and heated to 75°C. Part B is prepared and heated to 75°C. At this temperature, part B is poured into part A under progressive stirring speed. Below 65°C the ingredients of part D are added separately. After cooling down under moderate stirring to 55°C part C is added. The pH is then checked and adjusted with sodium hydroxide. The mixture is homogenized for 30 sec at

16000rpm.

Manufacturing instruction:

Part A is prepared by incorporating all ingredients, then stirred under moderate speed and heated to 75°C. Part C is prepared and heated to 75°C. Part C is poured into the part A under moderate stirring. Immediately after the emulsification part B is added, then neutralized with a part of the triethanolamine. The mixture is homogenized for 30 sec. After cooling down under moderate stirring Cyclopentasiloxane (and) Dimethiconol are added. Below 35°C the pH is checked and adjusted with triethanolamine.

Manufacturing instruction

Part A and part B are heated up to 80°C. Part A is blended into part B under stirring and homogenized with an UltraTurrax at 11 000 rpm for 30 sec. Part C is heated to 60°C and added slowly to the emulsion. After cooling down to 40°C part D is incorporated at room temperature and part E is added.

Example 13: Daily Care Lotion

Manufacturing instruction

Part A and B are heated to 75°C. Part A is added into part B under continuous stirring and homogenized with 11000 rpm for 1 minute. After cooling down to 50°C part C is added under continuous stirring. After cooling further down to 30°C part D is added. Afterwards the pH is adjusted between 6.00 - 6.50.

Example 14: Daily Care with UV Protection

Manufacturing instruction:

Part A and B are heated separately to 75°C. After adding part B into part A the mixture is homogenized with Ultra Turrax for one minute at 11000 rpm. After cooling down to 50°C part C is added. Afterwards the mixture is homogenized for one minute at 16000 rpm. At a temperature < 40°C part D is added. At room temperature the pH-value is adjusted with part E between 6.00 and 6.50.

Manufacturing instruction:

Part A and B are heated separately up to 75°C, part C is heated to 60°C. Afterwards part B is poured into part A under stirring. The mixture is homogenized with an Ultra Turrax for 30 sec. at 11 000 rpm and part C is incorporated. After cooling down to 40°C part D is added. At room temperature the pH-value is adjusted with Sodium Hydroxide between 6.30 and 6.70 and part F is added.

Manufacturing instruction:

Example 17: Sunscreen Cream

Manufacturing instruction:

Part A and part B are heated separately to 75°C. Part B is added into part A under continuous stirring and afterwards homogenized with Ultra Turrax for 30sec at 11000 rpm . After cooling down to 60°C part C is added. At 40°C part C is added and homogenized for 15sec at 11000 rpm. At room temperature the pH-value is adjusted with part E.

Example 18: UVA/UVB Daily Care Lotion, type O/W

Manufacturing instruction:

Part A and B are heated separately to 75°C; part C to 60°C. Part B is poured into part A under stirring. After one-minute of homogenization at 11000 rpm part C is added to the mixture of A/B. After cooling down to 40°C part D is incorporated. At room temperature the pH value is adjusted with part E between 6.3 and 7.0. Finally part F is added.

Manufacturing instruction:

Part A and part B are heated separately to 75°C. Part A is poured into part B under stirring. Immediately after the emulsification, part C is added to the mixture and homogenized with an Ultra Turrax at 11000 rpm for 30 sec. After cooling down to 65°C Sodium Acrylates Copolymer (and) Mineral Oil (and) PPG-1 Trideceth-6 At 50°C is added slowly to the UV absorber dispersion. At about 35-30°C part F is incorporated. The pH is adjusted with part G between 5.5 and 6.5.

Example 20: UV-A/UV-B Every Day Protection Lotion O/W

Manufacturing instruction:

Part A and part B are heated separately up to 80°C. Part A is poured into part B while stirring and homogenized with an Ultra Turrax by 11000 rpm for 30 sec. After cooling down to 60°C part C is incorporated. At40°C part D is added slowly under continuous stirring. The pH is adjusted with part E between 6.50 - 7.00.

Example 21: Spravable Sunscreen Lotion

Manufacturing instruction:

Part A and part B are heated separately up to 80°C, part C is heated to 50°C. Part B is poured into part A and homogenized with an Ultra Turrax for 1 minute at 11000 rpm. After cooling down to 50°C part C is added under continuous stirring. At 40°C part D is incorporated and homogenized again for 10 sec. at 11000 rpm. The pH is adjusted with part E.

Example 22: O/W Every Day UV Protection Lotion

Manufacturing instruction:

Part A and part B are heated separately up to 75°C, part C is heated to 60°C. Afterwards part B is poured into part A under stirring. The mixture is homogenized with an Ultra Turrax for 30 sec. at 11 000 rpm and part C is incorporated. After cooling down to 40°C part D is added. At room temperature the pH-value is adjusted with Sodium Hydroxide between 6.30 and 6.70 and part F is added.

Example 23: Water resistant Sunscreen Emulsion

Manufacturing instruction:

Part A and part B are heated separately to 80°C. Part A is poured into part B under continuous stirring. Afterwards the mixture is homogenized with an Ultra Turrax at 11 000 rpm for 1 min. After cooling down to 60°C part C is incorporated. At 40°C part D is added and the mixture homogenized for a short time again. At 35°C part E is added and at room temperature Fragrance is added. Finally the pH is adjusted with Sodium Hydroxide.

Example 24: UVA/UVB Sun Protection Lotion, O/W type

-47 -

Manufacturing instruction:

Part A and part B are heated separately up to 80°C. Part B is poured into part A under moderate stirring. The mixture is homogenized with an Ultra Turrax at 11000 rpm for 1 minute. After cooling down to 70°C part C is added under stirring. After cooling further down to 50°C part D is incorporated very slowly. At 40°C part E is added. At room temperature the pH adjusted with part F to 7.00 and part G is added.

Example 25: UVA/UVB Sun Protection Lotion, O/W type

Manufacturing instruction:

Part A and part B are heated separately up to 80°C. Part B is poured into part A under moderate stirring. The mixture is homogenized with an Ultra Turrax at 11000 rpm for

1 minute. After cooling down to 70°C add part C is added under stirring. After cooling further down to 50°C part D is incorporated very slowly. At 40°C part E is added. At room temperature the pH is adjusted with part F to 7.00 and part G is added.

Example 26: Sunscreen Lotion

Manufacturing instruction

Part A and part B are heated separately up to 75°C. Part B is poured into part A under progressive stirring speed. At a temperature < 65°C the ingredients of part D are added separately. After cooling down to 55°C under moderate stirring part C is added. At a temperature < 35°C the pH is checked and adjusted with Sodium Hydroxide and homogenized with an Ultra Turrax for 30 sec. at 11 000 rpm. At room temperature part F is added. Example 27: W/O Sunscreen Lotion

Manufacturing instruction:

Part A is heated to 80°C whilst stirring. Part B is added into part A and homogenized with an

Ultra Turrax at 11 000 rpm for one minute. After cooling down to 30°C part C is incorporated.

Example 28: Skin Protection Sunscreen Lotion W/O

Manufacturing instruction:

Part A is heated separately to 80°C under gentle stirring. Part B is added to part A and homogenized for one minute at 11000 rpm. After cooling down to 30°C part C is added under continuous stirring.

Example 29: Sunscreen

This Sunscreen may also be used as an anti-wrinkle perception modifier.

Manufacturing instruction

Mix part A and heat up to 60°C to 65 °C and add Disp. Slowly under fast stirring.

Add part B under moderate stirring at 60 °C.

Add part B into part A under stirring at 60 °C-75 °C.

Add part C under stirring until homogenization (emulsification at fast stirring, may be with ultra turrax).

Add part D under moderate stirring (60 °C).

Finally add part E under stirring (60 °C) and cool down under moderate stirring.

Example 30: PEG-free sunscreen

Claims

Claims:

1. Use of the compounds of formula

(1) . wherein

A is a radical of formula (1 a) ; or (1b)

i and R₅ independently from each other are hydrogen; Cι-Cι_βalkyl; or C₆-d₂aryl; R₂, R₃ and R₄ independently from each other are hydrogen; or a radical of formula

are a radical of formula (1c); Re, R7, Re, Rg and R10 independently from each other are hydrogen; hydroxy; halogen; Cr

Cι₈alkyl; Cι-Cι₈alkoxy; C₆-d₂aryl; biphenylyl; C₆-Cι₂aryloxy; Ci-Ciβalkylthio; carboxy;

-COOM; Cι-Cιs-alkylcarboxyl; aminocarbonyl; or mono- or di-CrCι₈alkylamino; d-

Cι₀acylamino; -COOH; M is an alkali metal ion; x is 1 or 2; and y is a number from 2 to 10; for the protection of human and animal hair and skin against the damaging effect of UV radiation.

2. Use according to claim 1, which relates to compounds of formula

(2) wherein

Ri, e, Re, R7 und R₈ are defined as in claim 1.

3. Use according to claim 1 or 2, wherein Riand R₅ are hydrogen.

4. Use according to one of claims 1 to 3, wherein R₆ and R₈ are hydrogen.

5. Use according to one of claims 1 to 4, wherein

R₇ is hydrogen; hydroxy; d-C₅alkyI; C C₅alkoxy; -COOM; -COOH; or COOR₁₀; M Is an alkali metal ion; and R₁₀ is d-C₅alkyl.

6. Use according to claim 1, which relates to compounds of formula

wherein

Ri, R2, R3, Rg and R10 are defined as in claim 1.

7. Use according to claim 6, wherein

R11 R2, R3, Rg and R10 are hydrogen; or, independently from each other, d-Cι₈alkyl.

8. Use according to any of claims 1 to 5, wherein the compound of formula

is used.

9. A cosmetic preparation comprising at least one compound of formula (1) according to claim 1 together with cosmetically tolerable carriers or adjuvants.

10. Cosmetic preparation according to claim 9 comprising the UV filter combination (A) comprising

(ai) at least one symmetrical triazine derivative of formula (1) and

(a₂) at least one aminobenzophenone derivative of formula

wherein

Ri and R₂ independently from each other are; Ci-doalkyl; d-doalkenyl; C₃-

Ciocycloalkyl; C₃-Cιocycloalkenyl; or Ri and R₂ together with the linking nitrogen atom form a 5- or 6-membered heterocyclic ring; ni is a number from 1 to 4; when nι = 1,

R₃ is a saturated or unsaturated heterocyclic radical; hydroxy-Cι-C₅alkyl; cyclohexyl optionally substituted with one or more Cι-C₅alkyl; phenyl optionally substituted with a heterocyclic radical, aminocarbonyl or d-C₅alkylcarboxy;

R₃ is an alkylene-, cycloalkylene, alkenylene or phenylene radical which is optionally substituted by a carbonyl- or carboxy group; a radical of formula *— CH— C=C-CH₂— or

R₃ together with A forms a bivalent radical of the formula (1a)

wherein n₂ is a number from 1 to 3;

R₃ is an alkanetriyl radical;

R₃ is an alkaπetetrayl radical;

A is -0-; or-N(R₅)-; and

R₅ is hydrogen; d-Csalkyl; or hydroxy-Ci-Csalkyl.

11. Cosmetic preparation according to claim 10 comprising the UV filter combination (A1 ) comprising (a₃) the compound of formula (6) or (9); and

(a₄) the compound of formula

12. Cosmetic preparation according to claim 9 comprising the UV filter combination (B) comprising (bi) at least one symmetrical triazine derivative of formula (1); and (b₂) at least one aminobenzophenone derivative of the formula

R¹ and R² independently from each other are hydrogen, Cι-C₂₀alkyl; C₂-C₂₀alkenyl; C₃-

C₁₀cycloalkenyl; wherein R¹ and R² may form a five- or six-membered ring; R³ and R⁴ independently from each other are Cι-C₂oalkyl; C₂-C₂₀alkenyl; C₃-

Ciocycloalkenyl, d-doalkoxy, Cι-C₂₀alkoxycarbonyl, Cι-C₂oalkylamino, di(d-

C₂oalkyl)amino, optionally substituted aryl or heteroaryl; X is hydrogen; COOR⁶; CONR^eR⁷; R⁵, R⁶, R⁷ independently from each other are hydrogen, Cι-C₂c.alkyl; C₂-C₂₀alkenyl; C₃-

Ciocycloalkyl; C₃-Cιocycloalkenyl; (Y-0)_q-Z; optionally substituted aryl; Y is -(CH₂)₂-; -(CH₂)₃-; -(CH₂)₄-; -CH(CH₃)-CH₂-; Z is -CH;₂-CH₃; -CH -CH₂-CH₃; -CH₂-CH₂-CH₂-CH₃; CH(CH₃)-CH₃; m is O; 1; 2; or 3; n is O; 1; 2; 3; or 4; and q is a number from 1 to 20.

13. Cosmetic preparation according to claim 12 comprising the UV filter combination (B1) comprising (b₃) the compound of formula (6) or (9); and

(b ) the compound of formula

14. Cosmetic preparation according to claim 9 comprising the UV filter combination (C) comprising (ci) at least one symmetrical triazine derivative of formula (1); and (c₂) at least one benzotriazole derivative of formula

. wherein

T₂ is CrCioalkyl, or phenyl-substituted d-C alkyl.

15. Cosmetic preparation according to claim 14 comprising the UV filter combination (C1) comprising (c₃) the compound of formula (6) or (9); and

(c₄) the compound of formula

16. Cosmetic preparation according to claim 9 comprising the UV filter combination (D) comprising (di) at least one symmetrical triazine derivative of formula (1); and

(d₂) at least one compound of formula

in which Ri and R₂, independently of one another, are C₃-Cι₈alkyl; C₂-Cι₈alkenyl; a radical of the formula -CH₂-CH(-OH)-CH₂-θ-T₁ ," or

Ri and R₂ are a radical of the formula (4a) — Rjjj-Si— O- -S rl-R,, R,,

Rι₂ is a direct bond; a straight-chain or branched C C alkylene radical or a radical of the formula -C H- or — C_ H— o- ;

Rι₃, Rι₄ and Rι₅, independently of one another, are Cι-Cι₈alkyl; Cι-Cι₈alkoxy or a radical

Rl6 of the formula — o-si — R,_R

Ri₆ is Cι-C₅alkyl; mi and m₃, independently of one another, are 1 to 4; pi is 0 or a number from 1 to 5; ι is a radical of the formula

(1b) or of the formula

Q1 \ N (1d)

Rs is hydrogen; Cι-C₁₀alkyl, -(CH₂CHR₅-θ) -R₄ ; or a radical of the formula

-CH₂-CH(-OH)-CH₂-0-Tι;

R is hydrogen; M; Cι-C₅alkyl; or a radical of the formula -(CH₂)_m-θ-T₁ ;

R₅ is hydrogen; or methyl;

T₁ is hydrogen; or d-C₈alkyl;

Q₁ Cι-Cι₈alkyl;

M is a metal cation; m₂ is 1 to 4; and

17. Cosmetic preparation according to claim 16 comprising the UV filter combination (D1) comprising (d₃) the compound of formula (6) or (9); and

(d₄) the compound of formula

18. Cosmetic preparation according to claim 9 comprising the UV filter combination (E) comprising (ei) at least one symmetrical triazine derivative of formula (1); and (e₂) at least one hydroxyphenyltriazine compound of formula

Ri, R₂ and R₃ are each independently of the others Cι-Cι₈alkyl; d-Cioalkenyl; or phenyl- Cι-C₄alkyl; P is hydrogen; or Ci-Csalkyl.

19. Cosmetic preparation according to claim 18 comprising the UV filter combination (E1) comprising (d₃) the compound of formula (6) or (9); and

(d ) the compound of formula

20. Cosmetic preparation according to claim 9 comprising the UV filter combination (F) comprising (fi) at least one symmetrical triazine derivative of formula (1), preferably the compound of formula (6) or (9); and (f₂) at least one dibenzoylmethane derivative of

^formu^la

21. Cosmetic preparation according to claim 9 comprising the UV filter combination (G) comprising

(gi) at least one symmetrical triazine derivative of formula (1), preferably the compound of formula (6) or (9); and (g₂) disodium phenyl dibenzimidazole tetrasulfonate.

22. Cosmetic preparation according to claim 9 comprising the UV filter combination (H) comprising

(hi) at least one symmetrical triazine derivative of formula (1); and (h₂) at least one benzoxazole-substituted triazine of the formula

Ri, R₂ and R₃ independently from each other are branched or unbranched Cι-C ₂alkyl.

23. Cosmetic preparation according to claim 22 comprising the UV filter combination (H1) comprising (h₃) the compound of formula (6) or (9); and (h₄) 1,3,5-triazine-2,4,6-triamine, N,N'-bis[4-[5-(1,1-dimethylpropyl)-2-benzoxazolyl]phenyl]-

N"-(2-ethylhexyl).

24. Cosmetic preparation according to claim 22 or 23 comprising the UV filter combination (H2) comprising

(h_s) the compound of formula (6) or (9); and (h₆) at least one of the compound of formula (h₂1), wherein (hβ Ri and R₂ are tert.amyl; and R₃ is tertbutyl; or wherein (h_κ) Ri and R₂ are tert.butyl and R₃ is tert.octyl; or wherein (hrø) Ri and R₂ are tert.butyl; and R₃ is 2-ethylhexyl; or wherein (h_M) Ri and R₂ are tertamyl; and R₃ is 2-ethylhexyl.

25. Cosmetic preparation according to claim 9 comprising the UV filter combination (I) comprising

(ii) at least one symmetrical triazine derivatives of formula (1 ), preferably the compound of formula (6) or (9); and (i₂) 2-(2H-benzotriazol-2-yl)-4-methyl-6-[2-methyl-3-[1 ,3,3,3-tetramethyM -

[(trimethylsilyl)oxy]disiloxanyl]propyl]-.

26. Cosmetic preparation according to claim 9 comprising the UV filter combination (K) comprising

(ki) at least one symmetrical triazine derivative of formula (1), preferably the compound of formula (6) or (9); and (k₂) siloxanes and silicones, di-Me, 1-[[4-[3-ethoxy-2-(ethoxycarbonyl)-3-oxo-1-proρe- nyl]phenoxy]methyl]ethenyl Me, 3-[4-[3-ethoxy-2-(ethoxycarbonyl)-3-oxo-1 -prope- nyl]phenoxy]-1-propenyl Me, wherein

Me is hydrogen.

27. Cosmetic preparation according to claim 9 comprising the UV filter combination (L) comprising

(Ii) at least one symmetrical triazine derivatives of formula (1 ), preferably the compound of formula (6) and/or (9); and (l₂) (+/-)-1,7,7-trimethyl-3-[(4-methylphenyl)methylene]bicyclo[2.2.1]heptan-2-one.

28. Cosmetic preparation according to claim 9 comprising the UV filter combination (M) (mι)at least one symmetrical triazine derivatives of formula (1), preferably the compound of formula (6) and/or (9); and (m₂)α-(2-oxoborn-3-ylidene)toluene-4-sulphonic acid and its salts.

29. Cosmetic preparation according to claim 9 comprising the UV filter combination (N) comprising

(ni) at least one symmetrical triazine derivatives of formula (1), preferably the compound of formula (6) and/or (9); and (n₂) methyl N,N,N-trimethyl-4-[(4,7,7-trimethyl-3-oxobicyclo[2,2,1]hept-2-ylidene)methyl]- anilinium sulphate.

30. Cosmetic preparation according to claim 9 comprising the UV filter combination (O) comprising

(oi) at least one symmetrical triazine derivatives of formula (1), preferably the compound of formula (6) and/or (9); and (o₂) 2-ethylhexyl 2-cyano,3,3-diphenylacrylate.

31. Cosmetic preparation according to claim 9 comprising the UV filter combination (P) comprising

(pi) at least one symmetrical triazine derivatives of formula (1), preferably the compound of formula (6) and/or (9); and (p₂) 2- ethylhexyl 4-methoxycinnamate.

32. Cosmetic preparation according to claim 9 comprising the UV filter combination (Q) comprising

(q ) at least one symmetrical triazine derivatives of formula (1), preferably the compound of formula (6) and/or (9); and (q₂) benzoic acid, 4,4',4"-( ,3,5-triazine-2,4,6-triyltriimino)tris-,tris(2-ethylhexyl)ester.

33. Cosmetic preparation according to claim 9 comprising the UV filter combination (R) comprising

(η) at least one symmetrical triazine derivatives of formula (1), preferably the compound of formula (6) and/or (9); and (r₂) 2-phenyl-1 H- beπzimidazole-5-sul phonic acid.

34. Cosmetic preparation according to claim 9 comprising the UV filter combination (S) comprising

(Si) at least one symmetrical triazine derivatives of formula (1), , preferably the compound of formula (6) and/or (9); and (s₂) Benzoic acid,4,4'-[[6-[[4-[[(1,1-dimethylethyl)amino]carbonyl]phenyl]amino]1,3,5-triazine-

2,4-diyl]diimino]bis-,bis(2-ethylhexyl)ester.

35. Cosmetic composition according to any of claims 9 to 34 wherein the compound of formula (1), formula (6) or formula (9) is present in the composition in the micronized state.

36. Use of the compounds of formula (1) as as an anti-wrinkle perception modifier.

37. A process for the preparation of the compound of formula (1 ), comprising reacting a halogen triazine compound of formula (1d) in a Friedel-Crafts-reaction with an optionally substituted aromatic hydrocarbon of formula (1e) or (1f) to the compound of formula (1) according to the following reaction scheme:

00 (1) wherein

X is fluoro; chloro; oder bromo; and Ri, Rz, R3, Rg, 0) x and y are defined as in claim 1.