ES2354870T3 - DERIVATIVES OF TRIAZINE AND ITS USES AS SOLAR PROTECTORS. - Google Patents

Abstract

A compound of formula ** Formula ** wherein R 1 is a radical C1-C18 alkyl, C2-C18 alkenyl, C6-C10 aryl or C6-C10 heteroaryl each unsubstituted or mono or polysubstituted by hydroxy, C1-C18 alkyl, alkoxy C1-C18, amino, C1-C5 monoalkylamino or by C1-C5 dialkylamino; C5-C7 cycloalkyl or C5-C7 cycloalkenyl each substituted or unsubstituted by C1-C5 alkyl; -OR '; or - NR'R "; R2 is hydrogen; a radical C1-C18 alkyl, C2-C18 alkenyl; C6-C10 aryl or C6-C10 heteroaryl each unsubstituted or mono or polysubstituted by hydroxy, C1-C18 alkoxy, cyano, amino, C1-C5 monoalkylamino or by C1-C5 dialkylamino; -OR '; or -NR'R "; or R1 and R2 together form a 5- to 7-membered heterocyclic or carbocyclic ring; A is C1-C5 alkyl; a C6-C10 aryl or heteroaryl radical substituted with C1-C18 alkoxy or C1-C18 alkyl or hydroxy or unsubstituted; or a radical of formula (1a) ** Formula ** R 'and R "are each independently hydrogen from each other; C1-C18 alkyl substituted by a group of quaternary ammonium, amino, C1-C18 alkoxy, C1-C18 alkyl, halo, mono or polyhydroxy, or unsubstituted, phenyl or C5-C7 cycloalkyl; R3 is hydrogen; or C1-C6 alkyl; and n is 0 or 1.

Description

The present invention relates to new triazine derivatives, a process for the preparation of such compounds and the use of such compounds for cosmetic preparations.

The new triazine derivatives correspond to formula 5

where

R1 is a C1-C18 alkyl, C1-C18 alkenyl, C6-C10 aryl or C6-C10 heteroaryl radical each unsubstituted or mono or polysubstituted by hydroxy, C1-C18 alkyl, C1-C18 alkoxy, amino, C1-C5 monoalkylamino or by C1-C5 dialkylamino; C5-C7 cycloalkyl or C5-C7 cycloalkenyl each substituted or unsubstituted by C1-C5 alkyl; -OR ’; or -NR’R ";

R2 is hydrogen; a C1-C18 alkyl radical, C2-C18 alkenyl; C6-C10 aryl or C6-C10 heteroaryl each unsubstituted or mono or polysubstituted by hydroxy, C1-C18 alkyl, C1-C18 alkoxy, cyano, amino, C1-C5 monoalkylamino or by C1-C5 dialkylamino; -OR ’; or -NR’R "; or

R1 and R2 together form a 5- to 7-membered heterocyclic or carbocyclic ring;

A is C1-C5 alkyl; a C6-C10 aryl or C6-C10 heteroaryl radical substituted with C1-C18 alkoxy or C1-C18 alkyl or hydroxy or unsubstituted; or a radical of formula (1a)

 twenty

R 'and R "are each independently hydrogen from each other; C1-C18 alkyl substituted by a group of quaternary ammonium, amino, C1-C18 alkoxy, C1-C18 alkyl, halo, mono or polyhydroxy, or unsubstituted, phenyl or cycloalkyl C5-C7;

R3 is hydrogen; or C1-C6 alkyl; Y

n is 0 or 1. 25

C1-C18 alkyl denotes straight or branched chain hydrocarbon radicals, for example methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl , 1,3-dimethylbutyl, n-hexyl, 1-ethylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetra-methylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl, 1 , 1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl, tridecyl, tetradecyl, pentadecyl or hexadecyl or octadecyl. 30

C1-C18 alkoxy denotes straight or branched chain radicals, for example methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, amyloxy, isoamyloxy or tert-amyloxy, n-hexyloxy, 1- methylhexyloxy, n-heptyloxy, isoheptyloxy, 1,1,3,3-tetramethylbutoxy, 1-methylheptyloxy, 3-methylheptyloxy, n-octyloxy, 2-ethylhexyloxy, 1,1,3-trimethylhexyloxy, 1,1,3,3- tetramethylpentyloxy, nonyloxy, decyloxy, undecyloxy, 1-methylundecyloxy, dodecyloxy, tridecyloxy, tetradecyloxy, pentadecyloxy, hexadecyloxy or octadecyloxy. 35

C2-C18 alkenyl is, for example, allyl, metalyl, isopropenyl, 2-butenyl, 3-butenyl, isobutenyl, n-penta-2,4-dienyl, 3-methyl-but-2-enyl, n-oct-2 -enyl, n-dodec-2-enyl, isododecenyl, n-dodec-2-enyl or n-octadec-4-enyl.

C6-C10 aryl is, for example, phenyl or naphthyl.

A heterocyclic ring is a heteroaromatic system that contains at least one oxygen, sulfur and / or nitrogen heteroatom 5 in the ring structure. Preferred heteroaryl groups preferably contain from 2 to 15 carbon atoms.

Examples of mono or C1-C5 dialkylamino are methylamino, ethylamino, propylamino, n-butylamino, sec-butylamino, tert-butylamino, pentylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino and methyl-ethylamino. 10

Preference is given to triazine derivatives of formula (1) wherein

R1 and R2 are each independently of the other phenyl or C1-C18 alkyl each substituted or unsubstituted by C1-C5 alkyl, hydroxy or C1-C5 alkoxy; -OR ’; or -NR’R "; or R1 and R2 together form a 5- to 7-membered heterocyclic or carbocyclic ring. 15

More especially preferred are the compounds of formula (1) wherein

R1 is C1-C5 alkyl; C1-C5 alkoxy; or phenyl substituted with C1-C5 alkoxy, hydroxy or C1-C5 alkyl or unsubstituted.

Compounds of formula (1) in which

R2 is hydrogen; C1-C5 alkyl; C1-C5 alkoxy; phenyl substituted with C1-C5 alkoxy, hydroxy or C1-C5 alkyl or unsubstituted; Y

n is 1.

Preference is also given to compounds of formula (1) wherein

R1 and R2 together are a radical - (CH2) 2-5- that is not additionally substituted or substituted by one or more C1-C5 alkyl and is interrupted or not interrupted by one or two groups -O- and / or - NH- and / or

Very special preference is given to compounds of formula (1) where

R1 and R2 are both a radical;

 30

R5 is hydrogen; or C1-C5 alkyl.

A in formula (1) is especially amino; phenyl; or C1-C5 alkoxyphenyl.

R3 in formula (1) is especially hydrogen.

Special preference is given to compounds of formula (1) wherein R1 and R2 are C1-C5 alkyl.

The examples of compounds according to the invention are listed in Table 1 below:

 Table 1

 Compound of formula

 R1 R2

 (2)

 (3)

 (4)

 (5)

 (6)

 (7)

 (8)

 (9)

 (10)

 (eleven)

    * -O-CH3  

 (12)

        H

(continuation)

 Compound of formula

 R1 R2

 (13)

 (14)

 (fifteen)

 (16)

           H

 (17)

    * -CH3  

 (18)

    * -O-C2H5  

 (19)

 (twenty)

        ** - CN

 (twenty-one)

 (22)

 (2. 3)

 (24)

(continuation)

 Compound of formula

 R1 R2

 (25)

 (26)

        H

 (27)

           H

 (28)

           H

 (29)

 (30)

 (31)

       * -CH3  

Especially preferred are the compounds of the formulas

Y

The triazine derivatives of formula (1) according to the invention are prepared in a manner already known by reaction of a diaminotriazine compound of formula 5

with a compound of formula (1b)

Y

 10

where

R4 is C1-C5 alkyl and R1, R2, R3, A and n are as defined for formula (1), to form a compound of formula (1).

The reaction is carried out in the presence of an acid, with or without the addition of one or more solvents at a reaction temperature of 0 to 200 ° C.

Generally 0.8 to 2.0 moles of the compound of formula (1b) and 0.8 to 2.0 moles of a compound of formula (1c) are used per free amino group of the compound (1a).

The reaction is preferably carried out in DMSO, N-methylpyrrolidone, DMF or DMA. 5 It is also possible, however, to use protic solvents, such as ethanol, methanol, isobutanol or isopropanol. The reaction can also be carried out in an aliphatic or aromatic solvent, such as hexane, toluene or xylene. It is also possible to use ethers, such as diethyl ether and tetrahydrofuran, or halogenated solvents, such as chloroform or dichloromethane.

The reaction is preferably carried out as a reaction in a single reactor. The individual reagents can, however, be added in any order. For example, the catalyst may be present from the beginning or may be introduced later. It is also possible to first initiate the reaction between (1b) and (1c) in the presence of the catalyst and only then add the triazine compound of formula (1a). It is also possible to first react the compound of formula (1a) with the compound of formula (1b) in the presence of a catalyst and then add 15 (1c).

The reaction can be carried out at a temperature of 0 to 200 ° C, preferably 20 to 100 ° C and especially 50 to 80 ° C.

The reaction times depend on the reaction temperature. Within the preferred temperature range, the reactions are usually completed in 1 to 6 hours. At low temperatures, the reaction time is considerably increased and may be 48 hours or more.

Organic and inorganic acids from Brönstedt or Lewis or mixtures thereof are used as catalysts. Examples of typical acids are phosphoric acid, trifluoroacetic acid, oxalic acid, methanesulfonic acid, toluenesulfonic acid, phenylsulfonic acid and trifluoromethanesulfonic acid. Acidic anhydrides are also effective, for example trifluoromethanesulfonic anhydride, methanesulfonic anhydride and acetic anhydride. Preference is given, however, to the use of Lewis acids, such as phosphorus oxychloride, copper chlorides, zinc chloride, lanthanum chloride, chromium chlorides, iron chlorides, aluminum chloride, titanium chlorides, germanium chloride , and hydrates thereof. It is also possible to use acidic ion exchangers. 30

The product is isolated according to conventional techniques, such as filtration, centrifugation, phase separation and liquid extraction. The products are purified, among others, by recrystallization from a solvent or a mixture of solvents, giving preference to solvents or solvent mixtures containing alcohols. Purification can also be carried out by chromatographic methods and by distillation. 35

The compounds of formula (1) according to the invention are especially suitable as UV filters, that is to protect organic materials that are sensitive to ultraviolet light, especially human and animal skin and hair, against the harmful effect of UV radiation. The compounds are therefore suitable as protective agents against sunlight in cosmetic preparations, as in pharmaceutical and veterinary preparations. The compounds 40 can be used either in the dissolved state or in the micronized state.

The invention therefore relates to a cosmetic preparation containing at least one compound of formula (1), and to cosmetically tolerable carriers or adjuvants.

In addition to the UV absorber according to the invention, the cosmetic preparation may also include one or more UV protective substances among the following classes of substances:

1. derivatives of p-aminobenzoic acid, for example 2-ethylhexyl ester of 4-dimethylaminobenzoic acid;

2. Salicylic acid derivatives, for example 2-ethylhexyl ester of salicylic acid;

3. benzophenone derivatives, for example 2-hydroxy-4-methoxybenzophenone and its derivative of 50 5-sulfonic acid;

4. dibenzoylmethane derivatives, for example 1- (4-tert-butylphenyl) -3- (4-methoxyphenyl) -propane-1,3-dione;

5. diphenylacrylates, for example 2-ethylhexyl 2-cyano-3,3-diphenylacrylate, and 3- (benzofuranyl) 2-cyanoacrylate;

6. 3-imidazol-4-ylacrylic acid and esters;

7. 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; 5

8. UV polymeric absorbents, for example the benzylidene malonate derivatives described in EP-A-709 080;

9. Cinnamic acid derivatives, for example the ester of 4-methoxycinnamic acid 2-ethylhexyl and isoamyl ester or derivatives of cinnamic acid disclosed in US-A-5 601 811 and WO 97/00851;

10. Camfor derivatives, for example 3- (4'-methyl) benzylidene-bornan-2-one, 3-benzylidene-bornan-2-10 one, polymer N- [2 (and 4) -2-oxiborn-3 -iliden-methyl) -benzyl] acrylamide, 3- (4'-trimethylammonium) -benzylidene-bornan-2-one methyl sulfate, 3,3 '- (1,4-phenylenedimetin) -bis (7,7- dimethyl-2-oxo-bicyclo [2.2.1] heptane-1-methanesulfonic acid) and its salts, 3- (4'-sulfo) benzylidene-bornan-2-one and its salts; camforbenzalkonium methosulfate;

11. Hydroxyphenyltriazine compounds, for example 2- (4'-methoxyphene-4,6-bis (2'-hydroxy-4'-n-octyl-15 xiphenyl) -1,3,5-triazine; 2,4-bis {[4- (3- (2-Propyloxy) -2-hydroxypropyloxy) -2-hydroxy] -phenyl} -6- (4-methoxyphenyl) -1,3,5-triazine; 2,4-bis {[4 - (2-ethylhexyloxy) -2-hydroxy] -phenyl} -6- [4- (2-methoxyethyl-carboxy) -phenylamino] -1,3,5-triazine; 2,4-bis {[4- (tris (trimethylsilyloxy-silylpropyloxy) -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- (3-20 (2-20) -propyloxy) -2-hydroxy-propyloxy) -2-hydroxy] -phenyl} -6- [4-ethylcarboxy) -phenylamino] -1,3,5-triazine;

12. Benzotriazole compounds, for example 2,2'-methylene-bis (6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) -phenol

13. Trianilino-s-triazine derivatives, for example 2,4,6-trianilin- (p-carbo-2'-ethyl-1'-oxy) -1,3,5-triazine 25 and the UV absorbers disclosed in US-A-5 332 568, EP-A-517 104, EP-A-507 691, WO 93/17002 and EP-A-570 838; US-A-5928 630, DE 4 105 923 A1.

14. 2-Phenylbenzimidazol-5-sulfonic acid and its salts;

15. mentyl o-aminobenzoate;

16. TiO2 (encapsulated differently), ZnO and mica. 30

The UV absorbers described in "Sunscreens", Eds. N. J. Lowe, N. A. Shaath, Marcel Dekker, Inc., New York and Basel or in Cosmetics & Toiletries (107), 50 et seq. (1992) can also be used as additional UV protective substances.

Special preference is given to the sun protection agents indicated in the following Table:

 INCI

 Chemical Name CAS No.

 3-BENCILIDEN ALCANFOR

 1,7,7-trimethyl-3- (phenylmethylene) -bicyclo [2.2.1] heptan-2-one 15087-24-8

 4-METHYLBENCILIDENE REACH

 (+/-) - 1,7,7-Trimethyl-3 - [(4-methylphenyl) -methylene] bicyclo [2.2.1] heptan-2-one 36861-47-9

(continuation)

 INCI

 Chemical Name CAS No.

 BENZOFENONA-10

 (2-hydroxy-4-methoxyphenyl) - (4-methyl-phenyl) methanone 1641-17-4

 BENZOFENONA-1

 2,4-dihydroxybenzophenone 131-56-6

 BENZOFENONA-2

 2,2 ’, 4,4’-tetrahydroxybenzophenone 131-55-5

 BENZOFENONA-3

 2-hydroxy-4-methoxybenzophenone; 131-57-7

 BENZOFENONA-4

 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid 4065-45-6

 BENZOFENONA-6

 2,2’-dihydroxy-4,4’-dimethoxybenzophenone 131-54-4

 BENZOFENONA-8

 2,2’-dihydroxy-4-methoxybenzophenone 131-53-3

 BENCILID ACID SULPHONIC REACH

 alpha- (2-oxoborn-3-ylidene) -toluen-4-sulfonic acid and its salts 56039-58-8

 METOXI-DIBENZOILMETHANE BUTIL

 1- [4- (1,1-dimethylethyl) phenyl] -3- (4-methoxyphenyl) propane-1,3-dione 70356-09-1

 REACH BENZALCONY METOSULPHATE

 methyl N, N, N-trimethyl-4 - [(4,7,7-trimethyl-3-oxobicyclo [2,2,1] hept-2-ylide) -methyl] anilinium 52793-97-2

 CINOXATE

 2-ethoxyethyl p-methoxycinnamate 104-28-9

 DEA-METOXYCINAMATE

 p-methoxyhydrocinamate diethanolamine salt 56265-46-4

 DIISOPROPIL METHYL CINAMATE

 2-Propeneic acid methyl ester, 3- [2,4-bis (1-methyl ethyl) phenyl] 32580-71-5

 DIPROPILEN GLICOL SALICILATO

 Dipropylene Glycol Salicylate 7491-14-7

 ETIL DIHYDROXIPROPIL PABA

 ethyl 4-bis (2-hydroxypropyl) -amino-benzoate 58882-17-0

 ETHYL DIISOPROPIL CINAMATE

 ethyl 3- [2,4-bis (1-methyl ethyl) phenyl] -acrylate 32580-72-6

 ETHYL METOXY-CINAMATE

 ethyl p-methoxycinnamate 1929-30-2

 GLICERIL OCTANOATE

 DIMETOXYCINAMATE

 GLICERIL PABA

 glyceryl 1- (4-aminobenzoate) 136-44-7

 HOMOSALATE

 3,3,5-Trimethylcyclohexyl-2-hydroxy-benzoate 118-56-9

 ISOAMIL p-METOXI-CINAMATO

 isopentyl p-methoxycinnamate 71617-10-2

 ISOPROPIL DIBENZOIL-METHANE

 1- [4- (1-Methylethyl) phenyl] -3-phenyl-propane-1,3-dione 63250-25-9

 ISOPROPIL METOXI-CINAMATO

 isopropyl p-methoxycinnamate 5466-76-2

 LAWSONIA

 2-hydroxy-1,4-naphthoquinone 83-72-7

 MENTRANTRANILATE

 mentyl o-aminobenzoate 134-09-8

 SALTILLATE MENU

 mentil salicylate 89-46-3

 OCTOCRYLENE

 2-ethylhexyl 2-cyano-3,3-diphenyl acrylate 6197-30-4

 ETILHEXIL DIMETIL PABA

 2-ethylhexyl 4- (dimethylamino) benzoate 21245-02-3

 ETILHEXIL METOXI-CINAMATO

 2-ethylhexyl 4-methoxycinnamate 5466-77-3

 ETILHEXIL SALICILATO

 2-ethylhexyl salicylate 118-60-5

(continuation)

 INCI

 Chemical Name CAS No.

 ETILHEXIL TRIAZONA

 Benzoic acid, 4,4 ', 4 "- (1,3,5-triazine-2,4,6-triyltriimino) tris-, tris (2-ethylhexyl) ester; 2,4,6-trianilino- (p- carbo-2'-ethylhexyl-1'-oxy) -1,3,5- triazine 88122-99-0

 PABA

 4-aminobenzoic acid 150-13-0

 PEG-25 PABA

 Benzoic acid, 4-amino-, ethyl ester, polymer with oxirane 113010-52-9

 PABA DIMETABLE PENTIL

 amyl dimethyl PABA 14779-78-3

 SULPHONIC PHENYLBENZIMIDAZOL ACID

 2-phenyl-1H-benzimidazol-5-sulfonic acid 27503-81-7

 BENZILIDENA ALCANFOR POLYACRILAMIDOMETIL

    113783-61-2

 TEA-SALICILATO

 triethanolamine salicylate 2174-16-5

 DI-SULPHONIC TEREFTALIUD ACID

 3,3 ’- (1,4-phenylenedimethylene) bis [7,7-dimethyl-2- oxo-bicyclo acid [2.2.1] heptane-1-methanesulfonic acid] 90457-82-2

 TITANIUM DIOXIDE

 titanium dioxide 13463-67-7

 DIGALOIL TRIOLATE

 digaloil trioleate 17048-39-4

 ZINC OXIDE

 zinc oxide 1314-13-2

 Methylene bis-benzotriazolyl tetramethylbutylphenol

 2,2’-methylene-bis [6- (2H-benzotriazol-2-yl) - 4-103597-45-1 (1,1,3,3-tetramethylbutyl) -phenol]

 Bis-ethylhexyloxyphenol methoxyphenyltriazine

 2,4-bis {[4- (2-ethylhexyloxy) -2-hydroxy] -phenyl} - 6- (4-methoxyphenyl) - (1,3,5) -triazine 187393-00-6

 BISIMIDAZILATE

 1H-benzimidazol-4,6-disulfonic acid, 2,2 ′ - (1,4-phenylene) bis-, disodium salt 180898-37-7

 DIETILHEXIL BUTAMIDO TRIAZONA

 Benzoic acid, 4,4 '- [[6 - [[4 - [[(1,1-dimethyl-ethyl) amino] carbonyl] phenyl] amino] -1,3,5-triazine-2,4-diyl] diimino] bis-, bis (2-ethyl-hexyl) ester 154702-15-5

 DROMETRIZOL TRISI-LOXANO

 phenol, 2- (2H-benzotriazol-2-yl) -4-methyl-6- [2- methyl-3- [1,3,3,3-tetramethyl-1 - [(tri-methylsilyl) 155633-54- 8

 oxy] disiloxanil] propyl] -

 BENCILIDEN POLISYLOXAN MALONATE

 alpha- (trimethylsilyl) -omega- (trimethyl-silyl-oxy) poly [oxy (dimethyl) silylene] -co- [oxy- (methyl) (2- {p- [2,2-bis (ethoxycarbonyl) vinyl] - phenoxy} -1-methylenenetyl) silylene] -co- [oxy- (methyl) (2- {p- [2,2- bis (ethoxycarbonyl) vinyl] -phenoxy} prop-1-enyl) silylene] 207574-74- one

 hexyl ester 2- (4-diethylamino-2-hydroxybenzoyl) -benzoic acid 302776-68-7

Each of the sun protection agents mentioned above, especially the sun protection agents in Table 1 indicated as preferred, may be used in admixture with the UV absorbers according to the invention. It will be understood in this regard that, in addition to the UV absorbers according to the invention, it is also possible to use more than one of the additional protective agents against sunlight, for example, two, three, five, five or six agents additional protectors against sunlight.

Preference is given to the use of mixing ratios of UV absorbers in accordance with the agents of the invention / additional protective agents against sunlight from 1:99 to 99: 1, especially from 1:95 to 95: 1 and preferably from 10:90 to 90:10, based on weight. Of special interest are the mixing ratios from 20:80 to 80:20, especially 10 from 40:60 to 60:40 and preferably about 50:50. Such mixtures can be used, among others, to improve solubility or increase UV absorption.

Appropriate blends can be used especially conveniently in the cosmetic preparations described below.

Cosmetic preparations are especially suitable as UV filters, that is to say for the protection of organic materials that are sensitive to ultraviolet light, especially skin and hair, against the harmful effects of UV radiation.

UV absorbers can be used either in a dissolved state or in a micronized state.

Any known process suitable for the preparation of microparticles can be used for the preparation of micronized UV absorbers, for example:

- wet grinding with a hard grinding medium, for example zirconium silicate and a protective surfactant or a protective polymer in water or in a suitable organic solvent;

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

- by means of expansion in accordance with the RESS (Rapid Expansion of Supercritical Solutions) process of supercritical fluids (eg CO2) 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; 30

- by reprecipitation from suitable solvents, including supercritical fluids (GASR process = Recrystallization with Solvent Gas / PCA process = Precipitation with Compressed Solvents).

As milling apparatus for precipitation of the micronized organic UV absorbers, for example, a jet mill, ball mill, vibratory mill or hammer mill, preferably a high speed mixing mill, can be used. The milling is preferably carried out with a grinding aid, for example an alkylated vinyl pyrrolidone polymer, to a vinyl pyrrolidone / vinyl acetate copolymer, an acyl glutamate, an alkyl polyglucoside, ceteareth-25 or a phospholipid.

The micronized UV absorbers thus obtained usually have an average particle size 40 of 0.02 to 2, preferably 0.05 to 1.5, and more especially 0.1 to 1.0 nm.

UV absorbers can also be used in the form of dry powder. For that purpose, UV absorbers are subjected to known grinding methods, such as vacuum atomization, counter current spray drying, etc. Such powders have a particle size of 0.1 nm to 2 mm. To avoid agglomeration, UV absorbers can be coated with a surface active compound before the spraying process, for example with an anionic, non-ionic or amphoteric surfactant, for example a known phospholipid or polymer, such as PVP, an acrylate, etc.

Cosmetic preparations contain, for example, 0.1 to 30% by weight, preferably 0.1 to 15% by weight and especially 0.5 to 10% by weight, based on the total weight of the composition, of one or more UV absorbers and at least one cosmetically tolerable adjuvant.

Cosmetic preparations can be prepared by physical mixing of the UV absorber (s) with the adjuvant using usual methods, for example simply by stirring together the individual components, especially making use of the dissolution properties of cosmetic absorbents and known from UV, for example OMC, isooctyl ester of salicylic acid, among others. The UV absorber can be used, for example, without further treatment, or in a micronized state, or in the form of a powder.

Cosmetic preparations may be, for example, creams, gels, lotions, alcoholic solutions and aqueous / alcoholic solutions, emulsions, wax / fat compositions, stick preparations, powders or ointments. twenty

As the emulsions containing oil and water (for example the emulsions or microemulsions of W / O, O / W, O / W / O and W / O / W) 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, 25 based on the total weight of the composition, at least one component of the oil, from 0 to 30% by weight, especially from 1 to 30% by weight and preferably from 4 to 20% by weight, based on the total weight of the composition, of at least one emulsifier,

10 to 90% by weight, especially 30 to 90% by weight, based on the total weight of the composition, water, and 0 to 88.9% by weight, especially 1 to 50% by weight, of additional cosmetically tolerable adjuvants 30.

As oil components of oil-containing compositions (eg oils, emulsions or microemulsions of W / O, O / W, O / W / O and W / O / W), for example, based Guerbet alcohols are considered in fatty alcohols having 6 to 18, preferably 8 to 10, carbon atoms, C6-C24 linear fatty acid esters with C3-C24 linear alcohols, C6-C13 branched carboxylic acid esters with C6 linear fatty alcohols - C24, C6-C24 linear fatty acid esters with branched alcohols, especially 2-ethylhexanol, hydroxycarboxylic acid esters with C6-C22 linear or branched fatty alcohols, especially dioctyl malate, linear and / or branched fatty acid esters with polyhydric alcohols ( for example propylene glycol, diol dimer or triol trimer) and / or alcohols of Guerbet, triglycerides based on C6-40 C10 fatty acids, liquid mixtures of mono / di / triglycerides based on fatty acids C6-C18, esters of C6-C24 fatty alcohols and / or Guerbet alcohols with aromatic carboxylic acids, especially benzoic acid, esters of C2-C12 dicarboxylic acids with linear or branched alcohols having 1 to 22 carbon atoms or polyols which they have 2 to 10 carbon atoms and 2 to 6 hydroxy groups, vegetable oils (such as sunflower oil, olive oil, soybean oil, rapeseed oil, 45 almond oil, jojoba oil, orange oil, wheat germ oil, peach seed oil and the coconut oil liquid components), branched primary alcohols, substituted cyclohexanes, linear and branched C6-C22 fatty alcohol carbonates, Guerbet carbonates, C6 alcohol benzoic acid esters - C22 linear and / or branched (for example Finsolv® TN), dialkyl symmetric or asymmetric linear or branched ethers having a total of 12 to 50 36 carbon atoms, especially 12 to 24 carbon atoms, for example di-n-octyl ether, di-n-decyl ether, di-n-nonyl ether, di-n-undecyl ether, di-n-dodecyl ether, n-hexyl n-octyl ether, n -octyl n-decyl ether, n-decyl n-undecyl ether, n-undecyl n-dodecyl ether, n-hexyl n-undecyl ether, di-tert-butyl ether, diisopentyl ether, di-3-ethyldecyl ether, tert- butyl n-octyl ether, isopentyl n-octyl ether and 2-methyl pentyl-n-octyl ether; ring opening products of epoxidized fatty acid esters with polyols, silicone oils and / or 55 aliphatic or naphthenic hydrocarbons. Also important are monoesters of fatty acids with alcohols having 3 to 24 carbon atoms. That group of substances includes the esterification products of fatty acids having 8 to 24 carbon atoms, 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, elaewestric 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 5 oxosynthesis aldehydes of Roelen or in dimerization of unsaturated fatty acids) with alcohols, for example, isopropyl alcohol, caproic alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauric alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleil alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linoyl alcohol, linolenyl alcohol, elaeoestearil alcohol, a raquidil alcohol, gadoleil alcohol, behenyl alcohol, erucil alcohol and brasidyl alcohol and mixtures of technical grade thereof (obtained, for example, in the high pressure hydrogenation of technical grade methyl esters based on fats and oils or aldehydes of Roelen oxosynthesis and as monomeric fractions in the dimerization of unsaturated fatty alcohols). Of particular importance are isopropyl myristate, C16-C18 alkyl esters of isononanoic acid, 2-ethylhexyl ester of stearic acid, cetyl oleate, glycerol tricaprilate, caprinate / caprilate of coconut fatty alcohol and n-butyl stearate. Other oil components that can be used are dicarboxylic acid esters, such as di-n-butyl adipate, di (2-ethylhexyl) adipate, di (2-ethylhexyl) succinate and diisotridecyl acetate, and also diol esters, such as ethylene glycol dioleate, ethylene glycol diisotridecanoate, propylene glycol di (2-ethylhexanoate), propylene glycol diisoesterate, propylene glycol dipelargonate, butanediol diisoesterate and neopentyl glycol dicaprilat. Preferred mono or polyols are ethanol, isopropanol, propylene glycol, hexylene glycol, glycerol and sorbitol. It is also possible to use di and / or trivalent metal salts (alkaline earth metal, Al3 + among others) of one or more alkylcarboxylic acids.

The oil components may be used in an amount, for example, 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. 25

Any emulsifier that can be conventionally used for the compositions can be used.

As emulsifiers, for example, non-ionic surfactants of the following groups are considered:

- addition products of 2 to 30 moles of ethylene oxide and / or 0 to 5 mol of propylene oxide 30 with linear fatty alcohols having 8 to 22 carbon atoms, with fatty acids having 12 to 22 atoms carbon and with alkylphenols having 8 to 15 carbon atoms in the alkyl group, for example ceteareth-20 or ceteareth-12;

- C12-C22 fatty acid mono and diesters of addition products of 1 to 30 moles of ethylene oxide with polyols having 3 to 6 carbon atoms, especially with glycerol; 35

- glycerol mono and diesters and sorbitan mono and diesters of saturated and unsaturated fatty acids having 6 to 22 carbon atoms and ethylene oxide addition products thereof, for example glyceryl stearates, glyceryl isostearates, glyceryl oleates, sorbitan oleates or sorbitan sesquioleates;

- C8-C22 alkyl mono and oligoglycosides and ethoxylated analogs thereof, with preferred oligomerization grades 40 being 1.1 to 5, especially 1.2 to 1.4, and glucose being preferred as the component sugar;

- addition products of 2 to 60 moles, especially 15 to 60 moles, of ethylene oxide with castor oil and / or hardened castor oil;

- polyol esters and especially polyglycerol esters, for example diisoestearoyl polyglyceryl-3-45 diisoesterates, polyglyceryl-3-diisoestearates, triglyceryl diisoesterates, polyglyceryl-2-sesquiisoesterates or polyglyceryl dimerates. Mixtures of compounds of a plurality of these classes of substances are also suitable;

- partial esters based on saturated, unsaturated, linear or branched C6-C22 fatty acids, ricinoleic acid and also 12-hydroxystearic acid and glycerol, polyglycerol, pentaerythritol, 50 dipentaerythritol, sugar alcohols (for example sorbitol), alkyl glycosides ( for example methyl glycoside, butyl glycoside, lauryl glycoside) and also polyglucosides (for example cellulose), for example polyglyceryl-2-dihydroxystearates or polyglyceryl-2-diricinoleates;

- mono, di and tri-alkyl phosphates and also mono, di and / or tri-PEG-alkyl phosphates and salts thereof;

- wool wax alcohols; 55

- one or more ethoxylated esters of natural derivatives, for example polyethoxylated esters of hydrogenated castor oil;

- silicone oil emulsifiers, for example silicone polyol;

- polysiloxane / polyalkyl / polyether copolymers and the corresponding derivatives, for example cetyl dimethicone copolyol; 5

- mixed ethers of pentaerythritol, fatty acids, citric acid and fatty alcohol (see DE-A-1 165 574) and / or mixed esters of fatty acids having 6 to 22 carbon atoms, methylglucose and polyols, preferably glycerol or polyglycerol , for example polyglyceryl-3-glucose distearates, polyglyceryl-3-glucose dioleates, methyl glucose dioleates or dicocoyl pentaerythril distearyl citrates and also

- polyalkylene glycols. 10

The addition products of ethylene oxide and / or propylene oxide with fatty alcohols, fatty acids, alkylphenols, glycerol mono and diesters and also sorbitan mono and diesters of fatty acids, or with castor oil, are known, commercially available products . They are usually homologous mixtures, whose average degree of alkoxylation corresponds to the ratio of the amounts of ethylene oxide and / or propylene oxide and the substrate with which the addition reaction is carried out. C12-C18 fatty acid mono and diesters of addition products of ethylene oxide with glycerol are known, for example, from DE-A-2 024 051 as fat restoration substances for cosmetic preparations.

C8-C18 alkyl mono and oligoglycosides, their preparation and use are known in the state of the art. They are specially prepared by reacting glucose or oligosaccharides with primary alcohols having 8 to 18 carbon atoms. Suitable glycoside radicals include monoglycosides in which a cyclic sugar radical is glycosidically linked to fatty alcohol and also with oligomeric glycosides having an oligomerization degree preferably approximately up to 8. The oligomerization degree is an average statistical value based on a usual homologous distribution for such technical grade products. 25

It is also possible to use zwitterionic surfactants as emulsifiers. The term "zwitterionic surfactants" especially denotes surface active compounds that carry at least one quaternary ammonium group and at least one carboxylate and / or sulfonate group in the molecule. Zwitterionic surfactants that are especially suitable are the so-called betaines, such as N-alkyl-N, N-dimethylammonium glycinates, for example cocoalkyldimethylammonium glycinate, N-30 acylaminopropyl-N, N-dimethylammonium glycinates, for example cocoacylaminopropyldimethylammonium 2 -alqul-3-carboxymethyl-3-hydroxyethylimidazolines each having 8 to 18 carbon atoms in the alkyl group or in the acyl group and also cocoacylaminoethylhydroxyethylcarboxymethyl glycinate. Special preference is given to the fatty acid amide derivative known by the name CTFA cocamidopropyl betaine. The ampholytic surfactants are also suitable as emulsifiers. It is understood that ampholytic surfactants especially means those which, in addition to containing a C8-C18 alkyl or acyl group, contain at least one free amino group and at least one -COOH or -SO3H group in the molecule and are capable of forming internal salts . Examples of suitable ampholytic surfactants include N-alkylglycins, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycins, N-alkyltaurines, N-40 alkylsarcosines, 2-alkylamino propyl amino acids , each having approximately 8 to 18 carbon atoms in the alkyl group. Ampholytic surfactants to which special preference is given are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and C12-C18 acylsarcosine. In addition to the ampholytic emulsifiers, quaternary emulsifiers are also considered, with special preference being given to those of the quaternary ester type, preferably salts of triethanolamine esters of the methyl quaternary fatty diacid.

Nonionic emulsifiers are preferred. Of the aforementioned non-ionic emulsifiers, special preference is given to ethoxylated fatty alcohols having 8 to 22 carbon atoms and 4 to 30 EO units. fifty

The emulsifiers can be used in an amount, 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. It is also possible, however, in principle to dispense with the use of emulsifiers.

The preparations according to the invention, for example creams, gels, lotions, alcoholic and aqueous / alcoholic solutions, emulsions, wax / fat compositions, stick preparations, powders or ointments, may also contain, as adjuvants and additives

additional, mild surfactants, super greasing agents, pearly waxes, consistency regulators, thickeners, polymers, silicone compounds, fats, waxes, stabilizers, active biogenic ingredients, active deodorant ingredients, anti-dandruff agents, film formers, swelling agents, others UV protection factors, antioxidants, hydrotropic agents, preservatives, insect repellents, self-tanning agents, solubilizers, perfuming oils, dyes, bacterial inhibiting agents and the like.

Suitable substances for use as super-greasing 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 acting simultaneously as foam stabilizers. 10

Examples of suitable mild surfactants, that is to say skin-tolerant surfactants especially well tolerated, include fatty alcohol polyglycol ether sulfates, monoglyceride sulfates, mono and / or dialkyl sulphosuccinates, fatty acid isethionates, fatty acid sarcosinates, taurids. fatty acid, fatty acid glutamates, α-olefin sulfonates, carboxylic ether acids, alkyl oligoglycosides, fatty acid glucamides, alkylamidobetaines and / or fatty acid-protein condensation products, the latter preferably based on wheat proteins.

Pearly waxes include, for example: alkyl glycol esters, especially ethylene glycol distearate; fatty acid alkanolamides, especially coconut fatty acid diethanolamide; partial glycerides, especially stearic acid monoglyceride; esters of polyvalent carboxylic acids, substituted with hydroxy or not substituted with fatty alcohols having 6-20 to 22 carbon atoms, especially long chain 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 that they have 2 to 15 carbon atoms and 2 to 10 hydroxy groups, and mixtures thereof.

Consistency regulators are especially fatty alcohols or hydroxy fatty alcohols having 12 to 22 carbon atoms and preferably 16 to 18 carbon atoms, and in addition partial glycerides, fatty acids and hydroxy fatty acids. Preference is given to a combination of such substances with alkyl oligoglycosides and / or fatty acid N-methylglucamides of identical chain length and / or polyglycerol poly-12-hydroxystearates. Suitable thickeners include, for example, types of Aerosil (hydrophilic silicic acids), polysaccharides, especially xanthan gum, guar-guar, agar-agar, alginates and tyloses, carboxymethyl cellulose and hydroxymethyl cellulose, also mono and diesters of polyethylene glycol of weight relatively high molecular weight of fatty acids, polyacrylates (for example Carbopol® of Goodrich or Synthalen® of Sigma), polyacrylamides, polyvinyl alcohol and polyvinylpyrrolidone, surfactants, for example glycerides of ethoxylated fatty acid, fatty acid esters with polyols, for example pentaerythritol or trimethylolpropane, fatty alcohol ethoxylates with restricted homologous distribution and alkyl oligoglycosides as well as electrolytes, such as sodium chloride or ammonium chloride. 40

Suitable cationic polymers are, for example, cationic cellulose derivatives, for example a quaternary hydroxymethyl cellulose which can be obtained under the Amerchol Polymer JR 400® brand, cationic starch, diallylammonium and acrylamide salt copolymers, vinylpyrrolidone / vinyl quaternary polymers imidazole, for example Luviquat® (BASF), condensation products of polyglycols and amines, quaternary collagen polypeptides, for example hydrolyzed hydroxypropyl laurildimony collagen (Lamequat®L / Grunau), wheat quaternary polypeptides, polyethyleneimine, cationic silicone polymers , for example, amidomethicones, copolymers of adipic acid and dimethylaminohydroxypropyldiethylenetriamine (Cartaretin® / Sandoz), copolymers of acrylic acid with dimethyldiallylammonium chloride (Merquat® 550 / Chemviron), polyamine polyamides, as described, for example, in FR-A-2 840, and the water-soluble crosslinked polymers thereof, 50 cationic derivatives of chitin, for example quaternary chitosan, optionally distributed as microcrystals; condensation products of dihaloalkyl, for example dibromobutane, with bisdialkylamines, for example bisdimethylamino-1,3-propane, cationic guar gum, for example Jaguar® C-17, Jaguar® C-16 from Celanese, quaternary ammonium salt polymers, for example Mirapol® A-1 5, Mirapol® AD-1, Mirapol® AZ-1 from Miranol. 55

As anionic, zwitterionic, amphoteric and non-ionic polymers are considered, for example, vinyl acetate / crotonic acid copolymers, vinyl pyrrolidone / vinyl acrylate copolymers, vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / copolymers maleic anhydride and esters thereof, uncrosslinked polyacrylic acids and polyacrylic acids crosslinked with polyols, copolymers of acrylamidopropyltrimethyl ammonium chloride 60

/ acrylate, octyl acrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers, polyvinyl pyrrolidone, vinyl pyrrolidone / vinyl acetate copolymers, vinyl pyrrolidone terpolymers / optionally dimethylaminoethyl cellulose / cetyl ethacrylates .

Suitable silicone compounds are, for example, dimethylpolysiloxanes, methylfe-5 nylpolysiloxanes, cyclic silicones, and also silicone compounds modified with amino, fatty acid, alcohol, polyether, epoxy, fluorine, glycoside and / or alkyl, which at room temperature can be in form either liquid or resinous. Also suitable are simethicones, which are mixtures of dimethicones having an average chain length of 200 to 300 units of dimethylsiloxane with hydrogenated silicates. A detailed study of Todd and 10 collaborators of suitable volatile silicones can also be found in Cosm. Toil 91, 27 (1976).

Typical examples of fats are glycerides, and as waxes can be taken into account, among others, beeswax, carnauba wax, candelilla wax, montana wax, paraffin wax, hydrogenated castor oils and fatty acid esters or microceras solid at room temperature optionally in combination with hydrophilic waxes, for example cetyl stearyl alcohol or partial glycerides. Metal salts of fatty acids, for example magnesium stearate or ricinoleate, aluminum and / or zinc, can be used as stabilizers.

Active biogenic ingredients are to be understood in the sense, for example, of tocopherol, tocopherol acetate, tocopherol palmitate, ascorbic acid, deoxyribonucleic acid, retinol, bisabolol, allantoin, phytantriol, panthenol, AHA acids, amino acids, ceramides, pseudoceramides, 20 Essential oils, plant extracts and vitamin complexes.

As active deodorant ingredients are considered, for example, antiperspirants, for example aluminum hydrochlorides (see J. Soc. Cosm. Chem. 24, 281 (1973)). Under the Locron® brand of Hoechst AG, Frankfurt (FRG), an aluminum hydrochloride corresponding to the formula Al2 (OH) 5Cl x 2.5 H2O is commercially available, for which use is especially preferred (see 25 J. Pharm Pharmacol. 26, 531 (1975)). In addition to hydrochlorides, it is also possible to use aluminum hydroxyacetates and acidic aluminum / zirconium salts. Stearase inhibitors can be added as additional active deodorant ingredients. Such inhibitors are preferably trialkyl citrates, such as trimethyl citrate, tripropyl citrate, triisopropyl citrate, tributyl citrate and especially triethyl citrate (Hydagen® CAT, Henkel KGaA, Düsseldorf / FRG), which inhibit enzymatic activity and therefore reduce formation Of smell. Other substances that are taken into account as esterase inhibitors are sterol sulfates or phosphates, for example lanosterol sulfate or phosphate, cholesterol, campesterol, stigmasterol and sitosterol, dicarboxylic acids and esters thereof, for example glutaric acid, monoethyl ester of the glutaric acid, diethyl ester of glutaric acid, adipic acid, monoethyl ester of adipic acid, diethyl ester of adipic acid, malonic acid and diethyl ester of malonic acid and hydroxycarboxylic acids and esters thereof, for example citric acid, malic acid, tartaric acid or diethyl ester of tartaric acid. Antibacterial active ingredients that influence microbial flora and kill or inhibit the growth of sweat-decomposing bacteria may also be present in preparations (especially in bar preparations). Examples include chitosan, phenoxyethanol and chlorhexidine gluconate. 5-Chloro-2- (2,4-dichlorophenoxy) -40 phenol (Irgasan®, Ciba Specialty Chemicals Inc.) has also proven to be especially effective.

As anti-dandruff agents, for example, climbazole, octopyrox and zinc pyrithione can be used. Typical film formers include, for example, chitosan, microcrystalline chitosan, quaternary chitosan, polyvinyl pyrrolidone, vinyl pyrrolidone / vinyl acetate copolymers, cellulose quaternary derivative polymers containing a high proportion of acrylic acid, collagen, hyaluronic acid and salts thereof and similar compounds. As swelling agents for aqueous phases, montmorillonites, clay mineral substances, Pemulen and also modified types of Carbopol (Goodrich) alkyl can be used. Other suitable polymers and swelling agents can be found in the review made by R. Lochhead in Cosm. Toil 108, 95 (1993). fifty

In addition to the primary substances for protection against sunlight it is also possible to use substances for protection against sunlight of antioxidant type that interrupts the activated photochemical reaction chain when UV radiation penetrates the skin or hair. Typical examples of such antioxidants are amino acids (for example glycine, histidine, tyrosine, tryptophan) and derivatives thereof, imidazoles (for example urocanic acid) and derivatives thereof, peptides, such as 55 D, L-carnosine, D- Camosin, L-carnosine and derivatives thereof (for example anserine), carotinoids, carotenes (for example α-carotene, β-carotene, lycopene) and derivatives thereof, chlorogenic acid and derivatives thereof, lipoic acid and derivatives thereof (for example dihydrolipoic acid), aurothioglycoside, propylthiouracil and other thiols (for example thioredoxin, glutathione, cysteine, cystine, cystamine and glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl, lauryl, palmitoyl, oleil, γ-60

linoleil, cholesteryl and glyceryl esters thereof) and also salts thereof, dilauryl thiodipropionate, distearyl thiodipropionate, thiodipropionic acid and derivatives thereof (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) and also sulfoximin compounds ( for example butionine sulfoximins, homocysteine sulfoximin, butionine sulfones, penta, hexa, heptathione sulfoximin) in very small tolerable amounts (for example from pmoles up to 5 µmol / kg), also chelating agents (metallic) (for example α-hydroxy fatty acids , palmitic acid, phytic acid, lactoferrin), α-hydroxy acids (for example citric acid, lactic acid, malic acid), humic acid, bile acid, bile extracts, bilirubin, biliverdin, EDTA, EGTA and derivatives thereof, acids unsaturated fatty acids and derivatives thereof (for example γ-linolenic acid, linoleic acid, oleic acid), folic acid and derivatives of l themselves, ubiquinone and ubiquinol and 10 derivatives thereof, vitamin C and derivatives (for example ascorbyl palmitate, ascorbyl magnesium phosphate, ascorbyl acetate), tocopherols and derivatives (for example vitamin E acetate), vitamin A and derivatives (for example, vitamin A palmitate) and also coniferyl benzoate of benzoin resin, rutinic acid and derivatives thereof, α-glycosylrutinic, ferulic acid, furfurylidene glucitol, carnosine, butyl hydroxytoluene, butyl hydroxyanisole, nordihydroguaarytic acid resins 15-nordihydroetone tri-hydroxy nibutyl trianedihydroxy nibutyl trichlorate , uric acid and derivatives thereof, mannose and derivatives thereof, superoxide dismutase, N- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] sulfanilic acid (and salts thereof, for example disodium salts), zinc and derivatives thereof (for example ZnO, ZnSO4), selenium and derivatives thereof (for example selenium methionine), stilbene and derivatives thereof (for example oxid or stilbene, trans-stilbene oxide) and suitable derivatives according to the invention (salts, esters, ethers, sugars, nucleotides, nucleosides, peptides and lipids) of those active ingredients mentioned. The HALS compounds can also be mentioned (= "Stabilized Amine Light Stabilizers"). The amount of antioxidants present is usually 0.001 to 30% by weight, preferably 0.01 to 3% by weight, based on the weight of the UV absorber (s). 25

To improve the flow behavior it is also possible to use hydrotropic agents, for example ethanol, isopropyl alcohol or polyols. The polyols that are taken into account for that purpose preferably have from 2 to 15 carbon atoms and at least two hydroxy groups.

The polyols may also contain additional functional groups, especially amino groups, and / or may be modified with nitrogen. Typical examples are as follows:

- glycerol;

- alkylene glycols, for example ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, hexylene glycol and also polyethylene glycols having an average molecular weight of 100 to 1000 Dalton;

- technical mixtures of oligoglycerol having an intrinsic degree of condensation of 1.5 to 10, for example technical mixtures of diglycerol having a diglycerol content of 40 to 50% by weight; 35

- methylol compounds, such as, especially, trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol and dipentaerythritol;

- lower alkyl glycosides, especially those having 1 to 8 carbon atoms in the alkyl radical, for example methyl and butyl glycoside;

- sugar alcohols having 5 to 12 carbon atoms, for example sorbitol or mannitol; 40

- sugars having 5 to 12 carbon atoms, for example glucose or sucrose;

- amino sugars, for example glucamine;

- dialcohol amines, such as diethanolamine or 2-amino-1,3-propanediol.

Suitable preservatives include, for example, phenoxyethanol, formaldehyde solution, Parabens, pentanediol or sorbic acid and the classes of additional substances listed in List 6, 45 Parts A and B of the Cosmetic Regulations.

Mixtures of natural and / or synthetic aromatic substances may be mentioned as perfume oils. Natural aromatic substances are, for example, floral extracts (lilac, lavender, roses, jasmine, neroli, ylang-ylang), stems and leaves (geranium, patchouli, petit grain), fruit (anise, coriander, cumin, juniper) , fruit skin (bergamot, lemons, oranges), roots (mace, angelica, 50 celery, cardamom, Costus, iris, Calmus), wood (pine, sandalwood, guayacan, cedar, rosewood), of grasses and grasses (tarragon, lemongrass, sage, thyme), of needles and branches (fir, pine, wild pine, mountain pine), of resins and balms (gálbano, elemí, benjuí, myrrh, olíbano, opopónaco). Also considered raw materials of animals, for example algalia and castóreo.

Typical synthetic aromatic substances are, for example, products of the ester, ether, aldehyde, ketone, alcohol or hydrocarbon type.

Compounds of ester type aromatic substances are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl format, glycinate ethylmethylphenyl, allylcyclohexyl propionate, stiralyl propionate and benzyl salicylate. The ethers include, for example, benzyl ethyl ether; aldehydes include, for example, linear alkanols having 8 to 18 carbon, citral, citronelal, citronellyl oxyacetaldehyde, cycladen aldehyde, hydroxycitronellal, lilial, and bourgeonal hydroatomers; ketones include, for example, ionones, α-isomethylionone and methyl cedryl ketone; alcohols include, for example, anethole, citronellol, eugenol, isoeugenol, geraniol, linalool, phenyl ethyl alcohol and terpinol; and hydrocarbons mainly include terpenes and balms. It is preferable, however, to use mixtures of different aromatic substances that together produce an attractive odor. Essential oils of relatively low volatility, which are mainly used as aroma components, are also suitable as perfume oils, for example sage oil, chamomile oil, clove oil, lemon balm oil, cinnamon leaf oil, Lemon flower oil, juniper berry oil, vetiver oil, olive oil, radish oil, labolanum oil and lavandina oil. Preference is given to the use of bergamot oil, dihydromyrcenol, lilial, liral, citronellol, phenyl ethyl alcohol, α-hexyl cinnamaldehyde, geraniol, benzyl acetone, cyclamen aldehyde, linalool, strong boisambrene, ambroxane, indole, hedion, sandelice, oil lemon, tangerine oil, orange oil, allyl amyl glycolate, cyclovertal, 20 lavandina oil, muscatel sage oil, β-damascone, bourbon geranium oil, cyclohexyl salicylate, vertofix coeur, iso-E-Super, Fixolide NP, Evernil, gamma iraldein, phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide, romillat, irotil and floramat alone or mixed together.

Substances that are suitable and allowed for cosmetic purposes, such as those collected, can be used as colorants, for example, in the publication "Kosmetische Färbemittel" 25 of the Farbstoffkommission der Deutschen Forschungsgemeinschaft, Verlag Chemie, Weinheim, 1984, pages 81 to 106. Usually they use the dyes in concentrations of 0.001 to 0.1% by weight, based on the total mixture.

Typical examples of bacterial inhibitory agents are preservatives that have a specific action against highly positive bacteria, such as 2,4,4'-trichloro-2'-hydroxydiphenyl ether, chlorhexidine (1,6-di (4-chlorophenyl-biguanido) ) hexane) or TCC (3,4,4'-trichlorocarbanilide). A lot of aromatic substances and essential oils also have antimicrobial properties.

Typical examples are the active ingredients eugenol, menthol and thymol in clove oil, peppermint oil and thyme oil. A natural deodorant agent of interest is farnesol terpene alcohol (3,7,11-trimethyl-2,6,10-dodecatrien-1-ol), which is present in lemon flower oil. Glycerol monolaurate has also proven to be a bacteriostatic agent. The amount of additional bacterial inhibitors present is usually 0.1 to 2% by weight, based on the solids content of the preparations.

It is also possible that cosmetic preparations contain, as adjuvants, defoamers, such as silicones, structuring agents, such as maleic acid, solubilizers, such as ethylene glycol, propylene glycol, glycerol or diethylene glycol, opacifiers, such as latex, styrene copolymers / PVP or styrene / acrylamide, complexing agents, such as EDTA, NTA, β-alannediacetic acid or phosphonic acids, propellants, such as propane / butane mixtures, N2O, dimethyl ether, CO2, N2 or air, called coupling components and developers with oxidation coloring precursors, reducing agents, such as thioglycolic acid and derivatives thereof, thiolactic acid, cysteamine, thiomalic acid or α-mercaptoethanesulfonic acid, or oxidation agents, such as hydrogen peroxide, potassium bromate or bromate of sodium.

They are considered as insect repellents, for example, N, N-diethyl-m-toluamide, 1,2-pentanediol or insect repellent 3535; Suitable self-tanning agents are, for example, dihydroxyacetone, erythrulose or mixtures of dihydroxyacetone and erythrulose. fifty

The cosmetic formulations according to the invention are contained in a wide variety of cosmetic preparations. For example, the following preparations are especially considered:

- skin care preparations, for example preparations for cleaning and washing the skin in the form of liquid or bar soaps, synthetic detergents or washing creams, 55

- bath preparations, for example liquid bath preparations (bubble baths, milks, shower preparations) or solid, for example bath cubes and bath salts;

- skin care preparations, for example skin emulsions, multi-emulsions or skin oils;

- preparations for personal cosmetic care, for example facial makeup in the form of day creams or powder creams, facial powders (loose or compact), cream or blush makeup, eye care preparations, for example, shadows, mascara, eyeliner, 5 eye creams or eye creams, lip care preparations, for example lipsticks, lip gloss, eyeliners, nail care preparations, such as nail polishes, enamel removers, nail hardeners or cuticle removers;

- foot care preparations, for example foot baths, foot powders, foot creams or foot balms, special deodorants and antiperspirants or 10 key remover preparations;

- protective preparations against sunlight, such as sun milk, lotions, creams or oils, sunscreen or tropical sunscreen, preparations before tanning or preparations after tanning;

- tanning preparations, for example self-tanning creams; fifteen

- depigmenting preparations, for example skin bleaching preparations or skin lightening preparations;

- insect repellents, for example oils, lotions, atomizers or insect repellent bars;

- deodorants, such as atomizer deodorants, pump-powered atomizers, gel, bar or ball deodorants; twenty

- antiperspirants, for example stick, cream or ball antiperspirants;

- preparations for cleaning and care of stained skin, for example synthetic detergents (liquids or solids), flaking preparations or scrubs or peeling masks;

- chemical hair removal preparations (depilation), for example hair removal powders, liquid hair removal preparations, cream or paste preparations 25 for hair removal, gel preparations for hair removal or foams in aerosol;

- shaving preparations, for example shaving soap, foaming shaving creams, non-foaming shaving creams, foams and gels, pre-shave preparations for dry shaving, after shaving or after shave lotions of shaving;

- fragrance preparations, for example fragrances (eau de Cologne, eau de toilette, eau de 30 parfum, parfum de toilette, perfume), scented oils or scented creams;

- cosmetic preparations for the treatment of hair, for example preparations for washing hair in the form of shampoos and conditioners, preparations for hair care, for example preparations for pretreatment, hair tonics, styling creams, styling gels, ointments, rinses capillaries, packaging for treatment, intensive treatments for hair, hair structuring preparations, for example hair waving preparations for permanent waves (soft, medium and strong wavy), hair straightening preparations, liquid hair conditioning preparations, hair foams, hair sprayers, bleaching preparations, for example hydrogen peroxide solutions, lightening shampoos, bleaching creams, bleaching powders, bleaching pastes or oils, 40 permanent, semi-permanent or temporary hair dyes, preparations containing dyes self oxidizers, or natural hair dyes, such as henna or chamomile.

The final formulations listed may exist in a variety of presentation forms, for example:

- in the form of liquid preparations such 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,

- in the form of an oil, a cream, milk or lotion,

- in the form of a powder, a lacquer, a pill or makeup,

- in the form of a bar,

- in the form of an atomizer (atomizer with propellant gas or pump-powered atomizer) or an aerosol,

- in the form of a foam, or

- in the form of a paste. 5

Of special importance as cosmetic preparations for the skin are protective preparations against sunlight, such as sun milk, lotions, creams, oils, sunscreen or tropical sunscreen, pre-tanning preparations or after-sun preparations, also tanning preparations. the skin, for example self tanning creams. Of particular interest are sunscreen creams, sunscreen lotions, sunscreen oils, sunscreen milks and sunscreen preparations in the form of an aerosol.

Of particular importance as cosmetic preparations for hair are the aforementioned preparations for the treatment of hair, especially preparations for washing hair in the form of shampoos, hair conditioners, 15 preparations for hair care, for example preparations for hair pretreatment, hair tonics, styling creams, styling gels, ointments, hair rinses, packaging for treatment, intensive hair treatments, hair straightening preparations, liquid preparations for conditioning hair, hair foams and atomizers for hair hair. Of special interest are preparations for washing hair in the form of shampoos. twenty

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 lauret-2-sulfate, 4.0% by weight of cocamidopropyl betaine, 3.0% by weight of sodium chloride, and water is added until 100% is completed.

For example, the following cosmetic formulations for hair can be used especially:

a1) a standard formulation that spontaneously emulsifies, consisting of the UV absorber according to the invention, PEG-6-C10 oxoalcohol and sorbitan sesquioleate, to which water and any desired quaternary ammonium compound are added, by Example 4% of minkamidopropyl dimethyl-2-hydroxyethylammonium chloride or Quaternium 80; 30

a2) a standard formulation that spontaneously emulsifies, 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 are added, for example 4% of minkamidopropyl dimethyl-2-hydroxyethylammonium chloride or Quaternium 80;

b) Quat doped solutions of the UV absorber according to the invention in butyl triglycol 35 and tributyl citrate;

c) mixtures or solutions of the UV absorber according to the invention with n-alkyl pyrrolidone.

The cosmetic preparation according to the invention is distinguished by an excellent protection of human skin against the harmful effect of sunlight. In the following Examples, the percentages are related to weight. The amounts of the triazine derivatives used are related to the pure substance.

Preparation Examples of the new compounds:

Example 1:

A suspension of 7 g (0.05 mol) of dimedone and 14.8 g (0.1 mol) of triethyl ester of orthoformic acid in 15 ml of isobutanol is refluxed for 2 hours. After cooling to room temperature, 4.6 g (0.025 mol) of 2,4-diamino-6-phenyl-1,3,5-triazine and 3 drops of trifluoromethanesulfonic anhydride are added. The reaction mixture is refluxed for 20 hours and then cooled to room temperature. The resulting crude product is filtered. The colorless product is obtained by means of column chromatography (silica gel) using a 9: 1 mixture of dichloromethane and methanol as eluent and dried at 60 ° C under vacuum. fifty

Yield: 1 g (8% of theory).

λmax = 320 nm; ε = 50 970, E (= extinction value) (1%, 1 cm) = 1045

γmax = 224 nm; ε = 35 699, E (1%, 1 cm) = 732

Example 2:

0.1 ml of trifluoromethanesulfonic anhydride, at 90 ° C, is added to a solution of 7.5 g (0.05 5 moles) of triethyl ester of orthoformic acid in 50 ml of isobutanol. Then 2.3 g (0.0125 mol) of 2,2-diamino-6-phenyl-1,3,5-triazine are introduced in portions over the course of 1.5 hours. The resulting solution is stirred for 30 minutes at 100 ° C. After the addition of 2.3 g (0.025 mol) of acetylacetone, the reaction mixture is refluxed for 4 hours. After cooling to room temperature, the suspension is filtered. The cake of the filtrate is recrystallized from ethyl acetate and dried in vacuo at 70 ° C. Yield: 1.3 g (26% of theory).

λmax = 322 nm; ε = 42 906, E (1%, 1 cm) = 1053 (in ethanol)

Example 3:

7.2 g (0.05 mol) of the cyclic isopropylidene ester of malonic acid, 14.8 g (0.1 15 mol) of triethyl ester of orthophoric acid and 4.6 g (0.025 mol) of diaminophenyltriazine are mixed in 150 ml of toluene and then refluxed for 1 hour. Within 2 hours, 2.5 g of phosphoryl chloride are added dropwise and the reaction mixture is refluxed for an additional 2 hours. After cooling to room temperature, 100 ml of water and 100 ml of ethyl acetate are added. The organic phase is separated and heated for 30 minutes at 40-50 ° C together with 5 g 20 of sodium sulfate and 5 g of Tonsil. After filtration of the mixture while it is still hot, the filtrate is concentrated to dryness by evaporation. After column chromatography (silica gel) using a 7: 3 mixture of toluene and acetone, the pure product is obtained, which is dried under vacuum at 80 ° C. Yield: 5 g (40% of theory).

 25

λmax = 332 nm; ε = 68 068, E (1%, 1 cm) = 1374 (in dioxane)

Example 4:

In a sulfonation vessel equipped with a reflux condenser and a calcium chloride drying tube, 4.78 g (0.025 mol) of 2,4-diamino-6-phenyl-1,3,5-triazine are mixed, 9.96 g (0.075 mol) of ethyl acetoacetate, 8.12 g (0.075 mol) of trimethyl ester of orthoformic acid and 1.03 g 5 (0.006 mol) of copper (II) chloride dihydrate in 50 ml of dimethylacetamide and Stir for 3 hours at 70 ˚C. After cooling to room temperature, the reaction mixture is stirred in 200 ml of a 10% sodium sulfate solution. The precipitate that forms is filtered, washed with water until neutral and recrystallized from ethanol. The product is dried under vacuum at 60 ° C. Yield: 4.1 g (35% of theory). 10

Yield: 4.1 g (35% of theory)

λmax = 319 nm; ε = 45 969, E (1%, 1 cm) = 983 (in ethanol)

Example 5:

3.22 g (0.025 mol) of melamine, 14.94 g (0.1225 mol) of ethyl acetoacetate, 12.18 g (0.125 mol) of orthoformic acid trimethyl ester and 1.03 g ( 0.006 mol) of copper (II) chloride dihydrate in 50 ml of N-methylpyrrolidone and stirred for 4 hours at 80 ° C. The cold reaction mixture is added to 400 ml of 5% aqueous sodium sulfate solution. The precipitate that forms is filtered, washed with water and recrystallized from ethanol. The product is dried under vacuum at 60 ° C. Yield: 6.5 g (48% of theory). twenty

γmax = 325 nm; ε = 790448, E (1%, 1 cm) = 1350 (in dioxane)

Example 6:

3.22 g (0.025 mol) of melamine, 16.60 g (0.113 mol) of cyclic isorpopilidene ester of malonic acid, 17.09 g (0.133 mol) of triethyl ester of orthophoric acid and 1.03 g (0.006 are stirred. 25 moles) of copper (II) chloride dihydrate in 50 ml of N-methylpyrrolidone for 6 hours at 80 ° C. The cold reaction mixture is added to 400 ml of 5% aqueous sodium sulfate solution. The resulting precipitate is filtered, washed with water and copious amounts of ethanol. The product is dried under vacuum at 60 ° C. Yield: 6.2 g (42% of theory).

λmax = 326 nm; ε = 61 956, E (1%, 1 cm) = 1053 (in dioxane)

Example 6: Parallel synthesis of the compounds of the general formula

General Procedure: 5

2,4-Diamino-6-phenyl-1,3,5-triazine (0.0013 mol, 0.24 g) is dissolved in N-methylpyrrolidone (1.15 ml). To the trimethyl ester solution of orthoformic acid (0.0038 mol, 0.42 ml), solution of dihydrated copper chloride (0.0013 mol, 0.22 g in 0.5 ml of NMP) and the appropriate acetone are added (0.0038 moles dissolved in 2 ml of NMP). The reaction mixture is stirred for 4 hours at 70 ° C. The crude product is precipitated by the addition of 10 ml of 10% 10% aqueous sodium sulfate solution, and then the precipitate is filtered and washed with copious amounts of ethanol. After column chromatography (Nucleosil 5C18) using a mixture of acetonitrile and water the pure product is obtained.

Example 7: Parallel synthesis of compounds of formula

 fifteen

General procedure:

Melamine (0.0013 mol, 0.17 g) is dissolved in N-methylpyrrolidone (1.42 ml). To the trimethyl ester solution of orthoformic acid (0.0057 mol, 0.59 ml), solution of dihydrated copper chloride (0.0013 mol, 0.22 g in 0.5 ml of NMP) and the appropriate ketone are added (0.0057 moles dissolved in 2 ml of NMP). The reaction mixture is stirred for 4 hours at 80˚C. The crude product 20 is precipitated by the addition of 10 ml of 10% aqueous sodium sulfate solution, and then the

precipitated and washed with copious amounts of ethanol. After column chromatography (Nucleosil 5C18) using a mixture of acetonitrile and water the pure product is obtained.

Example 8: Parallel synthesis of compounds of formula

General Procedure: 5

2,4-Diamino-6-p-methoxyphenyl-1,3,5-triazine (0.0005 mol, 0.11 g) is dissolved in N-methylpyrrolidone (0.6 ml). To the trimethyl ester solution of orthoformic acid (0.0013 mol, 0.14 ml), solution of dihydrated copper chloride (0.0013 mol, 0.22 g in 0.5 ml of NMP) and the appropriate ketone are added (0.0005 moles dissolved in 0.23 ml of NMP). The reaction mixture is stirred for 4 hours at 80˚C. The crude product is precipitated by the addition of 10 ml of 10% aqueous solution of 10% sodium sulfate, and then the precipitate is filtered and washed with copious amounts of ethanol. After column chromatography (Nucleosil 5C18) using a mixture of acetonitrile and water the pure product is obtained.

Example 9: Parallel synthesis of compounds of formula

 fifteen

General procedure:

2,4-Diamino-6-methyl-1,3,5-triazine (0.0013 mol, 0.16 g) is dissolved in N-methylpyrrolidone (1.5 ml). To the trimethyl ester solution of orthoformic acid (0.0038 mol, 0.42 ml), solution of dihydrated copper chloride (0.0013 mol, 0.22 g in 0.5 ml of NMP) and the appropriate ketone are added (0.0038 moles dissolved in 2 ml of NMP). The reaction mixture is stirred for 4 hours at 70 ° C. The crude product is precipitated by the addition of 10 ml of 10% aqueous sodium sulfate solution, and then the precipitate is filtered and washed with copious amounts of ethanol. After column chromatography (Nucleosil 5C18) using a mixture of acetonitrile and water the pure product is obtained.

Application Examples 25

Example 10: Sunscreen Lotion

 INCI Name% p / p

 Part A

 Glyceryl Stearate (y) Stearate PEG-100 Stearyl Alcohol Tripalmitin 5.00 1.00 0.70

 Dimethicone Alkyl Benzoate C12-15 Isopropyl Palmitate Ethylhexyl Methoxycinnamate

 2.00 5.00 5.00 3.00

 Part B

 Water Polysorbate 60 Glycerin qs * up to 100 0.50 3.00

 Part C

 Water Compound of formula 101 or 102 or 103 or 104 or 105 or 106 10.00 8.00

 Part D

 Phenoxyethanol (y) Methylparaben (y) Ethylparaben (y) Butylparaben (y) Propylparaben (e) Isobutylparaben Steareth-10 copolymer Alyl Ether / Acrylates 0.70 1.50

 Part E

 Water (e) Sodium Hydroxide qs

 Part F

 Fragrance qs

(* qs = from Latin quantum sufficit., sufficient quantity. (N. of T.))

This emulsion is easy to spread with good absorption properties.

Manufacturing instructions:

Heat part A and B separately up to 75˚C; part C at 60˚C. Then pour part B into part A with stirring. Homogenize with an Ultra Turrax homogenizer for 30 s at 11,000 rpm and add part C. Allow to cool to 40˚C and add part D. Adjust the pH value with Sodium Hydroxide to room temperature between 6.30 and 6.70 and add part F.

Example 11: Sunscreen Spray Lotion

 INCI Name% p / p

 Part A

 Cetil Phosphate Potassium 0.20

 Isohexadecane 7.00

 VP / Eicosano 1.50 copolymer

 C12-13 dialkyl tartrate 6.00

 Ethylhexyl Triazone 2.50

 C12-15 alkyl benzoate 4,50

 Part B

 Water qs up to 100

 Sorbeth-30 2.00

 Sorbitan Stearate (y) Cocoa de Sacarosa 4.00

 Titanium Dioxide (y) Alumina (y) Silica (y) Sodium Polyacrylate 2.50

 Part C

 Water 30.00

 Compound of formula 101 or 102 or 103 or 104 or 105 or 106 12.00

 Part D

 Phenoxyethanol (y) Methylparaben (y) Ethylparaben (y) Butylparaben (y) Propylparaben (e) Isobutylparaben 0.70

 Part E

 Water (y) Citric Acid qs

This emulsion contains a combination of insoluble UV absorber. The choice of emollients provides rapid absorption and a feeling of softness in the skin.

Instructions for its elaboration:

Heat part A and B separately up to 80˚C; part C at 50˚C. Pour part B into part A and homogenize with an Ultra Turrax homogenizer for 1 minute at 11,000 rpm. After cooling to 50˚C add part C under continuous stirring. At 40 ° C incorporate part D and homogenize again for 10 s at 11000 rpm. Adjust the pH with part E.

Example 12: Sunscreen lotion, water resistant

 INCI Name% p / p

 Part A

 Cetearyl Alcohol (y) Dicethyl Phosphate (y) Ceteth-10 Phosphate 4.00

 C12-15 Alkyl Benzoate 2.00

 Dicaprilil Ether 3.00

 Ethoxyglycol Oleate 2.00

 Stearic Acid 1.00

 Ethylhexyl Methoxycinnamate 3.00

 Copolymer of Sodium Acrylates (y) Soy Glycine (y) PPG-1 Trideceth-6 0.30

 Squalane 3.50

 VP / Eicosano Copolymer 2.00

 Part B

 Water qs up to 100

 Compound of formula 101 or 102 or 103 or 104 or 105 or 106 5.00

 Part C

 Diazolidinyl Urea (y) Yodopropinyl Butyl Carbamate 0.15

 Propylene Glycol 2.50

 Water 10.00

 Part D

 Cyclopentasiloxane (y) Dimethiconol 2.00

 Ethoxydiglycol 5.00

 Cyclopentasiloxane (y) Crosslinked Dimeticone / Vinyl Dimeticone Polymer 2.00

(continuation)

 INCI Name% p / p

 Part E

 Water (e) Sodium Hydroxide qs

 Part F

 Fragrance qs

O / W emulsion with a touch of softness and good rub-off properties. 10

Instructions for its elaboration:

Heat part A and part B separately to 75˚C. Pour part B into part A under progressive stirring speed. Under 65˚C add the ingredients of part D. separately. Let cool to 55˚C with moderate stirring and add part C. Under 35˚C check and adjust the pH with Sodium Hydroxide and homogenize with a homogenizer Ultra Turrax 15 for 30 s at 11 000 rpm. At room temperature add part F.

Example 13:

 INCI Name% p / p

 Part A

 Cetyl Potassium Phosphate 2.00

 Tricontanil PVP 1.00

 Capric / Capric Triglyceride 5.00

 C12 Alkyl Benzoate - 15 5.00

 Cetearyl Isononanoate 5.00

 Glyceryl Stearate 3.00

 Cetil Alcohol 1.00

 Dimethicone 0.10

 Ethylhexyl Methoxycinnamate 5.00

 Part B

 Water qs up to 100

 Glycerin 3.00

 Part C

 Copolymer of Steareth-10 Alil Ether / Acrylates 0.50

 Part D

 Compound of formula 101 or 102 or 103 or 104 or 105 or 106 8.00

 Part E

 Phenoxyethanol (y) Methylparaben (y) Ethylparaben (y) Butylparaben (y) Propylparaben (e) Isobutylparaben 1.00

 Part F

 Water (e) Sodium Hydroxide qs up to pH 7.00

 Part G

 Fragrance qs

This emulsion is soft spreads easily. The choice of the main light emollients gives the lotion a light and non-sticky feeling on the skin.

Instructions for its elaboration:

Heat part A and part B separately to 80˚C. Pour part B into part A under 5 moderate agitation. Homogenize with an Ultra Turrax homogenizer at 11000 rpm for 1 minute. Allow to cool to 70˚C and add part C with stirring. Cool further to 50˚C and incorporate TINOSORB® M very slowly. At 40˚C add part E. At room temperature adjust the pH with part F at 7.00 and add part G.

Example 14: Water resistant O / W emulsion 10

 INCI Name% p / p

 Part A

 Cetearyl Alcohol (y) Dicethyl Phosphate (y) Ceteth-10 Phosphate 4.00

 C12 Alkyl Benzoate - 15 2.00

 Dicaprilil Ether 3.00

(continuation)

 INCI Name% p / p

 Ethoxyglycol Oleate 2.00

 Stearic Acid 1.00

 Ethylhexyl Methoxycinnamate 3.00

 Copolymer of Sodium Acrylates (y) Soy Glycine (y) PPG-1 Trideceth-6 0.30

 Squalane 3.50

 VP / Eicosano Copolymer 2.00

 Part B

 Water qs up to 100

 Compound of formula 101 or 102 or 103 or 104 or 105 or 106 5.00

 Part C

 Diazolidinyl Urea (y) Yodopropinyl Butyl Carbamate 0.15

 Propylene Glycol 2.50

 Water 10.00

 Part D

 Cyclopentasiloxane (y) Dimethiconol 2.00

 Ethoxydiglycol 5.00

 Cyclopentasiloxane (y) Crosslinked Dimeticone / Vinyl Dimeticone Polymer 2.00

 Part E

 Water (e) Sodium Hydroxide qs

 Part F

 Fragrance l qs

O / W emulsion with a touch of softness and good rub-off properties.

Instructions for its elaboration:

Heat part A and part B separately to 75˚C. Pour part B into part A with progressive stirring speed. Below 65˚C, add the ingredients of part 5 separately. Allow to cool to 55˚C with moderate agitation and add part C. Below 35˚C, check and adjust the pH with Sodium Hydroxide and homogenize with a Ultra Turrax homogenizer for 30 s at 11 000 rpm.

At room temperature add part F.

Example 14: Sunscreen Lotion, type O / W 10

 INCI Name% p / p

 Part A

 Cetyl Potassium Phosphate 2.00

 Tricontanil PVP 1.00

 Capric / Capric Triglyceride 5.00

 C12 Alkyl Benzoate - 15 5.00

 Cetearyl Isononanoate 5.00

 Glyceryl Stearate 3.00

 Cetil Alcohol 1.00

 Dimethicone 0.10

 Ethylhexyl Methoxycinnamate 5.00

 Part B

 Water qs up to 100

 Glycerin 3.00

 Part C

 Copolymer of Steareth-10 Alil Ether / Acrylates 0.50

 Part D

 Compound of formula 101 or 102 or 103 or 104 or 105 or 106 20.00

 Part E

 Phenoxyethanol (y) Methylparaben (y) Ethylparaben (y) Butylparaben (y) Propylparaben (e) Isobutylparaben 1.00

(continuation)

 INCI Name% p / p

 Part F

 Water (e) Sodium Hydroxide qs up to pH 7.00

 Part G

 Fragrance qs

This emulsion is soft and spreads easily.

Instructions for its elaboration:

Heat part A and part B separately to 80˚C. Pour part B into part A under moderate agitation. Homogenize with an Ultra Turrax homogenizer at 11000 rpm for 1 minute. 5 Let cool to 70˚C and add part C with stirring. Cool further to 50˚C and incorporate TINOSORB® M very slowly. At 40˚C add part E. At room temperature adjust the pH with part F up to 7.00 and add part G.

REFERENCES CITED IN THE DESCRIPTION

This list of references cited by the applicant is solely for the convenience of the reader. It is not part of the European patent document. Although great care has been taken in the collection, errors or omissions cannot be excluded and the EPO rejects any responsibility in this regard. 5

Patent documents cited in the description

• EP 582189 A [0028] • EP 507691 A [0028]

• US 5338539 A [0028] • WO 9317002 A [0028]

• US 5518713 A [0028] • EP 570838 A [0028]

• EP 613893 A [0028] • US 5928630 A [0028] 10

• EP 709080 A [0028] • DE 4105923 A1 [0028]

• US 5601811 A [0028] • DE 1165574 A [0046]

• WO 9700851 A [0028] • FROM 2024051 A [0047]

• US 5332568 A [0028] • FR 2252840 A [0057]

• EP 517104 A [0028] 15

Literature cited in the non-patent description

• Todd et al. Cosm. Toil., 1976, vol. 91, 27 [0059]

• J. Soc. Cosm. Chem., 1973, vol. 24,281 [0062]

• J. Pharm. Pharmacol., 1975, vol. 26,531 [0062]

• R. Lochhead. Cosm. Toil., 1993, vol. 108, 95 [0063] 20

• Kosmetische Färbemittel. Farbstoffkommission der Deutschen Forschungsgemeinschaft. Verlag

Chemie, 1984, 81-106 [0070]

Claims (13)

1. A compound of formula

where R1 is a C1-C18 alkyl, C2-C18 alkenyl, C6-C10 aryl or C6-C10 heteroaryl radical each one unsubstituted or mono or polysubstituted by hydroxy, C1-C18 alkyl, C1-C18 alkoxy, amino, C1-C5 monoalkylamino or by C1-C5 dialkylamino; C5-C7 cycloalkyl or C5-C7 cycloalkenyl each substituted or unsubstituted by C1-C5 alkyl; -OR ’; or -NR’R "; R2 is hydrogen; a C1-C18 alkyl radical, C2-C18 alkenyl; C6-C10 aryl or C6-C10 heteroaryl each unsubstituted or mono or polysubstituted by hydroxy, C1-C18 alkoxy, cyano, amino, C1-C5 monoalkylamino or C1-C5 dialkylamino; -OR ’; or -NR’R "; or R1 and R2 together form a 5- to 7-membered heterocyclic or carbocyclic ring; A is C1-C5 alkyl; a C6-C10 aryl or heteroaryl radical substituted with C1-C18 alkoxy or C1-C18 alkyl or hydroxy or unsubstituted; or a radical of formula (1a) R 'and R "are each independently hydrogen from each other; C1-C18 alkyl substituted by a group of quaternary ammonium, amino, C1-C18 alkoxy, C1-C18 alkyl, halo, mono or polyhydroxy, or unsubstituted, phenyl or cycloalkyl C5-C7; R3 is hydrogen; or C1-C6 alkyl; and 20 n is 0 or 1.

2. A compound according to claim 1, wherein

R1 and R2 are each independently of the other C1-C18 alkyl or phenyl each substituted or unsubstituted by C1-C5 alkyl, hydroxy or C1-C5 alkoxy; -OR ’; or -NR’R "; or R1 and R2 together form a 5- to 7-membered heterocyclic or carbocyclic ring. 25

3. A compound according to either claim 1 or claim 2, wherein

R1 is C1-C5 alkyl; C1-C5 alkoxy; or phenyl substituted with C1-C5 alkoxy or hydroxy or C1-C5 alkyl or unsubstituted

4. A compound according to any one of claims 1 to 3, wherein

R2 is hydrogen; C1-C5 alkyl, C1-C5 alkoxy; phenyl substituted with C1-C5 alkoxy or C1-C5 alkyl, or hydroxy, or unsubstituted; Y n is 1.

5. A compound according to either claim 1 or claim 2, wherein

R1 and R2 together are a radical - (CH2) 2-5- that is not additionally substituted or substituted by one or more C1-C5 alkyl and is interrupted or not interrupted by one or two groups -O- and / or -NH - I

6. A compound according to claim 5, wherein

      R1 and R2 are both a radical Y       R5 is hydrogen; or C1-C5 alkyl.

7. A compound according to any one of claims 1 to 6, wherein

      A is amino; phenyl; or C1-C5 alkoxyphenyl.

8. A compound according to any one of claims 1 to 7, wherein

      R3 is hydrogen.

9. A process for the preparation of a triazine derivative of formula (1) according to claim 1, wherein the diaminotriazine compound of formula 15

with a compound of formula (1b) Y  twenty to form a compound of formula (1), wherein       R1 is C1-C5 alkyl and       R and R ’are as defined for formula (1), to form a compound of formula (1).

10. The use of a triazine derivative of formula (1) according to claim 1 for the protection of human and animal skin and hair against the harmful effect of UV radiation.

11. The use according to claim 10, wherein the triazine derivative of formula (1) is present in micronized form. 5

12. A cosmetic preparation containing at least one or more of the compounds of formula (1) according to claim 1 together with cosmetically tolerable carriers or adjuvants.

13. A preparation according to claim 12 further containing protective substances against UV radiation. 10