Title of Invention	COSMETIC PREPARATION COMPRISING A COMPOUND OF FORMULA (I)
Abstract	The present invention relates to a cosmetic preparation comprising at least one compound of formula R<SUB>1</SUB>is hydrogen; unsubstituted or halo-, amino-, mono- or di-C<SUB>1</SUB>-C<SUB>5</SUB>alkylamino-, cyano- or C<SUB>1</SUB>-C<SUB>5</SUB> alkoxy-substituted C<SUB>1</SUB>C<SUB>22</SUB>alkyl, C<SUB>5</SUB>-C<SUB>10</SUB>cycloalkyl, carboxy-C<SUB>1</SUB> -C<SUB>22</SUB>alkyl, carboxy-C<SUB>6</SUB>-C<SUB>10</SUB>aryl, C<SUB>6</SUB>-C<SUB>10</SUB>aryl, C<SUB>6</SUB>-C<SUB>10</SUB>aryl-C<SUB>1</SUB>-C<SUB>5</SUB>alkyl; carbamoyl; or sulfamoyl; R<SUB>2</SUB> is branched or unbranched C<SUB>6</SUB>-C<SUB>12</SUB>alkyl: R<SUB>3</SUB> is hydrogen; or C<SUB>1</SUB>-C<SUB>22</SUB>alkyl; and R<SUB>4</SUB>is hydrogen; hydroxy; C<SUB>1</SUB>-C<SUB>22</SUB>alkyl; or C<SUB>1</SUB>-C<SUB>22</SUB>alkoxy; together with cosmetically acceptable carriers or adjuvants.

Title of Invention

COSMETIC PREPARATION COMPRISING A COMPOUND OF FORMULA (I)

Abstract

The present invention relates to a cosmetic preparation comprising at least one compound of formula R1is hydrogen; unsubstituted or halo-, amino-, mono- or di-C1-C5alkylamino-, cyano- or C1-C5 alkoxy-substituted C1C22alkyl, C5-C10cycloalkyl, carboxy-C1 -C22alkyl, carboxy-C6-C10aryl, C6-C10aryl, C6-C10aryl-C1-C5alkyl; carbamoyl; or sulfamoyl; R2 is branched or unbranched C6-C12alkyl: R3 is hydrogen; or C1-C22alkyl; and R4is hydrogen; hydroxy; C1-C22alkyl; or C1-C22alkoxy; together with cosmetically acceptable carriers or adjuvants.

Full Text	Aminophenylbenzothiazole compounds The present invention relates to the use of aminophenylbenzothiazole compounds as UV filters, especially for protecting human and animal hair and skin from UV radiation, to processes for the preparation of those compounds and to cosmetic preparations comprising those compounds. The present invention relates to the use, as UV filters, of compounds of formula R1 and R2 are each independently of the other hydrogen; unsubstituted or halo-, amino-, mono- or di-C1-C6alkylamino-, cyano- or C1-Csalkoxy-substituted C1-C22alkyl, C5-C10cycloalkyI, carboxy-C1-C22alkyl, carboxy-C6-C10aryl, Ce-Cioaryl or C6-C10aryl-C1-Csalkyl; carbamoyl; or sulfamoyl; or R1 and R2, together with the nitrogen atom linking them, form a 5- to 7-membered heterocyclic radical; and R3 is hydrogen; or C1-C22alkyl; and R4 is hydrogen; hydroxy; C1-C22alkyl; or C1-C22alkoxy. C1-C22Alkyl radicals are straight-chain or branched alkyl radicals such as, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, amyl, isoamyl ortert-amyl, hexyl, 2-ethylhexyl, heptyl, octyl, isooctyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl or eicosyl. C6-C10CycloaJkyl is, for example, cyclopentyl, cycloheptyl, cyclooctyi, cyclononyl or cyclodecyl and, especially, cyclohexyl. Those radicals may be substituted, for example by one or more identical or different C1-C4alkyl radicals, especially by methyl, and/or by hydroxy. When cycloalkyi radicals are substituted by one or more substituents, they are preferably substituted by one, two or four, especially one or two, identical or different substituents. C6-C10Aryl is naphthyl or, especially, phenyl. C1-C22Alkoxy radicals are straight-chain or branched radicals such as, for example, methoxy, ethoxy, propoxy, butoxy or pentyloxy, hexyloxy, heptyloxy, octyloxy, isooctyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tetradecyloxy, pentadecyloxy, hexadecyloxy, hepta-decyloxy, octadecyloxy or eicosyloxy. Heterocyclic radicals contain one, two, three or four identical or different ring hetero atoms. Special preference is given to heterocycles containing one, two or three, especially one or two, identical or different hetero atoms. The heterocycles may be mono- or poly-cyclic, for example mono-, bi- or tri-cyclic. They are preferably mono- or bi-cyclic, especially monocyclic. The rings are preferably 5-, 6- or 7-membered. Examples of monocyclic and bicyclic heterocyclic systems from which radicals occunring in the compounds of formula (1) may be derived are, for example, pyR1ole, furan, thiophene, imidazole, pyrazole, 1,2,3-triazole, 1,2,4-triazole, pyridine, pyridazine, pyrimidine, pyrazine, pyran, thiopyran, 1,4-dioxane, 1,2-oxazine, 1,3-oxazine, 1,4-oxazine, indole, benzothiophene, benzofuran, pyR1olidine, piperidine, piperazine, morpholine and thiomorpholine. Unsaturated heterocycles may contain, for example, one, two or three unsaturated double bonds in the ring system. 5-membered and 6-membered rings in monocyclic and polycyciic heterocycles may, especially, also be aromatic. C6-C10AryJ and heteroaryl radicals may be unsubstltuted or may caR1y one or more, for example one, two, three or four, identical or different substituents, which may be located in any positions. Examples of such substituents are, e.g., C1-C4alkyl, halogen, hydroxy, C1-C4alkoxy, trifluoromethyl, cyano, hydroxycarbonyl, C1-C4alkoxycarbonyl, aminocarbonyl, amino, C1-C4alkylamino, di-C1-C4alkylamino and C1-C4alkylcarbonylamino. Halogen is fluorine, chlorine, bromine or iodine, preferably fluorine or chlorine. In accordance with the invention, preference is given to the use of UV filters of fonnula (1) wherein R4 is hydrogen. Preference is given especially to compounds of formula (1) wherein R1 and R2 are each independently of the other hydrogen; or d-C12alkyl unsubstituted or substituted by halogen, amino, mono- ordi-C1-Qalkylamino, cyano or by C1-C5alkoxy; and R3 is hydrogen; or C1-Csalkyl. Special preference is given to compounds of formula (1) wherein Ri and R2 are each independently of the other hydrogen; or C1-Ciaalkyl; or Ri and R2 together form a 5- to 7-membered heterocyclic radical; R3 is hydrogen; or C1-CsalkyI; and R4 is hydrogen. Very special preference is given to compounds of formula (1) wherein Ri is hydrogen; R2 is C1-C12alkyl; R3 is hydrogen; or C1-C5alkyI; and R4 is hydrogen; and especially to compounds of formula (1) wherein R2 is branched or unbranched C6-C12alkyI; very especially n-hexyl; n-octyl; or 2-ethylhexyl. Very special preference is also given to compounds of formula (1) wherein R4 is hydroxy. Examples of compounds used in accordance with the Invention are listed in Table 1, which follows: Aminophenylbenzothiazole compounds are known in the literature and some are commercially available. The compounds of formula (1) according to the invention can be prepared, for example, by condensation of Ra-substituted o-amino-thiophenols of fomnula Rj-jJ- I with R1, R2- and R4 -substituted p-amino-benzaldehydes, where appropriate in the presence of an oxidising agent [R.C. Elderfield, "Heterocyclic Compounds", Vol. 5, 508 ff, O. Sus et aJ, US Patent 3 257 204 (1966), HP. Lankelma et a/, J. Amer. Chem. Soc. 54, 379, (1932) or Stephens ef a/., J. Chem. Soc. (1950) 1722]. Condensation of o-amino-thiophenols with Ri- and Ra-substituted p-aminobenzoic acids in accordance with LC. Galatis, J. Amer. Chem. See. 70, 1967 (1948) also yields compounds of the general formula (1). The benzothiazole compounds of the general formula (1) wherein R, is hydrogen and R2 is an unsubstituted or substituted aralkyi radical are obtained by reaction of F^-substituted 2-{4'-aminophenyO-benzothiazoles with unsubstituted or substituted benzaldehydes to fomn the coR1esponding azomethines, which may be hydrogenated very simply using sodium boronate in polar solvents to form the coR1esponding 2-{4'-benzylaminophenyl)benzothiazole derivatives [J. H. Billmann et a/., J. OR2. Chem. 22, 1068, (1957)]. The benzothiazole compounds of the general formula (1) wherein R, and/or R2 is/are an unsubstituted or substituted alkyl or aralkyi radical can also be prepared by direct alkylation of commercially available 2-{4-aminophenyl)-6-methylbenzothiazole. As alkylating agents there can be used, analogously to DE-OS-51738, the appropriate alcohols under the action of strong acids. The compounds of formula (1) according to the invention wherein Ri is hydrogen are prepared from Ra-substituted 2-{4-aminophenyl)-benzothiazole by alkylation with the appropriate haloalkanes/haloaralkanes using a base, in accordance with the following Scheme: wherein R2, R3 and R4 are as defined in claim 1. The compounds of fonnula (1) wherein Ri and R2 are alkyl or aryl-alkyi are prepared from R3-substituted 2-(4-aminophenyl)-benzothiazole by alkylation with the appropriate haloal¬kanes/haloaralkanes using a base, in accordance with the following Scheme: As base there may be used a metal hydride, such as sodium hydride, an alkali metal alcohoiate such as, for example, sodium methanoiate, sodium ethanoiate or potassium tert-butanolate, or an alkali metal hydroxide, such as sodium hydroxide or potassium hydroxide, an amine base, such as EtsN, (isoprop)2EtN or quinalidine etc.. Likewise, basic ion exchangers may also be used. The reaction may also be caR1ied out without the addition of base. The reaction is preferably caR1ied out in dimethyl sulfoxide, N-methylpyR1olidone, dimethyl-formamide or dimethylacetamide, but protic solvents, such as methanol, ethanol, isobutanol, tert-butanol or isopropanol, are also possible. In addition, the reaction may also be caR1ied out in aliphatic or aromatic solvents, such as hexane, toluene or xylene. Ethers, such as diethyl ether and tetrahydrofuran, or halogenated solvents, such as chloroform or dichloromethane, are also possible. Likewise, solvent mixtures may also be used. The reaction may be caR1ied out at temperatures between -TS^C and the boiling point of the reaction mixture, preferably proceeding at from 10 to 120'C. Usually a laR2e excess of alkylating agent is used and alkylating agent remaining after the reaction is removed by vacuum distillation. Preference is given to the use of from 1.0 to 8.0 mol of the haloalkane/haloaralkane, based on 1 mol of aminophenylbenzothiazole. The products are purified by reC1-ystallisation from a suitable solvent or by column-chromato-graphic separation using a suitable eluant. The invention relates also to the process for the preparation of compounds of fonnula(1). ^,..^.v.vJMuo ui me rormuia (1) according to the present invention are particularly suitable as UV filters, i.e. for protecting ultraviolet-sensitive oR2anic materials, in particular the skin and hair of humans and animals, from the harmful effects of UV radiation. These compounds are therefore suitable as sunsC1-eens in cosmetic, pharmaceutical and veterinary medical preparations. These compounds can be used both in dissolved form and in the miC1-onized state. The UV absorbers according to the present invention can be used either in the dissolved state (soluble oR2anic filters, solubilized oR2anic filters) or in the miC1-onised state (nanoscalar oR2anic filters, particulate oR2anic filters, UV-absorber pigments). The triazine derivatives of formula (1) which have no alkyl substituents or only lower-alkyi substituents are characterized by a poor oil-solubility and a high melting point. They are therefore particularly suitable UV absorbers in the miC1-onized state. Any known process suitable for the preparation of miC1-oparticles can be used for the pre¬paration of the miC1-onised UV absorbers, for example: wet-milling (low viscous miC1-onisatlon process for pumpable dispersions), with a hard grinding medium, for example zirconium silicate balls in a ball mill and a protective surfactant or a protective polymer in water or in a suitable oR2anic solvent; wet-kneading (high viscous miC1-onisatlon process for non pump-able pastes) using a continuous or discontinuous (batch) kneader. For a wet-kneading process a solvent (water or cosmetically acceptable oils), a grinding-aid (surfactant, emulsifier) and a polymeric grinding aid may be used. Both processes may be used respectively spray-drying from a suitable solvent, for example aqueous suspensions or suspensions containing oR2anic solvents, or true solutions In water, ethanol, dichloroethane, toluene or N-methylpyR1olidone etc.. by the expansion according to the RESS process (Rapid Jxpansion of SuperC1-itical Solutions) of superC1-itical fluids (e.g. CO2) in which the UV filter or filters is/are dissolved, or the expansion of fluid carison dioxide together with a solution of one or more UV filters in a suitable oR2anic solvent; by reprecipitation from suitable solvents, including superC1-itical fluids (GASR process = Gas Anti-Solvent ReC1-ystallisation / PCA process = Precipitation with Compressed Anti-solvents). As milling apparatus for the preparation of the miC1-onised oR2anic UV absorbers there may be used, for example, a jet mill, ball mill, vibratory mill or hammer mill, preferably a high¬speed mixing mill. Even more preferable mills are modern ball mills, manufacturers of these mill-types are for example Netzsch (LMZ-mill), Drais (DCP-viscoflow or cosmo), Buhler AG (centrifugal mills) or Bachhofer. The grinding is preferably caR1ied out with a grinding aid. As kneading apparatus for the preparation of the miC1-onised oR2anic UV absorbers examples are typical sigma-hook batch kneaders but also serial batch kneaders (IKA-Werke) or continuous kneaders (Continua from Werner und Pfleiderer). Useful low molecular weight grinding aids for all the above miC1-onizing processes are sur¬factants and emulsifies as disclosed below in the chapters "emulsifiers" and "surfactants". Useful polymeric grinding aids for water dispersion are cosmetically acceptable water soluble polymers with MW > 5000 g/mol for example: aC1-ylates (Salcare types), modified or non-modified polysaccharides, poiyglucosides or xanthan gum. Furthermore an alkylated vinyl-pyR1olidone polymer, a vinylpyR1olidone/vinyl acetate copolymer, an acyl glutamate, an alkyl polyglucoside, ceteareth-25 or a phospholipid may be used. Oil dispersions may contain cosmetically acceptable waxy polymers or natural waxes as polymeric grinding aid to adjust viscosity during and after processing. Useful solvents are water, brine, (poly-)ethyleneglycol or glycerine for water-soluble dis¬persions and also cosmetically acceptable oils as desC1-ibed under "emollients" for oil-soluble dispersions. The miC1-onised UV absorbers so obtained usually have an average particle size from 0.02 to 2 miC1-ometers, preferably from 0.05 to 1.5 miC1-ometer and more especially from 0.1 to 1.0 miC1-ometers. The UV absoriaers can also be used dry in powder form. For that purpose the UV absorbers are subjected to known grinding methods, such as vacuum atomization, countercuR1ent spray-drying etc.. Such powders have a particle size of from 0.1 to 2 miC1-ometers. To avoid the occuR1ence of agglomeration, the UV absorbers can be coated with a surface-active compound prior to the pulverization process, for example with an anionic, non-ionic or amphoteric surfactant, e.g. a phospholipid or a known polymer, such as PVP, an aC1-ylate etc. The cosmetic formulations or pharmaceutical compositions according to the present inven¬tion can also contain one or more than one further UV filter as desC1-ibed 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 stiR1ing to¬gether the individual components, especially by making use of the dissolution properties of already known cosmetic UV absorbers, for example octyl methoxy cinnamate, salicylic acid isooctyl ester, etc. The UV absorber can be used, for example, without further treatment, or in the miC1-onised state, or in the form of a powder. Cosmetic or pharmaceutical preparations contain from 0.05-40% by weight, based on the total weight of the composition, of one UV absorber or UV absorber mixtures. Preference is given to the use of mixing ratios of the UV absorber of formula (1) according to the present invention and optionally further light-protective agents (as desC1-ibed in table 1-3) 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 mixing ratios of from 20:80 to 80:20, especially from 40:60 to 60:40 and preferably approximately 50:50. Such mixtures can be used, inter alia, to improve solubility or inC1-ease UV absorption. The cosmetic or pharmaceutical preparations may be, for example, C1-eams, gels, lotions, alcoholic and aqueous/alcoholic solutions, emulsions, wax/fat compositions, stick prepa¬rations, powders or ointments. In addition to the above mentioned UV filters, the cosmetic or pharmaceutical preparations may contain further adjuvants as desC1-ibed below. As water- and oil-containing emulsions (e.g. W/0, OAA/, 0/W/O and W/O/W emulsions or miC1-oemulsions) the preparations contain, for example, from 0.1 to 30 % by weight, pre¬ferably from 0.1 to 15 % by weight and especially from 0.5 to 10 % by weight, based on the total weight of the composition, of one or more UV absorbers, from 1 to 60 % by weight, especially from 5 to 50 % by weight and preferably from 10 to 35 % by weight, based on the total weight of the composition, of at least one oil component, from 0 to 30 % by weight, especially from 1 to 30 % by weight and 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 as desC1-ibed below. Fatty alcohols Guerbet alcohols based on fatty alcohols having from 6 to 18, preferably from 8 to 10 carbon atoms including cetyl alcohol, stearyl alcohol, cetearyl alcohol, oleyl alcohol, octydodecanol, benzoate of C12-C15 alcohols, acetylated lanoin alcohol, etc.. Esters of fatty acids Esters of linear C8-C24 fatty acids with linear C3-C24 alcohols, esters of branched Ce-Ciscar-boxylic acids with linear C8-C24 fatty alcohols, esters of linear C6-C24 fatty acids with branched alcohols, especially 2-ethylhexanol, esters of hydroxycarboxylic acids with linear or branched C8-C22 fatty alcohols, especially dioctyl malates, esters of linear and/or branched fatty acids with polyhydric alcohols (for example propylene glycol, dimer diol or trimer triol) and/or Guerbet alcohols, for example caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeo- stearic acid, arachidic acid, gadoleic acid, belienic acid and erucic acid and technical-grade mixtures thereof (obtained, for example, in the pressure removal of natural fats and oils, in the reduction of aldehydes from Roelen's oxosynthesis or in the dimerisation of unsaturated fatty acids) with alcohols, for example, isopropyt alcohol, caproic alcohol, capryl alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linoyl alcohol, linolenyl alcohol, elaeostearyl alcohol, arachidyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and technical-grade mixtures thereof (obtained, for example, in the high-pressure hydrogenation of technical-grade methyl esters based on fats and oils or aldehydes from Roelen's oxosynthesis and as monomer fractions in the dimerisation of unsaturated fatty alcohols). Examples of such ester oils are isopropyl myristate, isopropyl palmitate, isopropyl stearate, isopropyi isostearate, isopropyl oleate, n-butyl stearate, n-hexyl laurate, n-decyl oleate, iso-octyl stearate, iso-nonyl stearate, isononyl isononanoate, 2-ethylhexyl palmitate, 2-hexyllau-rate, 2-hexyldecyl stearate, 2-octyldodecyl palmitate, oleyl oleate, oleyl erucate, erucyl ole¬ate, erucyl erucate, cetearyl octanoate, cetyl palmitate, cetyl stearate, cetyl oleate, cetyl be-henate, cetyl acetate, myristyl myristate, myristyl behenate, myristyl oleate, myristyl stearate, myristyl palmitate, myristyl lactate, propylene glycol dicaprylate/caprate, stearyl heptanoate, diisostearyl malate, octyl hydroxystearate, etc.. Other adjuvants diethylhexyl 2,6- naphthalate, 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 dl(2-ethylhexanoate), propylene glycol dilsostearate, propylene glycol dipelaR2onate, butanedlol diisostearate and neopentyl glycol dicaprylate. Esters of C8-C24 fatty alcohols and/or Guerbet alcohols with aromatic carboxylic acids, saturated and/or unsaturated, especially benzoic acid, esters of C2-Ci2dicarboxylic acids with linear or branched alcohols having from 1 to 22 carbon atoms or polyols having from 2 to 10 carbon atoms and from 2 to 6 hydroxy groups. Natural or synthetic triglycerides including glycervl esters and derivatives Di- or tri-glycerides, based on Ce-Cia fatty acids, modified by reaction with other alcohols (caprylic/capric triglyceride, wheat germ glycerides, etc.). Fatty acid esters of polyglycerin ^^.v^.^aiyociyi-ii sucn as poiygiyceryl-4 caprate, polyglyceryl-2 isostearate, etc. or castor oil, hydrogenated vegetable oil, sweet almond oil, wheat germ oil, sesame oil, hydrogenated cottonseed oil, coconut oil, avocado oil, corn oil, hydrogenated castor oil, shea butter, cocoa butter, soybean oil, mink oil, sunflower oil, safflower oil, macadamia nut oil, olive oil, hydro¬genated tallow, apricot kernel oil, hazelnut oil, borage oil, etc. Waxes including esters of long-chain acids and alcohols as well as compounds having wax¬like properties, e.g., carnauba wax, beeswax (white or yellow), lanolin wax, candelilla wax, ozokerite, japan wax, paraffin wax, miC1-oC1-ystalline wax, ceresin, cetearyl esters wax, syn¬thetic beeswax etc. Also, hydrophilic waxes as cetearyl alcohol or partial glycerides. Pearlescent waxes: Ikylene glycol esters, especially ethylene glycol distearate; fatty acid alkanol amides, especially coco fatty acid diethanolamide; partial glycerides, especially stearic acid mono-glyceride; esters of polyvalent, unsubstituted or hydroxy-substituted carboxylic acids with fatty alcohols having from 6 to 22 carbon atoms, especially long-chained esters of tartaric acid; fatty substances, for example fatty alcohols, fatty ketones, fatty aldehydes, fatty ethers and fatty carbonates, which in total have at least 24 carbon atoms, especially laurone and distearyl ether; fatty acids, such as stearic acid, hydroxystearic acid or behenic acid, ring-opening products of olefin epoxides having from 12 to 22 carbon atoms with fatty alcohols having from 12 to 22 carbon atoms and/or polyols having from 2 to 15 carbon atoms and from 2 to 10 hydroxy groups, and mixtures thereof. Hydrocarbon oils: Mineral oil (light or heavy), petrolatum (yellow or white), miC1-oC1-ystalline wax, paraffinic and isoparaffinic compounds, hydrogenated isoparaffinic molecules as polydecenes and pol^u-tene, hydrogenated polyisobutene, squalane, isohexadecane, isododecane and others from plant and animal kingdom. Silicones or siloxanes (oR2anosubstituted polvsiloxanes) Dimethylpolysiloxanes, methylphenylpolysiloxanes, cyclic silicones, and also amino-, fatty acid-, alcohol-, polyether-, epoxy-, fluorine-, glycoside- and/or alkyl-modified silicone com¬pounds, which at room temperature may be in either liquid or resinous fonri. Linear poly-siloxanes, dimethicone (Dow Corning 200 fluid, Rhodia Mirasil DM), dimethiconol, cyclic silicone fluids, cyclopentasiioxanes volatiies (Dow Corning 345 fluid), phenyltrimethicone (Dow Corning 556 fluid). Also suitable are simethicones, which are mixtures of dimethicones having an average chain length of from 200 to 300 dimethylsiloxane units with hydrcgenated silicates. A detailed survey by Todd ef a/, of suitable volatile silicones may in addition be found in Cosm. Toil. 91. 27 (1976). Fluorinated or perfluorinated oils Perfluorohexane, dimethylcyclohexane, ethylcyclopentane, polyperfluoromethylisopropyl ether, Emulsifiers Any conventionally emulsifier can be used for the compositions. Emulsifier systems may comprise for example: carboxylic acids and their salts: alkaline soap of sodium, potassium and ammonium, metallic soap of calcium or magnesium, oR2anic basis soap such as lauric, palmitic, stearic and oleic acid etc.. Alkyl phosphates or phosphoric acid esters, acid phos¬phate, diethanolamlne phosphate, potassium cetyl phosphate. Ethoxylated carboxylic acids or polyethylene glycol esters, PEG-n acylates. Linear fatty alcohols having from 8 to 22 carbon atoms, branched from 2 to 30 mol of ethylene oxide and/or from 0 to 5 mol propylene oxide with fatty acids having from 12 to 22 carbon atoms and with alkylphenols having from 8 to 15 carbon atoms in the alkyl group. Fatty alcohol polyglycolether such as laureth-n, ceteareth-n, steareth-n, oleth-n. Fatty acid polyglycolether such as PEG-n stearate, PEG-n oleate, PEG-n cocoate. Monoglycerides and polyol esters. Cia-Ca fatty acid mono- and di-esters of addition products of from 1 to 30 mol of ethylene oxide with polyols. Fatty acid and polyglycerol ester such as monostearate glycerol, diisostearoyi polyglyceryi-3-diisostearates, polyglyceryl-3-cliisostearates, triglyceryl diisostearates, polyglyceryl-2-sesquiisostearates or poiyglyceryl dimerates. Mixtures of compounds from a plurality of those substance classes are also suitable. Fatty acid polyglycolesters such as monostearate diethylene glycol, fatty acid and polyethylene glycol esters, fatty acid and saccharose esters such as susro esters, glycerol and saccharose esters such as suC1-o glycerides. Sorbitol and sorbitan, sorbitan mono- and di-esters of saturated and unsaturated fatty acids having from 6 to 22 carbon atoms and ethylene oxide addition products. Polysorbate-n series, sorbitan esters such as sesquiisostearate, sorbitan, PEG-(6)-isostearate sorbitan, PEG-(10)-sorbitan laurate, PEG-17- dioleate sorbitan. Glucose derivatives, C8-C22 alkyl-mono and oligo-glycosides and ethoxylated analogues with glucose being prefeR1ed as the sugar component. 0/W emulsifiers such as methyl gluc8th-20 sesquistearate, sorbitan stearate/suC1-ose cocoate, methyl glucose sesquistearate, cetearyi alcohol/cetearyl glucoside. W/O emulsifiers such as methyl glucose dioleate/ methyl glucose isostearate. Sulfates and sulfonated derivatives, dialkylsulfosuccinates, dioctyl succinate, alkyl lauryl sulfonate, linear sulfonated parafins, sulfonated tetrapropylene sulfonate, sodium lauryl sulfates, ammonium and ethanolamine lauryl sulfates, lauyl ether sulfates, sodium laureth sulfates, sulfosuccinates, aceyl isothionates, alkanolamide sulfates, taurines, methyl taurines, imidazole sulfates. Amine derivatives, amine salts, ethoxylated amines, oxide amine with chains containing an heterocyde such as alkyl imidazolines, pyridine derivatives, isoquinoteines, cetyl pyridinium chloride, cetyl pyridinium bromide, quaternary ammonium such as cetyltrimethylbroimde amonium bromide (CTBA), stearylalkonium. Amide derivatives, alkanolamides such as acylamide DEA, ethoxylated amides such as PEG-n acylamide, oxydeamide. Poly-siloxane/polyalkyl/polyether copolymers and derivatives, dimethicone, copolyols, silicone polyethylene oxide copolymer, silicone glycol copolymer. Propoxylated or POE-n ethers (Meroxapols), Polaxamers or poly(oxyethylene)m-b!ock-poly(oxypropylene)n-block(oxy-ethylene). Zwitterionic surfactants that caR1y at least one quaternary ammonium group and at least one carboxylate and/or sulfonate group in the molecule. Zwitterionic suifactants that are especially suitable are betaines, such as N-alkyl-N,N-dimethylammonium glycinates, coco-alkyldimethylammonium glycinate, N-acylaminopropyl-N,N-dimethylammonium glycinates, cocoacylaminopropyldimethylammonium glycinate and 2-alkyl-3-carboxymethyl-3-hydroxy-ethylimidazolines each having from 8 to 18 carbon atoms in the alkyl or acyl group and also cocoacylaminoethylhydroxyethylcarboxymethylglycinate, N-alkylbetaine, N-alkylaminobe-taines. Alkytimidazolines, alkylopeptides, lipoaminoacids, self emulsifying bases and the compounds as desC1-ibed in K.F.DePolo, A short textbook of cosmetology. Chapter 8, Table 8-7, p250-251. Non ionic bases such as PEG-6 beeswax (and) PEG-6 stearate (and) polyglyceryl -2-iso-stearate [Apifac], glyceryl stearate (and) PEG-100 stearate. [Arlacel 165], PEG-5 glyceryl stearate [arlatone 983 S], sorbitan oleate (and) polyglyceryl-3 ricinoleate. [Arlacel 1689], sorbitan stearate and suC1-ose cocoate [arlatone 2121], glyceryl stearate and laureth-23 [Cerasynth 945], cetearyi alcohol and ceteth-20 [CetomaC1-ogol Wax], cetearyi alcohol and polysorbate 60 and PEG-150 and stearate-20[Polawax GP 200, Polawax NF], cetearyi alcohol and cetearyi polyglucoside [Emulgade PL 1618], cetearyi alcohol and ceteareth-20 [Emulgade 1000NI, Cosmowax], cetearyi alcohol and PEG-4Q castor oil [Emulgade F Special], cetearyl alcohol and PEG-40 castor oil and sodium cetearyl sulfate [Emulgade F], stearyl alcohol and steareth-7 and steareth-10 [Emulgator E 2155], cetearyl alcohol and szeareth-7 and steareth-10 [Emulsifying wax U.S.N.F], glyceryl stearate and PEG-75 stearate [Gelot 54], propylene glycol ceteth-3 acetate .[Hetester FCS], propylene glycol isoceth-3 acetate [Hetester PHA], cetearyl alcohol and ceteth-12 and Qleth-12 [Lanbritol Wax N 21], PEG -6 stearate and PEG-32 stearate [Tefose 1500], PEG-6 stearate and ceteth-20 and steareth-20 [Tefose 2000], PEG-6 stearate and ceteth-20 and glyceryl stearate and steareth-20 [Tefose 2561], glyceryl stearate and ceteareth-20 [Teginacid H, C, X]. Anionic alkaline bases such as PEG-2 stearate SE, glyceryl stearate SE [Monelgine, Cutina KD], propylene glycol stearate [Tegin P]. Anionic acid bases such as cetearyl Alcohol and Sodium cetearyl sulfate [Lanette N, Cutina LE, C1-odacol GP], cetearyl alcohol and sodium lauryl sulfate [Lanette W], trilaneth-4 phosphate and glycol stearate and PEG-2 stearate [Sedefos 75], glyceryl stearate and sodium lauryl sulfate [Teginacid Special]. Cationic acid bases such as cetearyl alcohol and cetrimonium bromide. The emulsifiers may be used in an amount of, for example, from 1 to 30 % by weight, especially from 4 to 20 % by weight and preferably from 5to 10 % by weight, based on the total weight of the composition. When formulated in OA/V emulsions, the prefeR1ed amount of such emulsifier system could represent 5% to 20% of the oil phase. Adjuvants and additives The cosmetic / pharmaceutical preparations, for example C1-eams, gels, lotions, alcoholic and aqueous/alcoholic solutions, emulsions, wax/fat compositions, stick preparations, powders or ointments, may in addition contain, as further adjuvants and additives, mild surfactants, su¬per-fatting agents, consistency regulators, thickeners, polymers, stabilisers, biogenic active ingredients, deodorising active ingredients, anti-dandruff agents, film fomners, swelling agents, further UV light-protective factors, antioxidants, hydrotropic agents, preservatives, insect repellents, self-tanning agents, solubilisers, perfume oils, colourants, bacteria-inhibiting agents and the like. Super-fatting agents Substances suitable for use as super-fatting agents are, for example, lanolin and lecithin and also polyethoxylated or aC1-ylated lanolin and lecithin derivatives, polyol fatty acid esters, monoglycerides and fatty acid alkanolamides, the latter simultaneously acting as foam stabilisers. Surfactants Examples of suitable mild surfactants, that is to say surfactants especially well tolerated by the skin, include fatty alcohol polyglycol ether sulfates, monoglyceride sulfates, mono- and/or di-alkyi sulfosuccinates, fatty acid isethionates, fatty acid sarcosinates, fatty acid tai/ides, fatty acid glutamates, a-olefin sulfonates, ethercarboxylic acids, alkyl oligoglucosides, fatty acid gtucamides, alkylamidobetaines and/or protein fatty acid condensation products, the latter preferably being based on wheat proteins. Consistency regulators/thickeners and rheology modifiers Silicon dioxide, magnesium silicates, aluminium silicates, polysaccharides or derivatives thereof for example hyaluronic acid, xanthan gum, guar-guar, agar-agar, alginates, caR1ageenan, gellan, pectins, or modified cellulose such as hydroxycellulose, hydroxypropyl-methylcellulose. In addition polyaC1-ylates or homopolymers of reticulated aC1-ylic acids and polyaC1-ylamides, carbomer (carbopol types 980, 981, 1382, ETD 2001, ETD2020, Ultrez 10) orSalcare range such as Salcare SC80(steareth-10 allyl ether/aC1-ylates copolymer), Salcare SC81(aC1-ylates copolymer), Salcare SC91 and Salcare AST{sodium aC1-ylates copoly-mer/PPG-1 trideceth-6), sepigel 305(polyaC1-ylamide/laureth-7), Simulgel NS and Simulgei EG (hydroxyethyi aC1-ylate / sodium aC1-yloyidimethyi taurate copolymer), Stabilen 30 (aC1-y¬lates / vinyl isodecanoate C1-osspolymer), Pemulen TR-1 (aC1-ylates / C10-30 alkyl aC1->Jate C1-osspolymer), Luvigel EM (sodium aC1-ylates copolymer), Aculyn 28 (aC1-ylates/beheneth-25 methaC1-ylate copolymer), etc.. Polymers Suitable cationic polymers are, for example, cationic cellulose derivatives, for example a quaternised hydroxymethyl cellulose obtainable under the name Polymer JR 400 from Amerchol, cationic starches, copolymers of diallylammonium salts and aC1-ylamides, quater¬nised vinylpyR1olidone/vinyl imidazole polymers, for example Luviquat® (BASF), condensation products of polyglycols and amines, quaternised collagen polypeptides, for example lauryl- dimonium hydroxypropyl hydrolyzed collagen (Lamequat®UGrunau), quaternised wheat poly¬peptides, polyethyleneimine, cationic silicone polymers, for example amidomethicones, copo¬lymers of adipic acid and dimethyiaminohydroxypropyldiethylen^riamine (Cartaretin/San-doz), copolymers of aC1-ylic acid with dimethyldiallylammonium chloride (Merquat 550/Chem-viron), poiyaminopolyamides, as desC1-ibed, for example, in FR-A-2 252 840, and the C1-oss-linked water-soluble polymers thereof, cationic chitin derivatives, for example of quaternised chitosan, optionally distributed as miC1-oC1-ystals; condensation products of dihalcalkyls, for example dibromobutane, with bisdialkylamines, for example bisdimethyfeimino-1,3-propane, cationic guar gum, for example Jaguar C-17, Jaguar C-16 from Celanese, quaternised ammonium salt polymers, for example Mirapol A-15, Mirapol AD-1, Mir^ol AZ-1 from . Miranol. As anionic, zwitterionic, amphoteric and non-ionic polymers there come into consideration, for example, vinyl acetate / C1-otonic acid copolymers, vinylpyR1didone / vinyl aC1-ylate copolymers, vinyl acetate / butyl maleate / isobornyl aC1-ylate copolymers, methyl vinyl ether / maleic anhydride copolymers and esters thereof, unC1-osslinked polyaC1-ylic acids and polyaC1-ylic acids C1-osslinked with polyols, aC1-ylamidopropyl-trimethylammonium chloride /aC1-ylate copolymers, octyl aC1-ylamide/hiethyl methaC1-ylatetert-butylaminoethyl meth-aC1-ylate/2-hydroxypropyl methaC1-ylate copolymers, polyvinylpyR1olidone, vinylpyR1olidone/-vinyl acetate copolymers, vinylpyR1olidone/dimethylaminoethyl methaC1-ylate/vinyl capro-lactam terpolymers and also optionally derivatised cellulose ethers and silicones. Furthermore the polymers as desC1-ibed in EP 1093796 (pages 3-8, paragraphs 17-68) may be used. Biogenic active ingredients Biogenic active ingredients are to be understood as meaning, for example, tocopherol, toco¬pherol acetate, tocopherol palmitate, ascorbic acid, deoxyribonucleic acid, retinol, bisabolol, allantoin, phytantriol, panthenol, AHA acids, amino acids, ceramides, pseudoceramides, essential oils, plant extracts and vitamin complexes. Deodorising active ingredients As deodorising active ingredients there come into consideration, for example, anti-perspirants, for example aluminium chlorohydrates (see J. Soc. Cosm. Chem. 24, 281 (1973)). Under the trade mark LoC1-on® of Hoechst AG, Frankfurt (FR2), there is available commercially, for example, an aluminium chlorohydrate coR1esponding to fonnula Al2(OH)5CI X 2.5 H2O, the use of which is especially prefeR1ed (see J. Pharm. Pharmacol. 26, 531 (1975)). Besides the chlorohydrates, it is also possible to use aluminium hydroxyacetates and acidic aluminium/zirconium salts. Esterase inhibitors may be added as further deodorising active ingredients. Such inhibitors are preferably trialkyl citrates, such as trimethyl citrate, tripropyl citrate, triisopropyl citrate, tributyl citrate and especially triethyl citrate (Hydagen CAT, Henl Anti-dandruff agents As anti-dandruff agents there may be used, for example, climbazole, octopirox and zinc pyri- thione. Film fonners Customary film formers include, for example, chitosan, miC1-oC1-ystalline chitosan, qufitemised chitosan, polyvinylpyn-olidone, vinylpyR1olidone/vinyl acetate copolymers, polymers of quaternary cellulose derivatives containing a high proportion of aC1-ylic acid, collagen, hyaluronic acid and salts thereof and similar compounds. Antioxidants In addition to the primary light-protective substances it is also possible to use secondary light-protective substances of the antioxidant kind that inteR1upt the photochemical reaction chain triggered when UV radiation penetrates the skin or hair. Typical examples of such anti¬oxidants are amino acids (e.g. glycine, histidine, tyrosine, tryptophan) and derivatives there¬of, imidazoles (e.g. urocanic acid) and derivatives thereof, peptides, such as D,L-carnosine, D-carnosine, L-camosine and derivatives thereof (e.g. anserine), carotinoids, carotenes, lycopene and derivatives thereof, chlorogenic acid and derivatives thereof, lipoic acid and derivatives thereof (e.g. dihydrolipoic acid), aurothioglycose, propylthiouracil and other thiols (e.g. thioredoxin, glutathione, cysteine, cystine, cystamine and the glycosyl, N-acetyl, mdhyl, ethyl, propyl, amyl, butyl, lauryl, palmitoyi, oleyl, linoleyl, cholesteryl and glyceryl esters thereof) and also salts thereof, dilauryl thiodipropionate, distearyl thiodipropionate, thiodi-propionic acid and derivatives thereof (esters, ethers, peptides, lipids, nucleotides, nucleo¬sides and salts) and also sulfoximine compounds (e.g. buthionine sulfoximines, homo¬cysteine sulfoximine, buthionine sulfones, penta-, hexa-, hepta-thionine sulfoximine), also (metal) chelating agents (e.g. hydroxy fatty acids, palmitic acid phytic acid, lactofeR1in), hydroxy acids (e.g. citric acid, lactic acid, malic acid), humic acid, bile acid, bile extracts, bilirubin, biliverdin, EDTA, EDDS, EGTA and derivatives thereof, unsaturated fatty acids and derivatives thereof (e.g. linolenic acid, linoleic acid, oleic acid), folic acid and derivatives thereof, ubiquinone and ubiquinol and derivatives thereof, vitamin C and derivatives (e.g. ascorbyl palmitate, magnesium ascorbyl phosphate, ascorbyl acetate), tocopherols and derivatives (e.g. vitamin E acetate), vitamin A and derivatives (e.g. vitamin A palmitate) and also coniferyl benzoate of benzoin resin, rutinic acid and derivatives thereof, glycosylrutin, ferulic acid, furfurylidene glucitol, carnosine, butyl hydroxytoluene, butyl hydroxyanisole, nordihydroguaiaretic acid, trihydroxybutyrophenone, uric acid and derivatives thereof, mannose and derivatives thereof, superoxide dismutase, N-[3-(3,5-di-tert-butyl-4-hydroxy-phenyl)propionyl]sulfanilic acid (and salts thereof, for example the disodium salts), zinc and derivatives thereof (e.g. ZnO, ZHSOA), selenium and derivatives thereof (e.g. selenium me¬thionine), stilbene and derivatives thereof (e.g. stilbene oxide, trans-stilbene oxide) and the derivatives suitable according to the invention (salts, esters, ethers, sugars, nucleotides, nucleosides, peptides and lipids) of those mentioned active ingredients. HALS (="Hindered Amine Light Stabilizers") compounds may also be mentioned. The amount of antioxidants present is usually from 0.001 to 30 % by weight, preferably from 0.01 to 3 % by weight, based on the weight of the UV absorber of formula (1). Hydrotropic agents To improve the flow behaviour it is also possible to employ hydrotropic agents, for example ethoxylated or non ethoxylated mono-alcohols, diols or polyols with a low number of carbon atoms or their ethers (e.g. ethanol, isopropanol, 1,2-dipropanediol, propylene glycol, glycerine, ethylene glycol, ethylene glycol monoethyl ether, ethylene glycol monobutylether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether and similar products). The polyols that come into consideration for that purpose have preferably from 2 to 15 carbon atoms and at least two hydroxy groups. The polyols may also contain further functional groups, especially amino groups, and/or may be modified with nitrogen. Typical examples are as follows: glycerol, alkylene glycols, for example ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, hexylene glycol and also polyethylene glycols having an average molecular weight of from 100 to 1000 Dalton; technical oligoglycerol mixtures having an intrinsic degree of condensation of from 1.5 to 10, for example technical diglycerol mixtures having a diglycerol content of from 40 to 50 % by weight; methylol compounds, such as, especially, trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol and dipentaerythritol; lower alkyl-glucosides, especially those having from 1 to 8 carbon atoms in the alky! radical, for example methyl and butyl glucoside; sugar alcohols having from 5 to 12 carbon atoms, for example sorbitol or mannitol; sugars having from 5 to 12 carbon atoms.for example glucose or saccharose; amino sugars, for example glucamine; dialcohol amines, such as diethanolamine or 2-amino-1,3-propanediol. Preservatives Suitable presen/atives include, for example, methyl-.ethyl-, propyl-, butyl- parabens, benzal-conium chloride, 2-Bromo-2-nitro-propane-1,3-dlol, dehydroacetic acid, diazolidinyl Urea, 2-dichloro-benzyl alcohol, DMDM hydantoin, formaldehyde solution, methyldibromogliJanitrile, phenoxyethanol, Sodium hydroxymethylglycinate, imidazolidinyl urea, Triclosan and further substance classes listed in the following reference: K.F.DePolo -A short textbook of cosmetology, Chapter 7, Table 7-2, 7-3, 7-4 and 7-5, p210-219. Bacteria-inhibiting agents Typical examples of bacteria-inhibiting agents are preservatives that have a specific action against gram-positive bacteria, such as 2,4,4'-trichloro-2-hydroxydiphenyl ether, chlorhexi-dine (1,6-di(4-chlorophenyl-biguanido)hexane) orTCC (3,4,4'-trichlorocarbanilide). A laR2e number of aromatic substances and ethereal oils also have antimiC1-obial properties. Typical examples are the active ingredients eugenol, menthol and thymol in clove oil, mint oil and thyme oil. A natural deodorising agent of interest is the terpene alcohol farnesol (3,7,11-tri-methyl-2,6,10-dodecatrien-1-ol), which is present in lime blossom oil. Glycerol mondaurate has also proved to be a bacteriostatic agent. The amount of the additional bacteria-inhbiting agents present is usually from 0.1 to 2 % by weight, based on the solids content ofthe preparations. Perfume oils There may be mentioned as perfume oils mixtures of natural and/or synthetic aromatic sub¬stances. Natural aromatic substances are, for example, extracts from blossom (lilies, laven¬der, roses, jasmine, neroli, ylang-ylang), from stems and leaves (geranium, patchouli, petit-grain), from fruit (aniseed, coriander, caR1away, juniper), from fruit pee! (beR2amot, lemons, oranges), from roots (mace, angelica, celery, cardamom, costus, iris, calmus), from wood (pinewood, sandalwood, guaiacum wood, cedarwood, rosewood), from herbs and grasses (taR1agon, lemon grass, sage, thyme), from needles and twigs (spruce, pine, Scots pine, mountain pine), from resins and balsams (galbanum, elemi, benzoin, myn-h, olibanum, opo-ponax). Animal raw materials also come into consideration, for example civet and castoreum. Typical synthetic aromatic substances are, for example, products of the ester, ether, alde¬hyde, ketone, alcohol or hydrocarbon type. Aromatic substance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linaiyl benzoate, benzyl formate, ethylmethylphenyl glycinate, allylcyclohexyl propionate, styrallyl propionate and ben¬zyl salicylate. The ethers include, for example, benzyl ethyl ether; the aldehydes include, for example, the linear alkanals having from 8 to 18 hydrocarbon atoms, citral, citronellal, citro-nellyl oxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bouR2eonal; the ke¬tones include, for example, the ionones, isomethylionone and methyl cedryl ketone; the alco¬hols include, for example, anethol, citronellol, eugenol, isoeugenol, geraniol, linalool, phenyl ethyl alcohol and terpinol; and the hydrocarbons include mainly the terpenes and balsams. It is preferable, however, to use mixtures of various aromatic substances that tcgether produce an attractive scent. Ethereal oils of relatively low volatility, which are chiefly used as aroma components, are also suitable as perfume oils, e.g. sage oil, camomile oil, clove oil, melissa oil, oil of cinnamon leaves, lime blossom oil, juniper benry oil, vetiver oil, olibanum oil, galba¬num oil, labolanum oil and lavandin oil. Preference is given to the use of beR2amot oil, di-hydromyrcenol, lilial, lyral, citronellol, phenyl ethyl alcohol, hexyl cinnamabehyde, geraniol, benzyl acetone, cyclamen aldehyde, linalool, boisambrene forte, ant)roxan, indole, hedione, sandelice, lemon oil, tangerine oil, orange oil, allyl amyl glycolate, cyclovertal, lavandin oil, muscatel sage oil, damascene, bourbon geranium oil, cyclohexyl salicylate, vertofix coeur, iso-E-Super, Fixolide NP, evernyl, iraldein gamma, phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide, romillat, irotyl and floramat alone or in admixture with one another. Colourants There may be used as colourants the substances that are suitable and permitted for cosmetic purposes, as compiled, for example, in the publication "Kosmetische Farbemittel" of the Farbstoffkommission der Deutschen Forschungsgemeinschaft, Verlag Chemie, Weinheim, 1984, pages 81 to 106. The colourants are usually used in concentrations of from 0.001 to 0.1 % by weight, based on the total mixture. Other adjuvants It is furthermore possible for the cosmetic preparations to contain, as adjuvants, anti-foams, such as silicones, structurants, such as maleic acid, solubilisers, such as ethylene glycol, propylene glycol, glycerol or diethylene glycol, opacifiers, such as latex, styrene/PVP or sty-rene/aC1-ylamide copolymers, complexing agents, such as EDTA, NTA, alaninediacetic acid or phosphonic acids, propellants, such as propane/butane mixtures, NP, dimethyl ether, CO2, N2 or air, so-called coupler and developer components as oxidation dye precursors, reducing agents, such as thioglycolic acid and derivatives thereof, thiolactic acid, cysteamine, thiomalic acid or mercaptoethanesulfonic acid, or oxidising agents, such as hydrogen peroxide, potassium bromate or sodium bromate. Suitable insect repellents are, for example, N,N-diethyl-m-toluamide, 1,2-pentanediol or in¬sect repellent 3535; suitable self-tanning agents are, for example, dihydroxyacetone and/or erythrulose or dihydroxy acetone and/or dihydroxy acetone precursors as desC1-ibed in WO 01/85124 and/or erythrulose. Polymeric beads or hollow spheres as SPF enhancers The combination of the UV-absorbers and UV-absorber combinations, listed above, with SPF enhancers, such as non-active ingredients like Styrene/aC1-yiates copolymer, silica beads, spheroidal magnesium silicate, C1-osslinked PolymethylmethaC1-ylates (PMMA ; Micopearl M305 Seppic), can maximize better the UV protection of the sun products. Holosphere additives (Sunspheres® ISP, Silica Shells Kobo.) deflect radiation and the effective path length of the photon is therefore inC1-eased.( EP0893119). Some beads, as mentioned pre¬viously, provide a soft feel during spreading. Moreover, the optical activity of such beads, e.g.MiC1-opearl M305, cans modulate skin shine by eliminating reflection plienomena and indirectly may scatter the UV light. When formulated in OAA/ emulsions, the preferably amount of such SPF enhancers should represent 1% to 10% of the total amount of the emulsion. Cosmetic or pharmaceutical preparations Cosmetic or pharmaceutical formulations are contained in a wide variety of cosmetic preparations. There come into consideration, for example, especially the following preparations: skin-care preparations, e.g. skin-washing and cleansing preparations in the form of tablet-form or liquid soaps, soapless deteR2ents or washing pastes, bath preparations, e.g. liquid (foam baths, milks, shower preparations) or solid bath preparations, e.g. bath cubes and bath salts; skin-care preparations, e.g. skin emulsions, multi-emulsions or skin oils; cosmetic personal care preparations, e.g. facial make-up in the form of day C1-eams or powder C1-eams, face powder (loose or pressed), rouge or C1-eam make-up, eye-care preparations, e.g. eyeshadow preparations, mascara, eyeliner, eye C1-eams or eye-fix C1-eams; lip-care preparations, e.g. lipsticks, lip gloss, lip contour pencils, nail-care preparations, such as nail varnish, nail varnish removers, nail hardeners or cuticle removers; foot-care preparations, e.g. foot baths, foot powders, foot C1-eams or foot balsams, special deodorants and antiperspirants or callus-removing preparations; light-protective preparations, such as sun milks, lotions, C1-eams or oils, sunblocks or tropicals, pre-tanning preparations or after-sun preparations; skin-tanning preparations, e.g. self-tanning C1-eams; depigmenting preparations, e.g. preparations for bleaching the skin or skin-lightening preparations; insect-repellents, e.g. insect-repellent oils, lotions, sprays or sticks; deodorants, such as deodorant sprays, pump-action sprays, deodorant gels, sticks or roll-ons; antiperspirants, e.g. antiperspirant sticks, C1-eams or roll-ons; preparations for cleansing and caring for blemished skin, e.g. synthetic deteR2ents (solid or liquid), peeling or sC1-ub preparations or peeling masks; I I .^,,.j I., v^ucinilgai lunii vucfjn'ai.iuii;, «.y. riair-reiTioving powders, liquid hair-removing preparations, C1-eam- or paste-form hair-removing preparations, hair-removing preparations in gel form or aerosol foams; shaving preparations, e.g. shaving soap, foaming shaving C1-eams, non-foaming shaving C1-eams, foams and gels, preshave preparations for dry shaving, aftershaves or aftershave lotions; fragrance preparations, e.g. fragrances (eau de Cologne, eau de toilette, eau de parfum, parfum de toilette, perfume), perfume oils or perfume C1-eams; cosmetic hair-treatment preparations, e.g. hair-washing preparations in the form of shampoos and conditioners, hair-care preparations, e.g. pretreatment preparations, hair tonics, styling C1-eams, styling gels, pomades, hair rinses, treatment packs, intensive hair treatments, hair-structuring preparations, e.g. hair-waving preparations for permanent waves (hot wave, mild wave, cold wave), hair-straightening preparations, liquid hair-setting preparations, hair foams, hairsprays, bleaching preparations, e.g. hydrogen peroxide solutions, lightening shampoos, bleaching C1-eams, bleaching powders, bleaching pastes or oils, temporary, semi-permanent or permanent hair colourants, preparations containing self-oxidising dyes, or natural hair colourants, such as henna or camomile. Presentation forms The final fomnulations listed may exist in a wide variety of presentation forms, for example: in the form of liquid preparations as a W/0, OA/V, 0/W/O, W/O/W or PIT emulsion and all kinds of miC1-oemulsions, in the form of a gel, in the fonn of an oil, a C1-eam, milk or lotion, in the fomi of a powder, a lacquer, a tablet ormake-up, in the forni of a stick, in the fonn of a spray (spray with propellent gas or pump-action spray) or an aerosol, in the form of a foam, or in the form of a paste. Of special importance as cosmetic preparations for the skin are light-protective preparations, such as sun milks, lotions, C1-eams, oils, sunblocks or tropicals, pretanning preparations or after-sun preparations, also skin-tanning preparations, for example seif-tanning C1-eams. Of particular interest are sun protection C1-eams, sun protection lotions, sun protection milk and sun protection preparations in tine form of a spray. Of special importance as cosmetic preparations for the hair are the above-mentioned prepa¬rations for hair treatment, especially hair-washing preparations in the fomn of shampoos, hair conditioners, hair-care preparations, e.g. pretreatment preparations, hair tonics, styling C1-eams, styling gels, pomades, hair rinses, treatment packs, intensive hair treatments, hair-straightening preparations, liquid hair-setting preparations, hair foams and hairsprays. Of special interest are hair-washing preparations in the form of shampoos. A shampoo has, for example, the following composition: from 0.01 to 5 % by weight of a UV absorber according to the invention, 12.0 % by vveight of sodium laureth-2-sulfate, 4.0 % by weight of cocamidopropyl betaine, 3.0 % by weight of sodium chloride, and water ad 100%. For example, especially the following hair-cosmetic formulations may be used: ai) spontaneously emulsifying stock formulation, consisting of the UV absorber according to the invention, PEG-6-CioOxoalcohol and sorbitan sesquioleate, to which water and any desired quaternary ammonium compound, for example 4 % minkamidopropyl dmethyl-2-hydroxyethylammonium chloride or Quatemium 80 is added; 82) spontaneously emulsifying stock formulation consisting of the UV absorber according to the invention, tributyl citrate and PEG-20-sorbitan monooleate, to which water and any desired quaternary ammonium compound, for example 4 % minkanidopropyl dimethyl-2-hydroxyethylammonium chloride or Quatemium 80 is added; b) quat-doped solutions of the UV absorber according to the invention in butyl triglycol and tributyl citrate; c) mixtures or solutions of the UV absorber according to the invention with n-alkylpyR1olidone. Other typical ingredients in such formulations are preservatives, bactericides and bacterio¬static agents, perfumes, dyes, pigments, thickening agents, moisturizing agents, humectants, fats, oils, waxes or other typical ingredients of cosmetic and personal care formulations such as alcohols, poly-alcohols, polymers, electrolytes, oR2anic solvents, silicon derivatives, Preparation Examples Example 1: General work procedure for the synthesis of dialkylated compounds of formula 2-(4-Aminophenyl)-6-methylbenzothJazole (0.12 mol) is dissolved in 200 ml of absolute tetrahydrofuran and cooled to -10°C. At from -5 to -10C, 6.34 g of (0.264mol) of sodium hydride is added, in portions, to the solution. The reaction mixture is stiR1ed at 10°C for 30 minutes. Then, 0.28 mol of the appropriate haloalkane dissolved in 200 ml of absolute tetrahydrofuran is added dropwise in such a manner that the reaction temperature does not exceed 10'C. The reaction mixture is then heated to boiling point and refluxed for about 20 hours. After the reaction is complete, 10 ml of methanol are added and the reaction mixture is then reduced to half its original volume using a rotary evaporator. After adding 200 ml of distilled water, the C1-ude product is extracted with ethyl acetate. Subsequent column chromatography over silica gel using a mixture of cyclohexane and ethyl acetate yields the pure product, which is dried under a high vacuum at SOX and 0.02 mbar. Example 2: General work procedure for the synthesis of monoalkylated compounds of 0.12 mol of 2-(4-aminophenyl)-6-methylbenzothiazole is dissolved in 200 ml of absolute tetrahydrofuran and cooled to -10°C. At from -5 to -10'C, 3.17g (0.132 mol) of sodium hydride are added, in portions, to the solution. The reaction mixture is then stin-ed at 10C for 30 minutes before 0.13 mol of the appropriate haloalkane dissolved in 200 ml of absolute tetrahydrofuran is added dropwise. After heating to boiling point, the reaction mixture is refluxed for about 20 hours until the reaction is complete 10 ml of methanol are then added and the reaction mixture is concentrated to half its original volume using a rotary evaporator. After adding 200 ml of distilled water, the C1-ude product is extracted with ethyl acetate. Subsequent column chromatography over silica gel using a mixture of cyclohexane and ethyl acetate yields the pure product, which is dried under a high vacuum at 80°C and 0.02 mbar. Example 3: General work procedure for the synthesis of compounds of These compounds may be prepared by condensation of the appropriately Ra-substituted substituted p-aminobenzoic acid derivatives in a manner known per se, for example in accordance with DE 2 333 378 or E. Bami et al., J. Heterocyclic Chem. 20, 1517-1521 (1983) or with the appropriate R1, R2- and R4-substituted p-aminobenzaldehyde derivatives, for example in accordance with DE 2 333 378 and the literature references cited herein. WE CLAIM : 1. A cosmetic preparation comprising at least one compound of formula R1is hydrogen; unsubstituted or halo-, amino-, mono- or di-C1-C5alkylamino-, cyano- or C1-C5 alkoxy-substituted C1-C22alkyl, C5-C10cycloalkyl, carboxy-C1 -Caaalkyl, carboxy-C6-C10aryl, C5-C10aryl, C6-Cioaryl-C1-C5alkyl; carbamoyl; or sulfamoyl; R2 is branched or unbranched C6-C12alkyl: R3 is hydrogen; or C1-C22alkyl; and R4 is hydrogen; hydroxy; C1-C22alkyl; or C1-C22alkoxy; together with cosmetically acceptable carriers or adjuvants. 2. A compound of formula R1 is hydrogen;C1-C22alkyl; or carboxy-C1-C22alkyI; R2 branched or unbranched C6-C12alkyl 7 FEB ZOOS JPLICATE

Full Text

Aminophenylbenzothiazole compounds
The present invention relates to the use of aminophenylbenzothiazole compounds as UV filters, especially for protecting human and animal hair and skin from UV radiation, to processes for the preparation of those compounds and to cosmetic preparations comprising those compounds.
The present invention relates to the use, as UV filters, of compounds of formula

R1 and R2 are each independently of the other hydrogen; unsubstituted or halo-, amino-, mono- or di-C1-C6alkylamino-, cyano- or C1-Csalkoxy-substituted C1-C22alkyl, C5-C10cycloalkyI, carboxy-C1-C22alkyl, carboxy-C6-C10aryl, Ce-Cioaryl or C6-C10aryl-C1-Csalkyl; carbamoyl; or sulfamoyl; or
R1 and R2, together with the nitrogen atom linking them, form a 5- to 7-membered heterocyclic radical; and
R3 is hydrogen; or C1-C22alkyl; and
R4 is hydrogen; hydroxy; C1-C22alkyl; or C1-C22alkoxy.
C1-C22Alkyl radicals are straight-chain or branched alkyl radicals such as, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, amyl, isoamyl ortert-amyl, hexyl, 2-ethylhexyl, heptyl, octyl, isooctyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl or eicosyl.
C6-C10CycloaJkyl is, for example, cyclopentyl, cycloheptyl, cyclooctyi, cyclononyl or cyclodecyl and, especially, cyclohexyl. Those radicals may be substituted, for example by one or more identical or different C1-C4alkyl radicals, especially by methyl, and/or by hydroxy. When cycloalkyi radicals are substituted by one or more substituents, they are preferably substituted by one, two or four, especially one or two, identical or different substituents.
C6-C10Aryl is naphthyl or, especially, phenyl.

C1-C22Alkoxy radicals are straight-chain or branched radicals such as, for example, methoxy, ethoxy, propoxy, butoxy or pentyloxy, hexyloxy, heptyloxy, octyloxy, isooctyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tetradecyloxy, pentadecyloxy, hexadecyloxy, hepta-decyloxy, octadecyloxy or eicosyloxy.
Heterocyclic radicals contain one, two, three or four identical or different ring hetero atoms. Special preference is given to heterocycles containing one, two or three, especially one or two, identical or different hetero atoms. The heterocycles may be mono- or poly-cyclic, for example mono-, bi- or tri-cyclic. They are preferably mono- or bi-cyclic, especially monocyclic. The rings are preferably 5-, 6- or 7-membered. Examples of monocyclic and bicyclic heterocyclic systems from which radicals occunring in the compounds of formula (1) may be derived are, for example, pyR1ole, furan, thiophene, imidazole, pyrazole, 1,2,3-triazole, 1,2,4-triazole, pyridine, pyridazine, pyrimidine, pyrazine, pyran, thiopyran, 1,4-dioxane, 1,2-oxazine, 1,3-oxazine, 1,4-oxazine, indole, benzothiophene, benzofuran, pyR1olidine, piperidine, piperazine, morpholine and thiomorpholine.
Unsaturated heterocycles may contain, for example, one, two or three unsaturated double bonds in the ring system. 5-membered and 6-membered rings in monocyclic and polycyciic heterocycles may, especially, also be aromatic.
C6-C10AryJ and heteroaryl radicals may be unsubstltuted or may caR1y one or more, for example one, two, three or four, identical or different substituents, which may be located in any positions. Examples of such substituents are, e.g., C1-C4alkyl, halogen, hydroxy, C1-C4alkoxy, trifluoromethyl, cyano, hydroxycarbonyl, C1-C4alkoxycarbonyl, aminocarbonyl, amino, C1-C4alkylamino, di-C1-C4alkylamino and C1-C4alkylcarbonylamino.
Halogen is fluorine, chlorine, bromine or iodine, preferably fluorine or chlorine.
In accordance with the invention, preference is given to the use of UV filters of fonnula (1)
wherein
R4 is hydrogen.

Preference is given especially to compounds of formula (1) wherein R1 and R2 are each independently of the other hydrogen; or d-C12alkyl unsubstituted or substituted by halogen, amino, mono- ordi-C1-Qalkylamino, cyano or by C1-C5alkoxy; and R3 is hydrogen; or C1-Csalkyl.
Special preference is given to compounds of formula (1) wherein
Ri and R2 are each independently of the other hydrogen; or C1-Ciaalkyl; or
Ri and R2 together form a 5- to 7-membered heterocyclic radical;
R3 is hydrogen; or C1-CsalkyI; and
R4 is hydrogen.
Very special preference is given to compounds of formula (1) wherein
Ri is hydrogen;
R2 is C1-C12alkyl;
R3 is hydrogen; or C1-C5alkyI; and
R4 is hydrogen;
and especially to compounds of formula (1) wherein
R2 is branched or unbranched C6-C12alkyI; very especially n-hexyl; n-octyl; or 2-ethylhexyl.
Very special preference is also given to compounds of formula (1) wherein R4 is hydroxy.
Examples of compounds used in accordance with the Invention are listed in Table 1, which follows:

Aminophenylbenzothiazole compounds are known in the literature and some are commercially available.
The compounds of formula (1) according to the invention can be prepared, for example, by
condensation of Ra-substituted o-amino-thiophenols of fomnula Rj-jJ- I with R1, R2-
and R4 -substituted p-amino-benzaldehydes, where appropriate in the presence of an oxidising agent [R.C. Elderfield, "Heterocyclic Compounds", Vol. 5, 508 ff, O. Sus et aJ, US Patent 3 257 204 (1966), HP. Lankelma et a/, J. Amer. Chem. Soc. 54, 379, (1932) or Stephens ef a/., J. Chem. Soc. (1950) 1722].

Condensation of o-amino-thiophenols with Ri- and Ra-substituted p-aminobenzoic acids in accordance with LC. Galatis, J. Amer. Chem. See. 70, 1967 (1948) also yields compounds of the general formula (1).
The benzothiazole compounds of the general formula (1) wherein R, is hydrogen and R2 is an unsubstituted or substituted aralkyi radical are obtained by reaction of F^-substituted 2-{4'-aminophenyO-benzothiazoles with unsubstituted or substituted benzaldehydes to fomn the coR1esponding azomethines, which may be hydrogenated very simply using sodium boronate in polar solvents to form the coR1esponding 2-{4'-benzylaminophenyl)benzothiazole derivatives [J. H. Billmann et a/., J. OR2. Chem. 22, 1068, (1957)].
The benzothiazole compounds of the general formula (1) wherein R, and/or R2 is/are an unsubstituted or substituted alkyl or aralkyi radical can also be prepared by direct alkylation of commercially available 2-{4-aminophenyl)-6-methylbenzothiazole. As alkylating agents there can be used, analogously to DE-OS-51738, the appropriate alcohols under the action of strong acids.
The compounds of formula (1) according to the invention wherein Ri is hydrogen are prepared from Ra-substituted 2-{4-aminophenyl)-benzothiazole by alkylation with the appropriate haloalkanes/haloaralkanes using a base, in accordance with the following Scheme:

wherein R2, R3 and R4 are as defined in claim 1.
The compounds of fonnula (1) wherein Ri and R2 are alkyl or aryl-alkyi are prepared from R3-substituted 2-(4-aminophenyl)-benzothiazole by alkylation with the appropriate haloal¬kanes/haloaralkanes using a base, in accordance with the following Scheme:

As base there may be used a metal hydride, such as sodium hydride, an alkali metal alcohoiate such as, for example, sodium methanoiate, sodium ethanoiate or potassium tert-butanolate, or an alkali metal hydroxide, such as sodium hydroxide or potassium hydroxide, an amine base, such as EtsN, (isoprop)2EtN or quinalidine etc.. Likewise, basic ion exchangers may also be used. The reaction may also be caR1ied out without the addition of base.
The reaction is preferably caR1ied out in dimethyl sulfoxide, N-methylpyR1olidone, dimethyl-formamide or dimethylacetamide, but protic solvents, such as methanol, ethanol, isobutanol, tert-butanol or isopropanol, are also possible. In addition, the reaction may also be caR1ied out in aliphatic or aromatic solvents, such as hexane, toluene or xylene. Ethers, such as diethyl ether and tetrahydrofuran, or halogenated solvents, such as chloroform or dichloromethane, are also possible. Likewise, solvent mixtures may also be used.
The reaction may be caR1ied out at temperatures between -TS^C and the boiling point of the reaction mixture, preferably proceeding at from 10 to 120'C.
Usually a laR2e excess of alkylating agent is used and alkylating agent remaining after the reaction is removed by vacuum distillation. Preference is given to the use of from 1.0 to 8.0 mol of the haloalkane/haloaralkane, based on 1 mol of aminophenylbenzothiazole.
The products are purified by reC1-ystallisation from a suitable solvent or by column-chromato-graphic separation using a suitable eluant.
The invention relates also to the process for the preparation of compounds of fonnula(1).

^,..^.v.vJMuo ui me rormuia (1) according to the present invention are particularly suitable
as UV filters, i.e. for protecting ultraviolet-sensitive oR2anic materials, in particular the skin and hair of humans and animals, from the harmful effects of UV radiation. These compounds are therefore suitable as sunsC1-eens in cosmetic, pharmaceutical and veterinary medical preparations. These compounds can be used both in dissolved form and in the miC1-onized state.
The UV absorbers according to the present invention can be used either in the dissolved state (soluble oR2anic filters, solubilized oR2anic filters) or in the miC1-onised state (nanoscalar oR2anic filters, particulate oR2anic filters, UV-absorber pigments).
The triazine derivatives of formula (1) which have no alkyl substituents or only lower-alkyi substituents are characterized by a poor oil-solubility and a high melting point. They are therefore particularly suitable UV absorbers in the miC1-onized state.
Any known process suitable for the preparation of miC1-oparticles can be used for the pre¬paration of the miC1-onised UV absorbers, for example:
wet-milling (low viscous miC1-onisatlon process for pumpable dispersions), with a hard grinding medium, for example zirconium silicate balls in a ball mill and a protective surfactant or a protective polymer in water or in a suitable oR2anic solvent;
wet-kneading (high viscous miC1-onisatlon process for non pump-able pastes) using a continuous or discontinuous (batch) kneader. For a wet-kneading process a solvent (water or cosmetically acceptable oils), a grinding-aid (surfactant, emulsifier) and a polymeric grinding aid may be used. Both processes may be used respectively spray-drying from a suitable solvent, for example aqueous suspensions or suspensions containing oR2anic solvents, or true solutions In water, ethanol, dichloroethane, toluene or N-methylpyR1olidone etc..
by the expansion according to the RESS process (Rapid Jxpansion of SuperC1-itical Solutions) of superC1-itical fluids (e.g. CO2) in which the UV filter or filters is/are dissolved, or the expansion of fluid carison dioxide together with a solution of one or more UV filters in a suitable oR2anic solvent;
by reprecipitation from suitable solvents, including superC1-itical fluids (GASR process = Gas Anti-Solvent ReC1-ystallisation / PCA process = Precipitation with Compressed Anti-solvents).

As milling apparatus for the preparation of the miC1-onised oR2anic UV absorbers there may be used, for example, a jet mill, ball mill, vibratory mill or hammer mill, preferably a high¬speed mixing mill. Even more preferable mills are modern ball mills, manufacturers of these mill-types are for example Netzsch (LMZ-mill), Drais (DCP-viscoflow or cosmo), Buhler AG (centrifugal mills) or Bachhofer. The grinding is preferably caR1ied out with a grinding aid. As kneading apparatus for the preparation of the miC1-onised oR2anic UV absorbers examples are typical sigma-hook batch kneaders but also serial batch kneaders (IKA-Werke) or continuous kneaders (Continua from Werner und Pfleiderer).
Useful low molecular weight grinding aids for all the above miC1-onizing processes are sur¬factants and emulsifies as disclosed below in the chapters "emulsifiers" and "surfactants".
Useful polymeric grinding aids for water dispersion are cosmetically acceptable water soluble polymers with MW > 5000 g/mol for example: aC1-ylates (Salcare types), modified or non-modified polysaccharides, poiyglucosides or xanthan gum. Furthermore an alkylated vinyl-pyR1olidone polymer, a vinylpyR1olidone/vinyl acetate copolymer, an acyl glutamate, an alkyl polyglucoside, ceteareth-25 or a phospholipid may be used. Oil dispersions may contain cosmetically acceptable waxy polymers or natural waxes as polymeric grinding aid to adjust viscosity during and after processing.
Useful solvents are water, brine, (poly-)ethyleneglycol or glycerine for water-soluble dis¬persions and also cosmetically acceptable oils as desC1-ibed under "emollients" for oil-soluble dispersions.
The miC1-onised UV absorbers so obtained usually have an average particle size from 0.02 to 2 miC1-ometers, preferably from 0.05 to 1.5 miC1-ometer and more especially from 0.1 to 1.0 miC1-ometers.
The UV absoriaers can also be used dry in powder form. For that purpose the UV absorbers are subjected to known grinding methods, such as vacuum atomization, countercuR1ent spray-drying etc.. Such powders have a particle size of from 0.1 to 2 miC1-ometers. To avoid the occuR1ence of agglomeration, the UV absorbers can be coated with a surface-active

compound prior to the pulverization process, for example with an anionic, non-ionic or amphoteric surfactant, e.g. a phospholipid or a known polymer, such as PVP, an aC1-ylate etc.
The cosmetic formulations or pharmaceutical compositions according to the present inven¬tion can also contain one or more than one further UV filter as desC1-ibed 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 stiR1ing to¬gether the individual components, especially by making use of the dissolution properties of already known cosmetic UV absorbers, for example octyl methoxy cinnamate, salicylic acid isooctyl ester, etc. The UV absorber can be used, for example, without further treatment, or in the miC1-onised state, or in the form of a powder.
Cosmetic or pharmaceutical preparations contain from 0.05-40% by weight, based on the total weight of the composition, of one UV absorber or UV absorber mixtures.
Preference is given to the use of mixing ratios of the UV absorber of formula (1) according to the present invention and optionally further light-protective agents (as desC1-ibed in table 1-3) 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 mixing ratios of from 20:80 to 80:20, especially from 40:60 to 60:40 and preferably approximately 50:50. Such mixtures can be used, inter alia, to improve solubility or inC1-ease UV absorption.

The cosmetic or pharmaceutical preparations may be, for example, C1-eams, gels, lotions, alcoholic and aqueous/alcoholic solutions, emulsions, wax/fat compositions, stick prepa¬rations, powders or ointments. In addition to the above mentioned UV filters, the cosmetic or pharmaceutical preparations may contain further adjuvants as desC1-ibed below.
As water- and oil-containing emulsions (e.g. W/0, OAA/, 0/W/O and W/O/W emulsions or miC1-oemulsions) the preparations contain, for example, from 0.1 to 30 % by weight, pre¬ferably from 0.1 to 15 % by weight and especially from 0.5 to 10 % by weight, based on the total weight of the composition, of one or more UV absorbers, from 1 to 60 % by weight, especially from 5 to 50 % by weight and preferably from 10 to 35 % by weight, based on the total weight of the composition, of at least one oil component, from 0 to 30 % by weight, especially from 1 to 30 % by weight and 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 as desC1-ibed below.
Fatty alcohols
Guerbet alcohols based on fatty alcohols having from 6 to 18, preferably from 8 to 10 carbon atoms including cetyl alcohol, stearyl alcohol, cetearyl alcohol, oleyl alcohol, octydodecanol, benzoate of C12-C15 alcohols, acetylated lanoin alcohol, etc..
Esters of fatty acids
Esters of linear C8-C24 fatty acids with linear C3-C24 alcohols, esters of branched Ce-Ciscar-boxylic acids with linear C8-C24 fatty alcohols, esters of linear C6-C24 fatty acids with branched alcohols, especially 2-ethylhexanol, esters of hydroxycarboxylic acids with linear or branched C8-C22 fatty alcohols, especially dioctyl malates, esters of linear and/or branched fatty acids with polyhydric alcohols (for example propylene glycol, dimer diol or trimer triol) and/or Guerbet alcohols, for example caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeo-

stearic acid, arachidic acid, gadoleic acid, belienic acid and erucic acid and technical-grade mixtures thereof (obtained, for example, in the pressure removal of natural fats and oils, in the reduction of aldehydes from Roelen's oxosynthesis or in the dimerisation of unsaturated fatty acids) with alcohols, for example, isopropyt alcohol, caproic alcohol, capryl alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linoyl alcohol, linolenyl alcohol, elaeostearyl alcohol, arachidyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and technical-grade mixtures thereof (obtained, for example, in the high-pressure hydrogenation of technical-grade methyl esters based on fats and oils or aldehydes from Roelen's oxosynthesis and as monomer fractions in the dimerisation of unsaturated fatty alcohols).
Examples of such ester oils are isopropyl myristate, isopropyl palmitate, isopropyl stearate, isopropyi isostearate, isopropyl oleate, n-butyl stearate, n-hexyl laurate, n-decyl oleate, iso-octyl stearate, iso-nonyl stearate, isononyl isononanoate, 2-ethylhexyl palmitate, 2-hexyllau-rate, 2-hexyldecyl stearate, 2-octyldodecyl palmitate, oleyl oleate, oleyl erucate, erucyl ole¬ate, erucyl erucate, cetearyl octanoate, cetyl palmitate, cetyl stearate, cetyl oleate, cetyl be-henate, cetyl acetate, myristyl myristate, myristyl behenate, myristyl oleate, myristyl stearate, myristyl palmitate, myristyl lactate, propylene glycol dicaprylate/caprate, stearyl heptanoate, diisostearyl malate, octyl hydroxystearate, etc..
Other adjuvants
diethylhexyl 2,6- naphthalate, 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 dl(2-ethylhexanoate), propylene glycol dilsostearate, propylene glycol dipelaR2onate, butanedlol diisostearate and neopentyl glycol dicaprylate. Esters of C8-C24 fatty alcohols and/or Guerbet alcohols with aromatic carboxylic acids, saturated and/or unsaturated, especially benzoic acid, esters of C2-Ci2dicarboxylic acids with linear or branched alcohols having from 1 to 22 carbon atoms or polyols having from 2 to 10 carbon atoms and from 2 to 6 hydroxy groups.
Natural or synthetic triglycerides including glycervl esters and derivatives
Di- or tri-glycerides, based on Ce-Cia fatty acids, modified by reaction with other alcohols
(caprylic/capric triglyceride, wheat germ glycerides, etc.). Fatty acid esters of polyglycerin

^^.v^.^aiyociyi-ii sucn as poiygiyceryl-4 caprate, polyglyceryl-2 isostearate, etc. or castor oil, hydrogenated vegetable oil, sweet almond oil, wheat germ oil, sesame oil, hydrogenated cottonseed oil, coconut oil, avocado oil, corn oil, hydrogenated castor oil, shea butter, cocoa butter, soybean oil, mink oil, sunflower oil, safflower oil, macadamia nut oil, olive oil, hydro¬genated tallow, apricot kernel oil, hazelnut oil, borage oil, etc.
Waxes including esters of long-chain acids and alcohols as well as compounds having wax¬like properties, e.g., carnauba wax, beeswax (white or yellow), lanolin wax, candelilla wax, ozokerite, japan wax, paraffin wax, miC1-oC1-ystalline wax, ceresin, cetearyl esters wax, syn¬thetic beeswax etc. Also, hydrophilic waxes as cetearyl alcohol or partial glycerides.
Pearlescent waxes:
Ikylene glycol esters, especially ethylene glycol distearate; fatty acid alkanol amides, especially coco fatty acid diethanolamide; partial glycerides, especially stearic acid mono-glyceride; esters of polyvalent, unsubstituted or hydroxy-substituted carboxylic acids with fatty alcohols having from 6 to 22 carbon atoms, especially long-chained esters of tartaric acid; fatty substances, for example fatty alcohols, fatty ketones, fatty aldehydes, fatty ethers and fatty carbonates, which in total have at least 24 carbon atoms, especially laurone and distearyl ether; fatty acids, such as stearic acid, hydroxystearic acid or behenic acid, ring-opening products of olefin epoxides having from 12 to 22 carbon atoms with fatty alcohols having from 12 to 22 carbon atoms and/or polyols having from 2 to 15 carbon atoms and from 2 to 10 hydroxy groups, and mixtures thereof.
Hydrocarbon oils:
Mineral oil (light or heavy), petrolatum (yellow or white), miC1-oC1-ystalline wax, paraffinic and isoparaffinic compounds, hydrogenated isoparaffinic molecules as polydecenes and pol^u-tene, hydrogenated polyisobutene, squalane, isohexadecane, isododecane and others from plant and animal kingdom.
Silicones or siloxanes (oR2anosubstituted polvsiloxanes)
Dimethylpolysiloxanes, methylphenylpolysiloxanes, cyclic silicones, and also amino-, fatty acid-, alcohol-, polyether-, epoxy-, fluorine-, glycoside- and/or alkyl-modified silicone com¬pounds, which at room temperature may be in either liquid or resinous fonri. Linear poly-siloxanes, dimethicone (Dow Corning 200 fluid, Rhodia Mirasil DM), dimethiconol, cyclic

silicone fluids, cyclopentasiioxanes volatiies (Dow Corning 345 fluid), phenyltrimethicone (Dow Corning 556 fluid). Also suitable are simethicones, which are mixtures of dimethicones having an average chain length of from 200 to 300 dimethylsiloxane units with hydrcgenated silicates. A detailed survey by Todd ef a/, of suitable volatile silicones may in addition be found in Cosm. Toil. 91. 27 (1976).
Fluorinated or perfluorinated oils
Perfluorohexane, dimethylcyclohexane, ethylcyclopentane, polyperfluoromethylisopropyl
ether,
Emulsifiers
Any conventionally emulsifier can be used for the compositions. Emulsifier systems may comprise for example: carboxylic acids and their salts: alkaline soap of sodium, potassium and ammonium, metallic soap of calcium or magnesium, oR2anic basis soap such as lauric, palmitic, stearic and oleic acid etc.. Alkyl phosphates or phosphoric acid esters, acid phos¬phate, diethanolamlne phosphate, potassium cetyl phosphate. Ethoxylated carboxylic acids or polyethylene glycol esters, PEG-n acylates. Linear fatty alcohols having from 8 to 22 carbon atoms, branched from 2 to 30 mol of ethylene oxide and/or from 0 to 5 mol propylene oxide with fatty acids having from 12 to 22 carbon atoms and with alkylphenols having from 8 to 15 carbon atoms in the alkyl group. Fatty alcohol polyglycolether such as laureth-n, ceteareth-n, steareth-n, oleth-n. Fatty acid polyglycolether such as PEG-n stearate, PEG-n oleate, PEG-n cocoate. Monoglycerides and polyol esters. Cia-Ca fatty acid mono- and di-esters of addition products of from 1 to 30 mol of ethylene oxide with polyols. Fatty acid and polyglycerol ester such as monostearate glycerol, diisostearoyi polyglyceryi-3-diisostearates, polyglyceryl-3-cliisostearates, triglyceryl diisostearates, polyglyceryl-2-sesquiisostearates or poiyglyceryl dimerates. Mixtures of compounds from a plurality of those substance classes are also suitable. Fatty acid polyglycolesters such as monostearate diethylene glycol, fatty acid and polyethylene glycol esters, fatty acid and saccharose esters such as susro esters, glycerol and saccharose esters such as suC1-o glycerides. Sorbitol and sorbitan, sorbitan mono- and di-esters of saturated and unsaturated fatty acids having from 6 to 22 carbon atoms and ethylene oxide addition products. Polysorbate-n series, sorbitan esters such as sesquiisostearate, sorbitan, PEG-(6)-isostearate sorbitan, PEG-(10)-sorbitan laurate, PEG-17- dioleate sorbitan. Glucose derivatives, C8-C22 alkyl-mono and oligo-glycosides and ethoxylated analogues with glucose being prefeR1ed as the sugar component. 0/W

emulsifiers such as methyl gluc8th-20 sesquistearate, sorbitan stearate/suC1-ose cocoate, methyl glucose sesquistearate, cetearyi alcohol/cetearyl glucoside. W/O emulsifiers such as methyl glucose dioleate/ methyl glucose isostearate. Sulfates and sulfonated derivatives, dialkylsulfosuccinates, dioctyl succinate, alkyl lauryl sulfonate, linear sulfonated parafins, sulfonated tetrapropylene sulfonate, sodium lauryl sulfates, ammonium and ethanolamine lauryl sulfates, lauyl ether sulfates, sodium laureth sulfates, sulfosuccinates, aceyl isothionates, alkanolamide sulfates, taurines, methyl taurines, imidazole sulfates. Amine derivatives, amine salts, ethoxylated amines, oxide amine with chains containing an heterocyde such as alkyl imidazolines, pyridine derivatives, isoquinoteines, cetyl pyridinium chloride, cetyl pyridinium bromide, quaternary ammonium such as cetyltrimethylbroimde amonium bromide (CTBA), stearylalkonium. Amide derivatives, alkanolamides such as acylamide DEA, ethoxylated amides such as PEG-n acylamide, oxydeamide. Poly-siloxane/polyalkyl/polyether copolymers and derivatives, dimethicone, copolyols, silicone polyethylene oxide copolymer, silicone glycol copolymer. Propoxylated or POE-n ethers (Meroxapols), Polaxamers or poly(oxyethylene)m-b!ock-poly(oxypropylene)n-block(oxy-ethylene). Zwitterionic surfactants that caR1y at least one quaternary ammonium group and at least one carboxylate and/or sulfonate group in the molecule. Zwitterionic suifactants that are especially suitable are betaines, such as N-alkyl-N,N-dimethylammonium glycinates, coco-alkyldimethylammonium glycinate, N-acylaminopropyl-N,N-dimethylammonium glycinates, cocoacylaminopropyldimethylammonium glycinate and 2-alkyl-3-carboxymethyl-3-hydroxy-ethylimidazolines each having from 8 to 18 carbon atoms in the alkyl or acyl group and also cocoacylaminoethylhydroxyethylcarboxymethylglycinate, N-alkylbetaine, N-alkylaminobe-taines. Alkytimidazolines, alkylopeptides, lipoaminoacids, self emulsifying bases and the compounds as desC1-ibed in K.F.DePolo, A short textbook of cosmetology. Chapter 8, Table 8-7, p250-251.
Non ionic bases such as PEG-6 beeswax (and) PEG-6 stearate (and) polyglyceryl -2-iso-stearate [Apifac], glyceryl stearate (and) PEG-100 stearate. [Arlacel 165], PEG-5 glyceryl stearate [arlatone 983 S], sorbitan oleate (and) polyglyceryl-3 ricinoleate. [Arlacel 1689], sorbitan stearate and suC1-ose cocoate [arlatone 2121], glyceryl stearate and laureth-23 [Cerasynth 945], cetearyi alcohol and ceteth-20 [CetomaC1-ogol Wax], cetearyi alcohol and polysorbate 60 and PEG-150 and stearate-20[Polawax GP 200, Polawax NF], cetearyi alcohol and cetearyi polyglucoside [Emulgade PL 1618], cetearyi alcohol and ceteareth-20 [Emulgade 1000NI, Cosmowax], cetearyi alcohol and PEG-4Q castor oil [Emulgade F

Special], cetearyl alcohol and PEG-40 castor oil and sodium cetearyl sulfate [Emulgade F], stearyl alcohol and steareth-7 and steareth-10 [Emulgator E 2155], cetearyl alcohol and szeareth-7 and steareth-10 [Emulsifying wax U.S.N.F], glyceryl stearate and PEG-75 stearate [Gelot 54], propylene glycol ceteth-3 acetate .[Hetester FCS], propylene glycol isoceth-3 acetate [Hetester PHA], cetearyl alcohol and ceteth-12 and Qleth-12 [Lanbritol Wax N 21], PEG -6 stearate and PEG-32 stearate [Tefose 1500], PEG-6 stearate and ceteth-20 and steareth-20 [Tefose 2000], PEG-6 stearate and ceteth-20 and glyceryl stearate and steareth-20 [Tefose 2561], glyceryl stearate and ceteareth-20 [Teginacid H, C, X].
Anionic alkaline bases such as PEG-2 stearate SE, glyceryl stearate SE [Monelgine, Cutina KD], propylene glycol stearate [Tegin P]. Anionic acid bases such as cetearyl Alcohol and Sodium cetearyl sulfate [Lanette N, Cutina LE, C1-odacol GP], cetearyl alcohol and sodium lauryl sulfate [Lanette W], trilaneth-4 phosphate and glycol stearate and PEG-2 stearate [Sedefos 75], glyceryl stearate and sodium lauryl sulfate [Teginacid Special]. Cationic acid bases such as cetearyl alcohol and cetrimonium bromide.
The emulsifiers may be used in an amount of, for example, from 1 to 30 % by weight, especially from 4 to 20 % by weight and preferably from 5to 10 % by weight, based on the total weight of the composition.
When formulated in OA/V emulsions, the prefeR1ed amount of such emulsifier system could represent 5% to 20% of the oil phase.
Adjuvants and additives
The cosmetic / pharmaceutical preparations, for example C1-eams, gels, lotions, alcoholic and aqueous/alcoholic solutions, emulsions, wax/fat compositions, stick preparations, powders or ointments, may in addition contain, as further adjuvants and additives, mild surfactants, su¬per-fatting agents, consistency regulators, thickeners, polymers, stabilisers, biogenic active ingredients, deodorising active ingredients, anti-dandruff agents, film fomners, swelling agents, further UV light-protective factors, antioxidants, hydrotropic agents, preservatives, insect repellents, self-tanning agents, solubilisers, perfume oils, colourants, bacteria-inhibiting agents and the like.

Super-fatting agents
Substances suitable for use as super-fatting agents are, for example, lanolin and lecithin and
also polyethoxylated or aC1-ylated lanolin and lecithin derivatives, polyol fatty acid esters,
monoglycerides and fatty acid alkanolamides, the latter simultaneously acting as foam
stabilisers.
Surfactants
Examples of suitable mild surfactants, that is to say surfactants especially well tolerated by the skin, include fatty alcohol polyglycol ether sulfates, monoglyceride sulfates, mono- and/or di-alkyi sulfosuccinates, fatty acid isethionates, fatty acid sarcosinates, fatty acid tai/ides, fatty acid glutamates, a-olefin sulfonates, ethercarboxylic acids, alkyl oligoglucosides, fatty acid gtucamides, alkylamidobetaines and/or protein fatty acid condensation products, the latter preferably being based on wheat proteins.
Consistency regulators/thickeners and rheology modifiers
Silicon dioxide, magnesium silicates, aluminium silicates, polysaccharides or derivatives thereof for example hyaluronic acid, xanthan gum, guar-guar, agar-agar, alginates, caR1ageenan, gellan, pectins, or modified cellulose such as hydroxycellulose, hydroxypropyl-methylcellulose. In addition polyaC1-ylates or homopolymers of reticulated aC1-ylic acids and polyaC1-ylamides, carbomer (carbopol types 980, 981, 1382, ETD 2001, ETD2020, Ultrez 10) orSalcare range such as Salcare SC80(steareth-10 allyl ether/aC1-ylates copolymer), Salcare SC81(aC1-ylates copolymer), Salcare SC91 and Salcare AST{sodium aC1-ylates copoly-mer/PPG-1 trideceth-6), sepigel 305(polyaC1-ylamide/laureth-7), Simulgel NS and Simulgei EG (hydroxyethyi aC1-ylate / sodium aC1-yloyidimethyi taurate copolymer), Stabilen 30 (aC1-y¬lates / vinyl isodecanoate C1-osspolymer), Pemulen TR-1 (aC1-ylates / C10-30 alkyl aC1->Jate C1-osspolymer), Luvigel EM (sodium aC1-ylates copolymer), Aculyn 28 (aC1-ylates/beheneth-25 methaC1-ylate copolymer), etc..
Polymers
Suitable cationic polymers are, for example, cationic cellulose derivatives, for example a quaternised hydroxymethyl cellulose obtainable under the name Polymer JR 400 from Amerchol, cationic starches, copolymers of diallylammonium salts and aC1-ylamides, quater¬nised vinylpyR1olidone/vinyl imidazole polymers, for example Luviquat® (BASF), condensation products of polyglycols and amines, quaternised collagen polypeptides, for example lauryl-

dimonium hydroxypropyl hydrolyzed collagen (Lamequat®UGrunau), quaternised wheat poly¬peptides, polyethyleneimine, cationic silicone polymers, for example amidomethicones, copo¬lymers of adipic acid and dimethyiaminohydroxypropyldiethylen^riamine (Cartaretin/San-doz), copolymers of aC1-ylic acid with dimethyldiallylammonium chloride (Merquat 550/Chem-viron), poiyaminopolyamides, as desC1-ibed, for example, in FR-A-2 252 840, and the C1-oss-linked water-soluble polymers thereof, cationic chitin derivatives, for example of quaternised chitosan, optionally distributed as miC1-oC1-ystals; condensation products of dihalcalkyls, for example dibromobutane, with bisdialkylamines, for example bisdimethyfeimino-1,3-propane, cationic guar gum, for example Jaguar C-17, Jaguar C-16 from Celanese, quaternised ammonium salt polymers, for example Mirapol A-15, Mirapol AD-1, Mir^ol AZ-1 from . Miranol. As anionic, zwitterionic, amphoteric and non-ionic polymers there come into consideration, for example, vinyl acetate / C1-otonic acid copolymers, vinylpyR1didone / vinyl aC1-ylate copolymers, vinyl acetate / butyl maleate / isobornyl aC1-ylate copolymers, methyl vinyl ether / maleic anhydride copolymers and esters thereof, unC1-osslinked polyaC1-ylic acids and polyaC1-ylic acids C1-osslinked with polyols, aC1-ylamidopropyl-trimethylammonium chloride /aC1-ylate copolymers, octyl aC1-ylamide/hiethyl methaC1-ylatetert-butylaminoethyl meth-aC1-ylate/2-hydroxypropyl methaC1-ylate copolymers, polyvinylpyR1olidone, vinylpyR1olidone/-vinyl acetate copolymers, vinylpyR1olidone/dimethylaminoethyl methaC1-ylate/vinyl capro-lactam terpolymers and also optionally derivatised cellulose ethers and silicones. Furthermore the polymers as desC1-ibed in EP 1093796 (pages 3-8, paragraphs 17-68) may be used.
Biogenic active ingredients
Biogenic active ingredients are to be understood as meaning, for example, tocopherol, toco¬pherol acetate, tocopherol palmitate, ascorbic acid, deoxyribonucleic acid, retinol, bisabolol, allantoin, phytantriol, panthenol, AHA acids, amino acids, ceramides, pseudoceramides, essential oils, plant extracts and vitamin complexes.
Deodorising active ingredients
As deodorising active ingredients there come into consideration, for example, anti-perspirants, for example aluminium chlorohydrates (see J. Soc. Cosm. Chem. 24, 281 (1973)). Under the trade mark LoC1-on® of Hoechst AG, Frankfurt (FR2), there is available commercially, for example, an aluminium chlorohydrate coR1esponding to fonnula Al2(OH)5CI X 2.5 H2O, the use of which is especially prefeR1ed (see J. Pharm. Pharmacol. 26,

531 (1975)). Besides the chlorohydrates, it is also possible to use aluminium hydroxyacetates and acidic aluminium/zirconium salts. Esterase inhibitors may be added as further deodorising active ingredients. Such inhibitors are preferably trialkyl citrates, such as trimethyl citrate, tripropyl citrate, triisopropyl citrate, tributyl citrate and especially triethyl citrate (Hydagen CAT, Henl Anti-dandruff agents
As anti-dandruff agents there may be used, for example, climbazole, octopirox and zinc pyri-
thione.
Film fonners
Customary film formers include, for example, chitosan, miC1-oC1-ystalline chitosan, qufitemised chitosan, polyvinylpyn-olidone, vinylpyR1olidone/vinyl acetate copolymers, polymers of quaternary cellulose derivatives containing a high proportion of aC1-ylic acid, collagen, hyaluronic acid and salts thereof and similar compounds.
Antioxidants
In addition to the primary light-protective substances it is also possible to use secondary light-protective substances of the antioxidant kind that inteR1upt the photochemical reaction chain triggered when UV radiation penetrates the skin or hair. Typical examples of such anti¬oxidants are amino acids (e.g. glycine, histidine, tyrosine, tryptophan) and derivatives there¬of, imidazoles (e.g. urocanic acid) and derivatives thereof, peptides, such as D,L-carnosine, D-carnosine, L-camosine and derivatives thereof (e.g. anserine), carotinoids, carotenes,

lycopene and derivatives thereof, chlorogenic acid and derivatives thereof, lipoic acid and derivatives thereof (e.g. dihydrolipoic acid), aurothioglycose, propylthiouracil and other thiols (e.g. thioredoxin, glutathione, cysteine, cystine, cystamine and the glycosyl, N-acetyl, mdhyl, ethyl, propyl, amyl, butyl, lauryl, palmitoyi, oleyl, linoleyl, cholesteryl and glyceryl esters thereof) and also salts thereof, dilauryl thiodipropionate, distearyl thiodipropionate, thiodi-propionic acid and derivatives thereof (esters, ethers, peptides, lipids, nucleotides, nucleo¬sides and salts) and also sulfoximine compounds (e.g. buthionine sulfoximines, homo¬cysteine sulfoximine, buthionine sulfones, penta-, hexa-, hepta-thionine sulfoximine), also (metal) chelating agents (e.g. hydroxy fatty acids, palmitic acid phytic acid, lactofeR1in), hydroxy acids (e.g. citric acid, lactic acid, malic acid), humic acid, bile acid, bile extracts, bilirubin, biliverdin, EDTA, EDDS, EGTA and derivatives thereof, unsaturated fatty acids and derivatives thereof (e.g. linolenic acid, linoleic acid, oleic acid), folic acid and derivatives thereof, ubiquinone and ubiquinol and derivatives thereof, vitamin C and derivatives (e.g. ascorbyl palmitate, magnesium ascorbyl phosphate, ascorbyl acetate), tocopherols and derivatives (e.g. vitamin E acetate), vitamin A and derivatives (e.g. vitamin A palmitate) and also coniferyl benzoate of benzoin resin, rutinic acid and derivatives thereof, glycosylrutin, ferulic acid, furfurylidene glucitol, carnosine, butyl hydroxytoluene, butyl hydroxyanisole, nordihydroguaiaretic acid, trihydroxybutyrophenone, uric acid and derivatives thereof, mannose and derivatives thereof, superoxide dismutase, N-[3-(3,5-di-tert-butyl-4-hydroxy-phenyl)propionyl]sulfanilic acid (and salts thereof, for example the disodium salts), zinc and derivatives thereof (e.g. ZnO, ZHSOA), selenium and derivatives thereof (e.g. selenium me¬thionine), stilbene and derivatives thereof (e.g. stilbene oxide, trans-stilbene oxide) and the derivatives suitable according to the invention (salts, esters, ethers, sugars, nucleotides, nucleosides, peptides and lipids) of those mentioned active ingredients. HALS (="Hindered Amine Light Stabilizers") compounds may also be mentioned. The amount of antioxidants present is usually from 0.001 to 30 % by weight, preferably from 0.01 to 3 % by weight, based on the weight of the UV absorber of formula (1).
Hydrotropic agents
To improve the flow behaviour it is also possible to employ hydrotropic agents, for example ethoxylated or non ethoxylated mono-alcohols, diols or polyols with a low number of carbon atoms or their ethers (e.g. ethanol, isopropanol, 1,2-dipropanediol, propylene glycol, glycerine, ethylene glycol, ethylene glycol monoethyl ether, ethylene glycol monobutylether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol

monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether and similar products). The polyols that come into consideration for that purpose have preferably from 2 to 15 carbon atoms and at least two hydroxy groups. The polyols may also contain further functional groups, especially amino groups, and/or may be modified with nitrogen. Typical examples are as follows: glycerol, alkylene glycols, for example ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, hexylene glycol and also polyethylene glycols having an average molecular weight of from 100 to 1000 Dalton; technical oligoglycerol mixtures having an intrinsic degree of condensation of from 1.5 to 10, for example technical diglycerol mixtures having a diglycerol content of from 40 to 50 % by weight; methylol compounds, such as, especially, trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol and dipentaerythritol; lower alkyl-glucosides, especially those having from 1 to 8 carbon atoms in the alky! radical, for example methyl and butyl glucoside; sugar alcohols having from 5 to 12 carbon atoms, for example sorbitol or mannitol; sugars having from 5 to 12 carbon atoms.for example glucose or saccharose; amino sugars, for example glucamine; dialcohol amines, such as diethanolamine or 2-amino-1,3-propanediol.
Preservatives
Suitable presen/atives include, for example, methyl-.ethyl-, propyl-, butyl- parabens, benzal-conium chloride, 2-Bromo-2-nitro-propane-1,3-dlol, dehydroacetic acid, diazolidinyl Urea, 2-dichloro-benzyl alcohol, DMDM hydantoin, formaldehyde solution, methyldibromogliJanitrile, phenoxyethanol, Sodium hydroxymethylglycinate, imidazolidinyl urea, Triclosan and further substance classes listed in the following reference: K.F.DePolo -A short textbook of cosmetology, Chapter 7, Table 7-2, 7-3, 7-4 and 7-5, p210-219.
Bacteria-inhibiting agents
Typical examples of bacteria-inhibiting agents are preservatives that have a specific action against gram-positive bacteria, such as 2,4,4'-trichloro-2-hydroxydiphenyl ether, chlorhexi-dine (1,6-di(4-chlorophenyl-biguanido)hexane) orTCC (3,4,4'-trichlorocarbanilide). A laR2e number of aromatic substances and ethereal oils also have antimiC1-obial properties. Typical examples are the active ingredients eugenol, menthol and thymol in clove oil, mint oil and thyme oil. A natural deodorising agent of interest is the terpene alcohol farnesol (3,7,11-tri-methyl-2,6,10-dodecatrien-1-ol), which is present in lime blossom oil. Glycerol mondaurate has also proved to be a bacteriostatic agent. The amount of the additional bacteria-inhbiting

agents present is usually from 0.1 to 2 % by weight, based on the solids content ofthe preparations.
Perfume oils
There may be mentioned as perfume oils mixtures of natural and/or synthetic aromatic sub¬stances. Natural aromatic substances are, for example, extracts from blossom (lilies, laven¬der, roses, jasmine, neroli, ylang-ylang), from stems and leaves (geranium, patchouli, petit-grain), from fruit (aniseed, coriander, caR1away, juniper), from fruit pee! (beR2amot, lemons, oranges), from roots (mace, angelica, celery, cardamom, costus, iris, calmus), from wood (pinewood, sandalwood, guaiacum wood, cedarwood, rosewood), from herbs and grasses (taR1agon, lemon grass, sage, thyme), from needles and twigs (spruce, pine, Scots pine, mountain pine), from resins and balsams (galbanum, elemi, benzoin, myn-h, olibanum, opo-ponax). Animal raw materials also come into consideration, for example civet and castoreum. Typical synthetic aromatic substances are, for example, products of the ester, ether, alde¬hyde, ketone, alcohol or hydrocarbon type. Aromatic substance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linaiyl benzoate, benzyl formate, ethylmethylphenyl glycinate, allylcyclohexyl propionate, styrallyl propionate and ben¬zyl salicylate. The ethers include, for example, benzyl ethyl ether; the aldehydes include, for example, the linear alkanals having from 8 to 18 hydrocarbon atoms, citral, citronellal, citro-nellyl oxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bouR2eonal; the ke¬tones include, for example, the ionones, isomethylionone and methyl cedryl ketone; the alco¬hols include, for example, anethol, citronellol, eugenol, isoeugenol, geraniol, linalool, phenyl ethyl alcohol and terpinol; and the hydrocarbons include mainly the terpenes and balsams. It is preferable, however, to use mixtures of various aromatic substances that tcgether produce an attractive scent. Ethereal oils of relatively low volatility, which are chiefly used as aroma components, are also suitable as perfume oils, e.g. sage oil, camomile oil, clove oil, melissa oil, oil of cinnamon leaves, lime blossom oil, juniper benry oil, vetiver oil, olibanum oil, galba¬num oil, labolanum oil and lavandin oil. Preference is given to the use of beR2amot oil, di-hydromyrcenol, lilial, lyral, citronellol, phenyl ethyl alcohol, hexyl cinnamabehyde, geraniol, benzyl acetone, cyclamen aldehyde, linalool, boisambrene forte, ant)roxan, indole, hedione, sandelice, lemon oil, tangerine oil, orange oil, allyl amyl glycolate, cyclovertal, lavandin oil, muscatel sage oil, damascene, bourbon geranium oil, cyclohexyl salicylate, vertofix coeur,

iso-E-Super, Fixolide NP, evernyl, iraldein gamma, phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide, romillat, irotyl and floramat alone or in admixture with one another.
Colourants
There may be used as colourants the substances that are suitable and permitted for cosmetic purposes, as compiled, for example, in the publication "Kosmetische Farbemittel" of the Farbstoffkommission der Deutschen Forschungsgemeinschaft, Verlag Chemie, Weinheim, 1984, pages 81 to 106. The colourants are usually used in concentrations of from 0.001 to 0.1 % by weight, based on the total mixture.
Other adjuvants
It is furthermore possible for the cosmetic preparations to contain, as adjuvants, anti-foams, such as silicones, structurants, such as maleic acid, solubilisers, such as ethylene glycol, propylene glycol, glycerol or diethylene glycol, opacifiers, such as latex, styrene/PVP or sty-rene/aC1-ylamide copolymers, complexing agents, such as EDTA, NTA, alaninediacetic acid or phosphonic acids, propellants, such as propane/butane mixtures, NP, dimethyl ether, CO2, N2 or air, so-called coupler and developer components as oxidation dye precursors, reducing agents, such as thioglycolic acid and derivatives thereof, thiolactic acid, cysteamine, thiomalic acid or mercaptoethanesulfonic acid, or oxidising agents, such as hydrogen peroxide, potassium bromate or sodium bromate.
Suitable insect repellents are, for example, N,N-diethyl-m-toluamide, 1,2-pentanediol or in¬sect repellent 3535; suitable self-tanning agents are, for example, dihydroxyacetone and/or erythrulose or dihydroxy acetone and/or dihydroxy acetone precursors as desC1-ibed in WO 01/85124 and/or erythrulose.
Polymeric beads or hollow spheres as SPF enhancers
The combination of the UV-absorbers and UV-absorber combinations, listed above, with SPF enhancers, such as non-active ingredients like Styrene/aC1-yiates copolymer, silica beads, spheroidal magnesium silicate, C1-osslinked PolymethylmethaC1-ylates (PMMA ; Micopearl M305 Seppic), can maximize better the UV protection of the sun products. Holosphere additives (Sunspheres® ISP, Silica Shells Kobo.) deflect radiation and the effective path length of the photon is therefore inC1-eased.( EP0893119). Some beads, as mentioned pre¬viously, provide a soft feel during spreading. Moreover, the optical activity of such beads,

e.g.MiC1-opearl M305, cans modulate skin shine by eliminating reflection plienomena and indirectly may scatter the UV light. When formulated in OAA/ emulsions, the preferably amount of such SPF enhancers should represent 1% to 10% of the total amount of the emulsion.
Cosmetic or pharmaceutical preparations
Cosmetic or pharmaceutical formulations are contained in a wide variety of cosmetic
preparations. There come into consideration, for example, especially the following
preparations:
skin-care preparations, e.g. skin-washing and cleansing preparations in the form of
tablet-form or liquid soaps, soapless deteR2ents or washing pastes,
bath preparations, e.g. liquid (foam baths, milks, shower preparations) or solid bath
preparations, e.g. bath cubes and bath salts;
skin-care preparations, e.g. skin emulsions, multi-emulsions or skin oils;
cosmetic personal care preparations, e.g. facial make-up in the form of day C1-eams or
powder C1-eams, face powder (loose or pressed), rouge or C1-eam make-up, eye-care
preparations, e.g. eyeshadow preparations, mascara, eyeliner, eye C1-eams or eye-fix
C1-eams; lip-care preparations, e.g. lipsticks, lip gloss, lip contour pencils, nail-care
preparations, such as nail varnish, nail varnish removers, nail hardeners or cuticle
removers;
foot-care preparations, e.g. foot baths, foot powders, foot C1-eams or foot balsams,
special deodorants and antiperspirants or callus-removing preparations;
light-protective preparations, such as sun milks, lotions, C1-eams or oils, sunblocks or
tropicals, pre-tanning preparations or after-sun preparations;
skin-tanning preparations, e.g. self-tanning C1-eams;
depigmenting preparations, e.g. preparations for bleaching the skin or skin-lightening
preparations;
insect-repellents, e.g. insect-repellent oils, lotions, sprays or sticks;
deodorants, such as deodorant sprays, pump-action sprays, deodorant gels, sticks or
roll-ons;
antiperspirants, e.g. antiperspirant sticks, C1-eams or roll-ons;
preparations for cleansing and caring for blemished skin, e.g. synthetic deteR2ents (solid
or liquid), peeling or sC1-ub preparations or peeling masks;

I I .^,,.j I., v^ucinilgai lunii vucfjn'ai.iuii;, «.y. riair-reiTioving powders,
liquid hair-removing preparations, C1-eam- or paste-form hair-removing preparations, hair-removing preparations in gel form or aerosol foams;
shaving preparations, e.g. shaving soap, foaming shaving C1-eams, non-foaming shaving C1-eams, foams and gels, preshave preparations for dry shaving, aftershaves or aftershave lotions;
fragrance preparations, e.g. fragrances (eau de Cologne, eau de toilette, eau de parfum, parfum de toilette, perfume), perfume oils or perfume C1-eams;
cosmetic hair-treatment preparations, e.g. hair-washing preparations in the form of shampoos and conditioners, hair-care preparations, e.g. pretreatment preparations, hair tonics, styling C1-eams, styling gels, pomades, hair rinses, treatment packs, intensive hair treatments, hair-structuring preparations, e.g. hair-waving preparations for permanent waves (hot wave, mild wave, cold wave), hair-straightening preparations, liquid hair-setting preparations, hair foams, hairsprays, bleaching preparations, e.g. hydrogen peroxide solutions, lightening shampoos, bleaching C1-eams, bleaching powders, bleaching pastes or oils, temporary, semi-permanent or permanent hair colourants, preparations containing self-oxidising dyes, or natural hair colourants, such as henna or camomile.
Presentation forms
The final fomnulations listed may exist in a wide variety of presentation forms, for example:
in the form of liquid preparations as a W/0, OA/V, 0/W/O, W/O/W or PIT emulsion and all
kinds of miC1-oemulsions,
in the form of a gel,
in the fonn of an oil, a C1-eam, milk or lotion,
in the fomi of a powder, a lacquer, a tablet ormake-up,
in the forni of a stick,
in the fonn of a spray (spray with propellent gas or pump-action spray) or an aerosol,
in the form of a foam, or
in the form of a paste.
Of special importance as cosmetic preparations for the skin are light-protective preparations, such as sun milks, lotions, C1-eams, oils, sunblocks or tropicals, pretanning preparations or

after-sun preparations, also skin-tanning preparations, for example seif-tanning C1-eams. Of particular interest are sun protection C1-eams, sun protection lotions, sun protection milk and sun protection preparations in tine form of a spray.
Of special importance as cosmetic preparations for the hair are the above-mentioned prepa¬rations for hair treatment, especially hair-washing preparations in the fomn of shampoos, hair conditioners, hair-care preparations, e.g. pretreatment preparations, hair tonics, styling C1-eams, styling gels, pomades, hair rinses, treatment packs, intensive hair treatments, hair-straightening preparations, liquid hair-setting preparations, hair foams and hairsprays. Of special interest are hair-washing preparations in the form of shampoos.
A shampoo has, for example, the following composition: from 0.01 to 5 % by weight of a UV absorber according to the invention, 12.0 % by vveight of sodium laureth-2-sulfate, 4.0 % by weight of cocamidopropyl betaine, 3.0 % by weight of sodium chloride, and water ad 100%.
For example, especially the following hair-cosmetic formulations may be used:
ai) spontaneously emulsifying stock formulation, consisting of the UV absorber according to the invention, PEG-6-CioOxoalcohol and sorbitan sesquioleate, to which water and any desired quaternary ammonium compound, for example 4 % minkamidopropyl dmethyl-2-hydroxyethylammonium chloride or Quatemium 80 is added;
82) spontaneously emulsifying stock formulation consisting of the UV absorber according to the invention, tributyl citrate and PEG-20-sorbitan monooleate, to which water and any desired quaternary ammonium compound, for example 4 % minkanidopropyl dimethyl-2-hydroxyethylammonium chloride or Quatemium 80 is added;
b) quat-doped solutions of the UV absorber according to the invention in butyl triglycol and tributyl citrate;
c) mixtures or solutions of the UV absorber according to the invention with n-alkylpyR1olidone.
Other typical ingredients in such formulations are preservatives, bactericides and bacterio¬static agents, perfumes, dyes, pigments, thickening agents, moisturizing agents, humectants, fats, oils, waxes or other typical ingredients of cosmetic and personal care formulations such as alcohols, poly-alcohols, polymers, electrolytes, oR2anic solvents, silicon derivatives,

Preparation Examples
Example 1: General work procedure for the synthesis of dialkylated compounds of formula
2-(4-Aminophenyl)-6-methylbenzothJazole (0.12 mol) is dissolved in 200 ml of absolute tetrahydrofuran and cooled to -10°C. At from -5 to -10C, 6.34 g of (0.264mol) of sodium hydride is added, in portions, to the solution. The reaction mixture is stiR1ed at 10°C for 30 minutes. Then, 0.28 mol of the appropriate haloalkane dissolved in 200 ml of absolute tetrahydrofuran is added dropwise in such a manner that the reaction temperature does not exceed 10'C. The reaction mixture is then heated to boiling point and refluxed for about 20 hours. After the reaction is complete, 10 ml of methanol are added and the reaction mixture is then reduced to half its original volume using a rotary evaporator. After adding 200 ml of distilled water, the C1-ude product is extracted with ethyl acetate. Subsequent column chromatography over silica gel using a mixture of cyclohexane and ethyl acetate yields the pure product, which is dried under a high vacuum at SOX and 0.02 mbar.

Example 2: General work procedure for the synthesis of monoalkylated compounds of

0.12 mol of 2-(4-aminophenyl)-6-methylbenzothiazole is dissolved in 200 ml of absolute tetrahydrofuran and cooled to -10°C. At from -5 to -10'C, 3.17g (0.132 mol) of sodium hydride are added, in portions, to the solution. The reaction mixture is then stin-ed at 10C for 30 minutes before 0.13 mol of the appropriate haloalkane dissolved in 200 ml of absolute tetrahydrofuran is added dropwise. After heating to boiling point, the reaction mixture is refluxed for about 20 hours until the reaction is complete 10 ml of methanol are then added and the reaction mixture is concentrated to half its original volume using a rotary evaporator. After adding 200 ml of distilled water, the C1-ude product is extracted with ethyl acetate. Subsequent column chromatography over silica gel using a mixture of cyclohexane and ethyl acetate yields the pure product, which is dried under a high vacuum at 80°C and 0.02 mbar.

Example 3: General work procedure for the synthesis of compounds of

These compounds may be prepared by condensation of the appropriately Ra-substituted

substituted p-aminobenzoic acid derivatives in a manner known per se, for example in accordance with DE 2 333 378 or E. Bami et al., J. Heterocyclic Chem. 20, 1517-1521 (1983) or with the appropriate R1, R2- and R4-substituted p-aminobenzaldehyde derivatives, for example in accordance with DE 2 333 378 and the literature references cited herein.

WE CLAIM :
1. A cosmetic preparation comprising at least one compound of formula

R1is hydrogen; unsubstituted or halo-, amino-, mono- or di-C1-C5alkylamino-, cyano- or C1-C5 alkoxy-substituted C1-C22alkyl, C5-C10cycloalkyl, carboxy-C1 -Caaalkyl, carboxy-C6-C10aryl, C5-C10aryl, C6-Cioaryl-C1-C5alkyl; carbamoyl; or sulfamoyl;
R2 is branched or unbranched C6-C12alkyl:
R3 is hydrogen; or C1-C22alkyl; and
R4 is hydrogen; hydroxy; C1-C22alkyl; or C1-C22alkoxy;
together with cosmetically acceptable carriers or adjuvants.
2. A compound of formula

R1 is hydrogen;C1-C22alkyl; or carboxy-C1-C22alkyI; R2 branched or unbranched C6-C12alkyl

7 FEB ZOOS
JPLICATE

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Patent Number

229716

Indian Patent Application Number

2585/CHENP/2004

PG Journal Number

13/2009

Publication Date

27-Mar-2009

Grant Date

19-Feb-2009

Date of Filing

17-Nov-2004

Name of Patentee

CIBA HOLDING INC

Applicant Address

Klybeckstrasse 141, CH-4057 Basel,

Inventors:

#	Inventor's Name	Inventor's Address
1	WAGNER, Barbara	Am Vogelsang 10, 79539 Lorrach,
2	EHLIS, Thomas	Harriet-Straub-Strasse 23, D-79100 Freiburg,
3	MONGIAT, Sébastien	9, rue des Fauvettes, F-68510 Sierentz,
4	EICHIN, Kai	Haagenerstrasse 31, D - 79599 Wittlingen,

PCT International Classification Number

C07D277/66

PCT International Application Number

PCT/EP2003/03870

PCT International Filing date

2003-04-14

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	2135/02	2002-12-16	EUROPEAN UNION
2	02405311.8	2002-04-17	EUROPEAN UNION