Indian Patents. 237349:"INDANYLIDENE COMPOUNDS OF THE FORMULA"

Title of Invention	"INDANYLIDENE COMPOUNDS OF THE FORMULA"
Abstract	Indanylidene compounds of the formula in which R1 and R2 are hydrogen; R3 and R4 are methyl; R5 to R7, independently of one another are hydrogen, C1-C20-alkyl, C1-C20-alkoxy, acetoxy, or Me-Si (OSiMe3)2 -CH2CH(CH3)CH2-O-, additionally two substituents of R5 to R7 on adjacent carbon atoms can together form a 1, 4-dioxalan ring. R8, is hydrogen, X is cyano; n is 1; R9 to R11 are methyl.

Full Text	Novel indanvlidene compounds The invention relates to novel indanylidene compounds, to a process for their preparation and to their use as UVA filters. Indanylidene compounds which have UV-absorbing properties are already known from EP-A 823 418. However, the indanylidene compounds previously described in EP-A 823 418 have a photostability which is too low for the application. Novel indanylidene compounds of the formula (Formula Removed) in which R1 to R4, independently of one another are hydrogen, C1-C20-alkyl or C5-C10-cyclo-alkyl, with the proviso that two substituents on adjacent carbon atoms can together also be an optionally substituted C1-C4-alkylene group; may also, independently of one another, be C2-C20-alkyl, in which at least one methylene group may be replaced by oxygen, C3-C20-alkenyl, C3-C20-alkinyl or a group S, where S may be a silane, an oligosiloxane or a polysiloxane group; - R5 to R8, independently of one another, are hydrogen, C1-C20-alkyl or C5-C10-cyclo-alkyl or C1-C20-alkoxy, C5-C10-cycloalkoxy, hydroxyl, acetoxy, acetamino, carboxyl, carbalkoxy or carbamoyl, additionally two substituents of R5 to R8 on adjacent carbon atoms can together form a 5-7-membered ring which contains up to three heteroatoms, in particular oxygen or nitrogen, where the ring atoms may be substituted by exocyclically double-bonded oxygen (keto group), also, in the case of alkoxy, may, independently of one another, be C2-C20-alkyl in which at least one methylene group may be replaced by oxygen, C3-C20-alkenyl, C3-C20-alkinyl or a group S, where S may be a silane, an oligosiloxane or a polysiloxane group; X is cyano, CON(R)2 or CO2R, where R is hydrogen or C1-C8-alkyl; n is 1 or 0; R9 to R11, in cases where n=l, may be hydrogen, C1-C20-alkyl or C5-C10-cycloalkyl, aryl or heteroaryl, additionally two substituents of R9 to R1' can, together with the B-atom form a 3-7-membered ring which may contain up to three heteroatoms, in particular oxygen or nitrogen, also, in cases where n=0, R9 and R10, together with the 13-atom, are an aryl or heteroaryl radical. have been found. The novel indanylidene compounds represent a surprising selection from the indanylidene compounds known from EP-A 823 418. They have a significantly higher photostability than the compounds mentioned in EP-A 823 418 and high compatibility with other UV filters, such as, for example, isooctyl p-methoxy-cinnamate. Preference is given to indanylidene compounds of the formula (Formula Removed) Particular preference is given to indanylidene compounds of the formula (Formula Removed) Specifically, the following preferred indanylidene compounds may be mentioned: 2-(5,6-Dimethoxy-3,3-dimethyl-l-indanylidene)-4,4-dimethyl-3-oxo-pentanonitrile, 2-(5-methoxy-3,3,4,6-tetramethyl-l-indanylidene)-4,4-dimethyl-3-oxo-pentano-nitrile, 2-(3,3,5,6-tetramethyl-1 -indanylidene)-4,4-dimethyl-3-oxo-pentanonitrile, 2-(3,3,6-trimethyl-l-indanylidene)-4,4-dimethyl-3-oxo-pentanonitrile, 2-(5,6-eth- ylenedioxo-3,3-dimethyl-l-indanylidene)-4,4-dimethyl-3-oxo-pentanonitrile, 2-(5-methoxy-3,3,6-trimethyl-l-indanylidene)-4,4-dimethyl-3-oxo-pentanonitrile, 2-[(5-methoxy-3,3-dimethyl-(2-methyl-3-( 1,3,3,3-tetramethyl-1 -(trimethyl-silyloxy)-disiloxanyl)-propyl)-indanylidene)]-4,4-dimethyl-3-oxo-pentanonitrile and 2-(6-acetoxy-3,3-dimethyl-5-methoxy-l-indanylidene)-4,4-dimethyl-3-oxo-pentanonitrile. The indanylidene compounds according to the invention can be prepared by (Knoevenagel) condensation of compounds of the formula (Formula Removed) where 1 O R to R have the meanings given above, with compounds of the formula (Formula Removed) where R9 to R11 and X have the meanings given above. The indanones used here can be prepared by Friedel-Crafts Reactions of (substituted) acrylic esters with (substituted) aromatics or, in the case of hydroxyl substituents, by Fries rearrangement of corresponding phenyl esters (F.-H. Marquardt, Helv. Chim. Actai59, 1476(1965)). The preparation of the indanylidene compounds according to the invention can, for example, be carried out as follows: The abovementioned indanones are condensed with equimolar amounts of pivaloyl-acetonitrile with the catalysis of ammonium acetate according to the conditions of a Knoevenagel condensation. The preparation can be illustrated by the reaction scheme below: (Formula Removed) The indanylidene compounds according to the invention can be used as UV absorbers, e.g. in cosmetic compositions, in particular for protecting against acute skin damage (sunburn) and also chronic skin damage (premature skin ageing), particularly in sunscreen compositions, daily care products and hair care products, but also for improving the photostability of technical products, such as paints, surface coatings, plastics, textiles, packaging materials and rubbers. The indanylidene compounds according to the invention can be used individually or in a mixture in the corresponding preparations; it is also possible to use them in combination with UV absorbers of other classes of substance, and also with the latter in any desired mixtures with one another. For example, the following UV absorbers may be mentioned: • p-aminobenzoic acid • ethyl p-aminobenzoate (25 mol) ethoxylated • 2-ethylhexyl p-dimethylaminobenoate • ethyl p-aminobenzoate (2 mol) N-propoxylated • glycerol p-aminobenzoate • homomethyl salicylate (homosalate) (Neo Heliopan®HMS) • ethylhexyl salicylate (Neo Heliopan®OS) • triethanolamine salicylate • 4-isopropylbenzyl salicylate • menthyl anthranilate (Neo Heliopan®MA) • ethyl diisopropylcinnamate • 2-ethylhexyl p-methoxycinnamate (Neo Heliopan®AV) • methyl diisopropylcinnamate • isoamyl p-methoxycinnamate (Neo Heliopan®E 1000) • p-methoxycinnamate acid diethanolamine salt • isopropyl p-methoxycinnamate • 2-ethylhexyl 2-cyano-3,3-diphenyl acrylate (Neo Heliopan®303) • ethyl 2-cyano-3,3'-diphenyl acrylate • 2-phenylbenzimidazolesulphonic acid and salts (Neo Heliopan®hydro) • 3-(4l-trimethylammonium)-benzylidene-boman-2-one methylsulphate • terephthalylidene-dibornanesulphonic acid and salts (Mexoryl®SX) • 4-t-butyl-4'-methoxy-dibenzoylmethane (Avobenzon) / (Neo Heliopan®357) • J3-imidazole-4(5)-acrylic acid (Urocanic acid) • 2-hydroxy-4-methoxybenzophenone (Neo Heliopan®BB) • 2-hydroxy-4-methoxybenzophenone-5-sulphonic acid • dihydroxy-4-methoxybenzophenone • 2,4-dihydroxybenzophenone • tetrahydroxybenzophenone • 2,2'-dihydroxy-4,4'-dimethoxybenzophenone • 2 -hydroxy-4-n-octoxybenzophenone • 2-hydroxy-4-methoxy-4'-methylbenzophenone • 3-(4'-sulpho)benzylidene-boman-2-one and salts • 3-(4'-methylbenzylidene)-d,l-camphor (Neo Heliopan"MBC) • 3-benzylidene-d,l-camphor • 4-isopropyldibenzoylmethane • 2,4,6-trianilino-(p-carbo-2'-ethylhexyl-1 '-oxy)-1,3,5-triazine • phenylene-bis-benzimidazyl-tetrasulphonic acid disodium salt (Neo Heliopan®AP) • 2,2'-(l,4-phenylene)-bis-(lH-benzimidazole-4,6-disulphonic acid), monosodium salt • N-[(2 and 4)-[2-(oxoborn-3-ylidene)methyl]benzyl]-acrylamide-polymer • phenol, 2-(2H-benzotriazol-2-yl)-4-methyl-6-(2-methyl-3(l,3,3,3-tetramethyl-l- (trimethylsilyl)-oxy)-disiloxyanyl)-propyl), (Mexoryl®XL) • bis-(2-ethylhexyl) 4,4'-[(6-[4-( 1,1 -dimethyl)-aminocarbonyl)-phenylamino]-1,3,5- triazine-2,4-diyl)diimino]-bis-(benzoate) (Uvasorb®HEB) • 2,2'-methylene-bis-(6-(2H-benztriazol-2-yl)-4-l,l,3,3-tetramethylbutyl)-phenol), (Tinosorb®M) • 2,4-bis-[4-(2-ethylhexyloxy)-2-hydroxyphenyl]-1,3,5-triazine • benzylidene malonate-polysiloxane (Parsol®SLX) • glycerylethyl hexanoate-dimethoxycinnamate • disodium 2,2'-dihydroxy-4,4'-dimethoxy-5,5'-disulpho-benzophenone • dipropylene glycol salicylate • sodium hydroxymethoxybenzophenonesulphonate • tris (2-ethylhexyl) 4,4',4-(l,3,5-triazine-2,4,6-triyltriimino)-tris-benzoate (Uvinul®T150) • 2,4-bis-[{(4-(2-ethyl-hexyloxy)-2-hydroxy}-phenyl]-6-(4-methoxyphenyl)-1,3,5- triazine, (Tinosorb®S) • 2,4-bis-[{(4-(3-sulphonato)-2-hydroxy-propyloxy)-2-hydroxy}-phenyl]-6-(4- methoxyphenyl)-l,3,5-triazine sodium salt • 2,4-bis-[ {(3-(2-propyloxy)-2-hydroxy-propyloxy)-2-hydroxy} -phenyl]-6-(4- methoxy-phenyl)-! ,3,5-triazine • 2,4-bis-[{4-(2-ethyl-hexyloxy)-2-hydroxy}-phenyl]-6-[4-(2-methoxyethyl- carbonyl)-phenylamino]-l,3,5-triazine • 2,4-bis-[{4-(3-(2-propyloxy)-2-hydroxy-propyloxy)-2-hydroxy}-phenyl]-6-[4-(2- ethylcarboxyl)-phenylamino] -1,3,5 -triazine • 2,4-bis-[{4-(2-ethyl-hexyloxy)-2-hydroxy}-phenyl]-6-(l-methyl-pyrrol-2-yl-)- 1,3,5-triazine • 2,4-bis-[{4-tris-(trimethylsiloxy-silylpropyloxy)-2-hydroxy}-phenyl]-6-(4-meth- oxyphenyl)-1,3,5-triazine • 2,4-bis-[{4-(2"-methylpropenyloxy)-2-hydroxy}-phenyl]-6-(4-methoxyphenyl)- 1,3,5-triazine • 2,4-bis-[{4-(l',l',l',3'5',5',5'-heptamethylsiloxy-2"-methyl-propyloxy)-2- hydroxy}-phenyl]-6-(4-methoxyphenyl)-l,3,5-triazine Particularly suitable UV absorbers are: • p-aminobenzoic acid • 3-(4'-trimethylammonium)-benzylidene-boman-2-one methylsulphate • homomethyl salicylate (Neo Heliopan®HMS) • 2-hydroxy-4-methoxy-benzophenone (Neo Heliopan®BB) • 2-phenylbenzimidazolesulphonic acid (Neo Heliopan®Hydro) • terephthalylidenedibornanesulphonic acid and salts (Mexoryl®SX) • 4-tert-butyl-4'-methoxydibenzoylmethane (Neo Heliopan®357) • 3-(4'-sulpho)benzylidene-bornan-2-one and salts • 2-ethylhexyl 2-cyano-3,3-diphenylacrylate (Neo Heliopan®303) • N-[(2 and 4)-[2-(oxoborn-3-ylidene)methyl]benzyl]-acrylamide polymer • 2-ethylhexyl p-methoxycinnamate (Neo Heliopan®AV) • ethyl p-aminobenzoate (25 mol) ethoxylated • isoamyl p-methoxycinnamate (Neo Heliopan®E1000) • 2,4,6-trianilmo-(p-carbo-2'-ethylhexyl-r-oxy)-l,3,5-triazine(Uvinul®T150) • phenol, 2-(2H-benzotriazol-2-yl)-4-methyl-6-(2-methyl-3(l,3,3,3-tetramethyl-l- (trimethylsilyl)-oxy)-disiloxyanyl)-propyl), (Mexoryl®XL) • bis-(2-ethylhexyl) 4,4'-[(6-[4-(l,l-dimethyl)-aminocarbonyl)-phenylamino]- 1,3,5-triazine-2,4-diyl)-diimino]-bis-(benzoate), (UvasorbHEB) • 3-(4'-methylbenzylidene)-d,l-camphor (Neo Helipan®MBC) • 3-benzylidenecamphor • 2-ethylhexyl salicylate (Neo Helipan®OS) • 2-ethylhexyl 4-dimethylaminobenzoate (Padimate O) • hydroxy-4-methoxybenzophenone-5-sulphonic acid and Na salt • 2,2'-methylene-bis-(6-(2H-benztriazol-2-yl)-4-l,l,3,3-tetramethylbutyl)-phenol), (Tinosorb®M) • phenylene-bis-benzimidazyltetrasulphonic acid disodium salt (Neo Heliopan®AP) • 2,4-bis-[{(4-(2-ethyl-hexyloxy)-2-hydroxy}-phenyl]-6-(4-methoxyphenyl)-l,3,5- triazine, (Tinosorb®S) • benzylidene malonate-polysiloxane (Parsol®SLX) • menthyl anthranilate (Neo Heliopan®MA) It may also be advantageous to use polymer-bonded or polymeric UV absorbers in preparations according to the present invention, in particular those described in WO-A-92/20690. The combination of the indanylidene compounds according to the invention with finely divided inorganic and organic pigments, such as, for example, titanium dioxide, zinc oxide and iron oxide and Tinosorb®M, in sunscreen and daily care products with UV protection is likewise possible. The list of UV filters given which can be used for the purposes of the present invention is not of course intended to be limiting. The total amount of all (mono- and polysulphonated) water-soluble UV filter substances in the finished cosmetic or dermatological preparations, for example of phenylene-bis-benzimidazyl-tetrasulphonic acid disodium salt or salts thereof and/or the corresponding disulphonic acid or salts thereof and/or 2-phenylbenzimidazole-5-sulphonic acid and salts thereof and/or 2-hydroxy-4-methoxybenzophenone-5- sulphonic acid and salts thereof and/or 4-(2-oxo-3-bornylidenemethyl)-benzenesulphonic acid and salts thereof and/or 2-methyl-5-(2-oxo-3-bornylidene-methyl)-benzenesulphonic acid and salts thereof and/or benzene-l,4-di-(2-oxo-3-bomylidenemethyl)-10-sulphonic acid and salts thereof, is advantageously chosen from the range from 0.1 to 10.0% by weight, preferably 0.5 to 6.0% by weight, based on the total weight of the preparations, if the presence of these substances is desired. The total amount of oil-soluble UV filter substances in the finished cosmetic or dermatological preparations, for example of tris(2-ethylhexyl) 4,4',4"-(l,3,5-triazine-2,4,6-triyltriimino)-tris-benzoate and/or 4-tert-butyl-4'-methoxy-dibenzoyl-methane and/or 4-methylbenzylidenecamphor and/or octyldimethyl-p-aminobenzoic acid and/or Mexoryl®XL and/or Uvasorb®HEB and/or Tinosorb®S and/or benzo-phenone-3 and/or Parsol®SLX and/or Neo Heliopan®MA is advantageously chosen from the range from 0.1 to 10.0% by weight, preferably 0.5 to 6.0% by weight, based on the total weight of the preparations, if the presence of these substances is desired. The total amount of 2-ethylhexyl p-methoxycinnamate and/or isoamyl p-methoxy-cinnamate in the finished cosmetic or dermatological preparations is advantageously chosen from the range from 0.1 to 15.0% by weight, preferably 0.5 to 7.5% by weight, based on the total weight of the preparations, if the presence of these substances is desired. The total amount of ethylhexyl 2-cyano-3,3-diphenylacrylate in the finished cosmetic or dermatological preparations is, if the presence of this substance is desired, advantageously chosen from the range from 0.1 to 15.0%, preferably 0.5 to 10.0% by weight, based on the total weight of the preparations. The total amount of one or more salicylic acid derivatives in the finished cosmetic or dermatological preparations is advantageously chosen from the range from 0.1 to 15.0% by weight, preferably 0.5 to 10.0% by weight, based on the total weight of the preparations. If ethylhexyl salicylate is chosen, it is advantageous to choose its total amount from the range from 0.1 to 5.0% by weight. If homomenthyl salicylate is chosen, it is advantageous to choose its total amount from range from 0.1 to 10.0% by weight. The indanylidene compounds according to the invention are also suitable to a particular degree for photostabilizing UV absorbers with low UV photostability. The photostabilization of the very photo-unstable compounds of the dibenzoylmethane, e.g. tert-butyl-4'-methoxydibenzoylmethane, is particularly successful. A further photostable UV filter combination is achieved using 0.1 to 10% by weight, preferably 1 to 10% by weight, of ethylhexyl p-methoxycinnamate or isoamyl p-methoxy cinnamate with 0.1 to 10% by weight, preferably 1 to 6% by weight, of the compound of the formula I, preferably in the ratio 1:1. The combinations of p-methoxycinnamic esters and dibenzoylmethane derivatives and compounds of the formula I can be formulated to be photostable by using, for example, 0.1 to 5% by weight, preferably 1 to 3% by weight, of 4-tert-butyl-4'-meth-oxydibenzoylmethane, 0.1 to 10% by weight, preferably 1 to 7.5% by weight of ethylhexyl p-methoxycinnamate or isoamyl p-methoxycinnamate and at least 0.2% by weight, preferably 1 to 6% by weight, of the compounds of the formula I, preferably in the ratio 1 part of dibenzoylmethane derivative, 2 parts p-methoxycinnamic ester and 2 parts of the indanylidene compounds according to the invention. hi addition, it is advantageous to add one or more very photostable UV absorbers to this three-way combination, such as, for example, methylbenzylidenecamphor, 2-eth-ylhexyl 2-cyano-3,3'-diphenylacrylate, octyltriazone, Uvasorb®HEB, Tinosorb®S, Tinosorb®M, ethylhexyl salicylate, homomenthyl salicylate, and phenylene-bisimidazolesulphonic acid or phenylene-bis-benzimidazole-tetrasulphonic acid disodium salt, Mexoryl®SX, Mexoryl®XL or Parsol®SLX. In addition, in cosmetic preparations, a synergistic increase in the sun protection factor is surprisingly achieved using indanylidene derivatives of the formula I in combination with other UV filters. Examples of a synergistic increase in the sun protection factor are cosmetic emulsions which comprise both a compound of the formula I and also ethylhexyl methoxycinnamate or octocrylene, or a combination of a compound of the formula I with ethylhexyl methoxycinnamate and 2-phenyl-benzimidazolesulphonic acid, or ethylhexyl methoxycinnamate and methyl-benzylidenecamphor, or ethylhexyl methoxycinnamate and 4-t-butyl-4'-methoxy-dibenzoylmethane, or Neo Heliopan® AP and ethylhexyl methoxycinnamate, or a combination of a compound of the formula I with octocrylene, methyl-benzylidenecamphor and zinc oxide. Combinations of a compound of the formula I with dibenzoylmethanes, methylbenzylidenecamphor, 2-phenylbenzimidazole-sulphonic acid, Neo Heliopan®AP, Mexoryl®SX, Mexoryl®XL, Parsol®SLX, Tinosorb®S, Tinosorb®M, Uvinul®T150, Uvasorb® HEB, and microfine pigments, zinc oxide and titanium oxide, also have synergistic increases in the sun protection factors. Said UV filter combinations are listed by way of example and are not to be understood as being limited to the abovementioned combinations. Thus, it is possible to use combinations of all UV absorbers already mentioned as particularly suitable on pages 8/9, and UV filters approved in the subsequent publications with compounds of the formula I or the abovementioned combinations, individually or in any desired mixtures. USA: Food and Drug Administration (FDA). Publication in monograph for Sunscreen Drug Products for Over-The-Counter Human Use. Europe: EC Directive 76/768 of the Council for adapting the legal provisions of the member states regarding cosmetic compositions to technical progress. Publications in the Official Journal of European Communities. Japan: Publication of the Cosmetics Directive of the Ministry of Health and Welfare (MHW). Germany: Publication in the Verordnung iiber kosmetische Mittel [Directive concerning cosmetic compositions] according to the Lebensmittel-und Bedarfsgegenstande-Gesetz (LMBG) [Act relating to Foods and Commodities]. Australia: Registration by Therapeutic Goods Administration (TGA) and publication in the Australian Register of Therapeutic Goods (ARTG). These combinations usually achieve a synergistic increase in the UV sun protection factor. The combination of compounds of the formula I with UV-A absorbers, particularly UV-A-II absorbers, gives broad protection against UV-A radiation (320-400 nm). In particular, a combination of compounds of the formula I with Neo Heliopan®AP (UV-AII absorber) is to be mentioned for broad UV-A protection performance. Further UV-A filters which are used in combination with compounds of the formula I alone or in combination of compounds of the formula I and Neo Heliopan®AP are Mexoryl®SX, Mexoryl®XL, Tinosorb®M Tinosorb®S, benzophenone-3, benzophenone-4, Neo Heliopan®357, Neo Heliopan®MA. For optimum broad-band protection against UV-A and UV-B radiation, the abovementioned combinations are to be combined with all UV-B filters and mixtures of these filters (cf. list on pages 6-9). Preferably suitable are Neo Heliopan®AV, Neo Heliopan®E 1000, Neo Heliopan®Hydro, Neo Heliopan®MBC, Neo Heliopan®303, Neo Heliopan®OS, Neo Heliopan®HMS, Uvinul®T150, Uvasorb®HEB, ethylhexyl dimethylaminobenzoate. Combining compounds of the formula I with Neo Heliopan®AP and a UV-B filter, e.g. ethylhexyl methoxycinnamate or UV-B filter mixtures, and coated or uncoated finely disperse metal oxides, such as, for example, zinc oxide, titanium dioxide, achieves UV broad-band protection performance with a critical wavelength λcnt of > 380 nm (cf. Diffey in Int. J. Cosm. Science 16,47 (1994)). Furthermore, the indanylidene compounds according to the invention can be combined alone or with other UV absorbers used for the protection of technical products. Examples of such UV absorbers are compounds from the series of benzotriazoles, benzophenones, triazines, cinnamic esters and oxalanilides. The indanylidene compounds according to the invention are crystalline and have to be dissolved sufficiently in cosmetic preparations to avoid the problem of recrystallization following a prolonged storage period. A sufficient amount of the oil components customarily used in cosmetic preparations, liquid oil-soluble UV absorbers or alcohols, e.g. ethanol, isopropanol or 1-butanol, is necessary to avoid re-crystallization. Particular preference is given to the use of the following oil components and/or UV absorbers for achieving adequate solubility of combinations of the indanylidene compounds according to the invention: ethylhexylmethoxycinnamate, isoamyl methoxycinnamate, octocrylene, ethylhexyl salicylate, homosalate, menthyl anthranilate, padimate O, diisopropyl adipate, C12-15-alkyl benzoate (Witconol TN), butylene glycol dicaprylate/dicaprate (Miglyol 8810), cocoglycerides (Myritol 331), caprylic/capric triglycerides (Miglyol 812), cetearyl isononanate (Cetiol SN), PVP/hexadecene copolymer (Unimer U151), adipic acid/diethylene glycol/isononanoic acid copolymer (Lexorez 100), propylene glycol dicaprylate/dicaprate (Myritol PC), hexyl laurate (Cetiol A), dicapryl ether (Cetiol OE), diethylhexyl naphthalate (Hallbrite®TQ), butyloctyl salicylate (Hallbrite®BHB), dibutyl adipate (Cetiol B), triethyl citrate (hydagen CAT), propylene glycol dibenzoate (Finsolv PG 22), tributyl citrate, dioctyl malate (Ceraphyl 45), dipropylen glycol dibenzoate (Benzoflex 245), acetyltributyl citrate (Citroflex A-4), acetyltriethyl citrate (Citroflex A-2). The list of said oils which can be used for the purposes of the present invention is not of course intended to be limiting. The use amount of all oil components in cosmetic emulsions with compounds of the formula I is 0.5 to 30% by weight, preferably 2 to 15% by weight. All said oil components and liquid oil-soluble UV filters are excellent solvents for all crystalline oil-soluble UV absorbers. It is a serious drawback if UV absorbers leave behind marks which can not be washed out of items of clothing. In particular it is known that the UV-A absorber tert-butylmethoxydibenzoylmethane produces marks on textiles which cannot be washed out. The indanylidene compounds according to the invention do not have this drawback since a mark formed on textiles can be very readily washed out. Sunscreen products should be water-resistant in order that sufficient UV protection is ensured for the user, in particular children, while swimming or bathing. Combinations of the indanylidene compounds according to the invention satisfy these requirements to a particularly good degree. In an O/W emulsion containing 3% by weight of a combination of the indanylidene compounds according to the invention, 97% substantivity of the UV absorber was measured following washing, and in a W/O emulsion, 95%. Furthermore, the water resistance of sun protection products containing water-soluble, mono- or polysulphonated UV filters, such as, for example, Neo Heliopan®AP, Mexoryl®SX, benzophenone-4, Neo Heliopan®Hydro and the oil-soluble UV absorbers listed on pages 6-9 can be significantly increased as a result of combination with compounds of the formula I. It may also be of considerable advantage to combine the UV absorbers mentioned according to the invention with chelating substances, as are listed, for example, in EP-A496434, EP-A313305 and WO-94/04128, or with polyaspartic acid and ethylenediamine-tetramethyl-phosphonic acid salts. Cosmetic and dermatological formulations for the purposes of the invention comprise one or more customary UV-A, UV-B and/or broad-band filters as individual substances or in any mixtures with one another, in the lipid phase and/or in the aqueous phase. They are satisfactory products in every respect which are surprisingly characterized by high UV-A protection performance and high sun protection factor. The invention further provides for the use of the UV absorbers according to the invention in combination with conventional UV absorbers for enhancing the protection against harmful UV radiation beyond the extent of the protection achieved using the same amounts of conventional or of UV filters according to the invention on their own (synergistic effect). The total amount of UV filter substances (UV-A, UV-B and/ or broad-band filters) in the finished cosmetic or dermatological preparations, whether as individual substance or in any mixtures with one another, is advantageously chosen from the range from 0.1 to 30% by weight, preferably 0.1 to 10.0% by weight, in particular 0.5 to 5.0% by weight, based on the total weight of the preparations. In addition, cosmetic and dermatological preparations according to the invention advantageously, but not obligatorily, comprise inorganic pigments based on finely disperse metal oxides and/or other metal compounds which are insoluble or sparingly soluble in water, in particular the oxides of titanium (TiO2), zinc (ZnO), iron (e.g. Fe2O3), zirconium (ZrO2), silicon (SiO2), manganese (e.g. MnO), aluminium (A12O3), cerium (e.g. Ce2O3), mixed oxides of the corresponding metals, and mixtures of such oxides. These pigments are X-ray-amorphous or non-X-ray-amorphous. Particular preference is given to pigments based on TiO2. X-ray-amorphous oxide pigments are metal oxides or semimetal oxides which reveal no or no recognizable crystalline structure in X-ray diffraction experiments. Such pigments are often obtainable by flame reaction, for example by reacting a metal or semimetal halide with hydrogen and air (or pure oxygen) in a flame. In cosmetic, dermatological or pharmaceutical formulations, X-ray-amorphous oxide pigments are used as thickeners and thixotropic agents, flow auxiliaries for emulsion and dispersion stabilization and as carrier substance (for example for increasing the volume of finely divided powders). X-ray-amorphous oxide pigments which are known and often used in cosmetic or dermatological galenics are, for example, high-purity silicon oxide. Preference is given to high-purity, X-ray-amorphous silicon dioxide pigments with a particle size in the range from 5 to 40 nm and an active surface area (BET) in the range from 50 to 400 m2/g, preferably 150 to 300 m2/g, where the particles are to be regarded as spherical particles of very uniform dimension. Macroscopically, the silicon dioxide pigments are recognizable as loose, white powders. Silicon dioxide pigments are sold commercially under the name Aerosil® (CAS-No. 7631-85-9) or Carb-O-Sil Advantageous Aerosil® grades are, for example, Aerosil®OX50, Aerosil® 130, Aerosil®!50, Aerosil®200, Aerosil®300, Aerosil®380, Aerosil®MQX 80, Aerosil® MOX 170, AerosifCOK 84, Aerosil® R 202, Aerosil®R 805, Aerosil®R 812, Aerosil®R 972, Aerosil®R 974, Aerosil®R976. According to the invention, cosmetic or dermatological light protection preparations comprise 0.1 to 20% by weight, advantageously 0.5 to 10% by weight, very particularly 1 to 5% by weight, of X-ray-amorphous oxide pigments. The non-X-ray-amorphous inorganic pigments are, according to the invention, advantageously in hydrophobic form, i.e. have been surface-treated to repel water. This surface treatment may involve providing the pigments with a thin hydrophobic layer by processes known per se. Such a process involves, for example, producing the hydrophobic surface layer by a reaction according to n TiO2 + m (RO)3Si-R' → n TiO2 (surf.) where n and m are stoichiometric parameters to be used as desired, and R and R' are the desired organic radicals. Hydrophobicized pigments prepared analogously to DE-A 33 14 742, for example, are advantageous. For example, mention may be made of TiO2 pigments, as are sold under the trade name T805 from Degussa. Preference is also given to TiO2/Fe2O3 mixed oxides, as are supplied, for example, under the trade name T817, also from Degussa. The total amount of inorganic pigments, in particular hydrophobic inorganic micro-pigments, in the finished cosmetic or dermatological preparations is advantageously chosen from the range from 0.1 to 30% by weight, preferably 0.1 to 10.0% by weight, in particular 0.5 to 6.0% by weight, based on the total weight of the preparations. The cosmetic and/or dermatological formulations according to the invention can have the customary composition and can be used for cosmetic and/or dermatological sun protection, and also for the treatment, care and cleansing of the skin and/or of the hair and as a make-up product in decorative cosmetics. Accordingly, the preparations according to the invention can, depending on their formulation, be used, for example, as skin protection cream, cleansing milk, sunscreen lotion, nourishing cream, day cream or night cream, etc. In some instances, it is possible and advantageous to use the preparations according to the invention as bases for pharmaceutical formulations. Preference is given, in particular, to those cosmetic and dermatological preparations in the form of a skin care or make-up product. Typical embodiments are creams, gels, lotions, alcoholic and aqueous/alcoholic solutions, emulsions or stick preparations. These compositions may also comprise, as further auxiliaries and additives, mild surfactants, co-emulsifiers, superfatting agents, pearlescent waxes, bodying agents, thickeners, polymers, silicone compounds, fats, waxes, stabilizers, biogenic active ingredients, deodorant active ingredients, antidandruff agents, film formers, swelling agents, hydrotropic agents, preservatives, insect repellants, tanning agents, artificial self-tanning agents (e.g. dihydroxyacetone), stabilizers, perfume oils, dyes, antimicrobial agents and the like. For use, the cosmetic and dermatological preparations according to the invention are applied to the skin and/or the hair in a sufficient amount in the manner customary for cosmetics. Particular preference is given to those cosmetic and dermatological preparations in the form of a cosmetic composition for the protection of the skin and hair. Advantageously, in addition to UV-A, UV-B and/or broad-band filters used according to the invention, these can comprise at least one inorganic pigment, preferably an inorganic micropigment. The cosmetic and dermatological preparations according to the invention can comprise cosmetic auxiliaries, as are customarily used in such preparations, e.g. pre servatives, bactericides, perfumes, antifoams, dyes, pigments which have a colouring action, thickeners, moisturizers and/or humectants, fats, oils, waxes or other customary constituents of a cosmetic or dermatological formulation, such as alcohols, polyols, polymers, foam stabilizers, electrolytes, organic solvents or silicone derivatives. Suitable nonionic emulsifiers or dispersants are the group formed by polyglyceryl-2 dipolyhydroxystearate (Dehymuls®PGPH), polyglyceryl-3 diisostearate (Lameform®TGI), polyglyceryl-4 isostearate (Isolan®GI 34), polyglyceryl-3 oleate, diisostearyl polyglyceryl-3 diisostearate (Isolan®PDI), polyglyceryl-3 methylglucose distearate (Tego Carey®450), polyglyceryl-3 beeswax (Cera Bellina®), polyglyceryl-4 caprate (polyglycerol caprate T2010/90), polyglyceryl-3 cetyl ether (Chimexane®NL), polyglyceryl-3 distearate (Cremophor®GS 32), polyglyceryl-2 stearate (Hostacerin®DGMS) and polyglyceryl polyricineoleate (Admul®WOL 1403), and mixtures thereof. The amounts of cosmetic or dermatological auxiliaries and carrier substances and perfume which can be used in each case can be determined easily by the person skilled in the art by simple trial and error, depending on the nature of the product in question. An additional content of antioxidants is generally preferred. According to the invention, favourable antioxidants which can be used are all antioxidants customary or suitable for cosmetic and/or dermatological applications. The antioxidants are advantageously chosen from the group consisting of amino acids (e.g. glycine, histidine, tyrosine, tryptophan) and derivatives thereof, imidazoles (e.g. urocanic acid) and derivatives thereof, peptides, such as D,L-carnosine, D-camosine, L-camosine and derivatives thereof (e.g. anserine), carotenoids, carotenes (e.g. α-carotene, ß-carotene, lycopene) and derivatives thereof, chlorogenic acid and derivatives thereof, lipoic acid and derivatives thereof (e.g. dihydrolipoic acid), aurothioglucose, propylthiouracil and other thiols (e.g. thioredoxin, glutathione, cysteine, cystine, cystamine and the glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl, γ-linoleyl, cholesteryl and glyceryl esters thereof) and salts thereof, dilauryl thiodipropionate, distearyl thiodipropionate, thiodipropionic acid and derivatives thereof (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts), and sulphoximine compounds (e.g. buthionine sulphoximines, homocysteine sulphoximine, buthionine sulphones, penta-, hexa-, heptathionine sulphoximine) in very low tolerated doses (e.g. pmol to umol/kg), and also (metal) chelating agents (e.g. α-hydroxy fatty acds, palmitic acid, phytic acid, lactoferrin), α-hydroxy acids (e.g. citric acid, lactic acid, maleic acid), humic acid, bile acid, bile extracts, bilirubin, biliverdin, EDTA, EGTA and derivatives thereof, unsaturated fatty acids and derivatives thereof (e.g. γ-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, Mg ascorbyl phosphate, ascorbyl acetate), tocopherols and derivates (e.g. vitamin E acetate), vitamin A and derivatives (vitamin A palmitate), and coniferyl benzoate of benzoin resin, rutinic acid and derivatives thereof, α-glycosylrutin, ferulic acid, furfurylideneglucitol, camosine, butylhydroxytoluene, butylhydroxyanisol, nordihydroguaiacic acid, nordihydroguaiaretic acid, trihydroxybutyrophenone, uric acid and derivatives thereof, mannose and derivatives thereof, zinc and derivatives thereof (e.g. ZnO, ZnSO4), selenium and derivatives thereof (e.g. selenomethionine), stilbenes and derivatives thereof (e.g. stilbene oxide, trans-stilbene oxide) and the derivatives (salts, esters, ethers, sugars, nucleotides, nucleosides, peptides and lipids) of said active ingredients suitable according to the invention. The amount of the abovementioned antioxidants (one or more compounds) in the preparations is preferably 0.001 to 30% by weight, particularly preferably 0.05 to 20% by weight, in particular 1 to 10% by weight, based on the total weight of the preparation. If vitamin E and/or derivatives thereof represent the antioxidant(s), it is advantageous to choose their respective concentrations from the range from 0.001 to 10% by weight, based on the total weight of the formulation. If vitamin A or vitamin A derivatives, or carotenes or derivatives thereof represent the antioxidant(s), it is advantageous to choose their respective concentrations from the range from 0.001 to 10% by weight, based on the total weight of the formulation. The lipid phase can advantageously be chosen from the following group of substances: mineral oils, mineral waxes; oils, such as triglycerides of capric or of caprylic acid, and also natural oils, such as, for example, castor oil; fats, waxes and other natural and synthetic fatty substances, preferably esters of fatty acids with alcohols of low carbon number, e.g. with isopropanol, propylene glycol or glycerol, or esters of fatty alcohols with alkanoic acids of low carbon number or with fatty acids; alkyl benzoate; silicone oils, such as dimethylpolysiloxane, diethylpolysiloxane, diphenyl-polysiloxane, and mixed forms thereof.. The oil phases of the emulsions, oleogels and hydrodispersions or lipodispersions for the purposes of the present invention are advantageously chosen from the group of esters of saturated and/or unsaturated, branched and/or unbranched alkanecarboxylic acids having a chain length of from 3 to 30 carbon atoms and saturated and/or unsaturated, branched and/or unbranched alcohols having a chain length of from 3 to 30 carbon atoms, from the group of esters of aromatic carboxylic acids and saturated and/or unsaturated, branched and/or unbranched alcohols having a chain length of from 3 to 30 carbon atom. Such ester oils can then advantageously be chosen from the group isopropyl myristate, isopropyl palmitate, isopropyl stearate, isopropyl oleate, n-butyl stearate, n-hexyl laurate, n-decyl oleate, isooctyl stearate, isononyl stearate, isononyl isononanate, 2-ethylhexyl palmitate, ethylhexyl laurate, 2-hexyl-decyl stearate, 2-octyldodecyl palmitate, oleyl oleate, oleyl erucate, erucyl oleate and synthetic, semisynthetic and natural mixtures of such esters, e.g. jojoba oil. In addition, the oil phase can advantageously be chosen from the group of branched and unbranched hydrocarbons and hydrocarbon waxes, silicone oils, dialkyl ethers, the group of saturated or unsaturated, branched or unbranched alcohols, and fatty acid triglycerides, namely the triglycerol esters saturated and/or unsaturated, branched and/or unbranched alkanecarboxylic acids having a chain length of from 8 to 24, in particular 12 to 18, carbon atoms. The fatty acid triglycerides can, for example, advantageously be chosen from the group of synthetic, semisynthetic and natural oils, e.g. olive oil, sunflower oil, soybean oil, peanut oil, rapeseed oil, almond oil, palm oil, coconut oil, palm kernel oil and the like. Any mixtures of such oil and wax components are also to be used advantageously for the purposes of the present invention. It may also be advantageous in some instances to use waxes, for example cetyl palmitate, as the sole lipid component of the oil phase. The oil phase is advantageously chosen from the group 2-ethylhexyl isostearate, octyldodecanol, isotridecyl isononanoate, isoeicosane, 2-ethylhexyl cocoate, C12-15-alkyl benzoate, caprylic/capric triglyceride, dicapryl ether. Particularly advantageous mixtures are those of the C12-15-alkyl benzoate and 2-ethylhexyl isostearate, those of C12-15-alkyl benzoate and isotridecyl isononanoate, those of the C12-15-alkyl benzoate, 2-ethylhexyl isostearate and isotridecyl isononanoate. The oil phase can also advantageously have a content of cyclic or linear silicone oils or consist entirely of such oils, although it is preferable to use an additional content of their oil phase components apart from the silicone oil or silicone oils. Cyclomethicone (octamethylcyclotetrasiloxane) is advantageously used as silicone oil to be used according to the invention. However, other silicone oils can also be used advantageously for the purposes of the present invention, for example hexameth-ylcyclotrisiloxane, polydimethylsiloxane, poly(methylphenylsiloxane). Also particularly advantageous are mixtures of cyclomethicone and isotridecyl isononanoate, and of cyclomethicone and 2-ethylhexyl isostearate. The aqueous phase of the preparations according to the invention optionally advantageously comprises alcohols, diols or polyols (lower alkyl), and ethers thereof, preferably ethanol, isopropanol, propylene glycol, glycerol, ethylene glycol-monoethyl or monobutyl ether, propylene glycol monomethyl, -monoethyl or monobutyl ether, diethylene glycol monomethyl or -monoethyl ether and analogous products, and also alcohols (lower alkyl), e.g. ethanol, 1,2-propanediol, glycerol, and, in particular, one or more thickeners which can advantageously be chosen from the group consisting of silicon dioxide, aluminium silicates, polysaccharides and derivatives thereof, e.g. hyaluronic acid, xanthan gum, hydroxypropylmethyl-cellulose, particularly advantageously from the group of polyacrylates, preferably a polyacrylate from the group of so-called Carbopols, for example Carbopol grades 980, 981, 1382, 2984, 5984, in each case individually or in combination. A comprehensive description of the raw materials and active ingredients used in cosmetic compositions is given in DE-A 199 19 630. It could not have been foreseen that the indanylidene compounds according to the invention represent an excellent selection compared with the compounds known from EP-A823418. Examples: Photostability By way of example, comparative measurements between the compounds of category A and the compounds of category B and the combination with other standard commercial UV filters such as OMC (= octyl methoxycinnamate) or BMDM (= tert-butylmethoxydibenzoylmethane) are listed below. The substances of category B demonstrate the improvement over the substances of category A. The irradiation was carried out in a Suntester from Heraeus at an irradiation intensity of 765 W/m2 (based on Global sensor). The values give the concentration decrease of the UV filters in percentage following irradiation (dose in J/cm2). Formulation according to formulation Example 1 (Table Removed) Tab.l Formulation according to formulation Example 12 (Table Removed) Tab.2 Formulation according to formulation Comparison Example 12 Example 4 Example 4 without A or B without OMC (Table Removed) Tab.3 Compounds in Tables 1-3: (Table Removed) Example 1 2-(5,6-Dimethoxy-3,3-dimethyl-l-indanylidene)-4,4-dimethyl-3-oxo-pentanonitrile (Figure Removed) 44 g (0.2 mol) of 5,6-dimethoxy-3,3-dimethyl-l-indanone, 25 g (0.2 mol) of pivaloylacetonitrile, 32 g of propionic acid and 17 g of ammonium acetate are mixed in 80 g of xylene and heated at 120°C for 7 hours. After the system has been cooled to room temperature and the organic phase has been washed, the xylene is distilled off, and the crude product which remains is recrystallized in methanol. Yield: 50% theory; E1/1 730 (λmax 373 nm). Example 2 2-(5-Methoxy-3,3,4,6-tetramethyl-l-indanylidene)-4,4-dimethyl-3-oxo-pentanonitrile (Figure Removed) The procedure was analogous to that in Example 1 starting from 5-methoxy-3,3,4,6-tetramethyl-1-indanone. Yield: 50% of theory; E1/1 588 (λmax 340 nm). Example 3 2-(3,3,5,6-tetramethyl-l-indanylidene)-4,4-dimethyl-3-oxo-pentanonitrile (Figure Removed) The procedure was analogous to that in Example 1 starting from 3,3,5,6-tetramethyl-1-indanone. Yield: 55% of theory; El/1 630 (λmax 342 nm). Example 4 2-(3,3,6-trimethyl-l-indanylidene)-4,4-dimethyl-3-oxo-pentanonitrile (Figure Removed) The procedure was analogous to that in Example 1 starting from 3,3,6-trimethyl-l-indanone. Yield: 45% of theory; E1/1 528/505 (λmax 335/316 nm). Example 5 2-(5,6-Ethylenedioxo-3,3-dimethyl-l-indanylidene)-4,4-dimethyl-3-oxo-pentano-nitrile (Figure Removed) The procedure was analogous to that in Example 1 starting from 5,6-ethylenedioxo-3,3-dimethyl-l-indanone. Yield: 55% of theory; E1/1 640 (λmax 369 nm). Example 6 2-(5-Methoxy-3,3,6-trimethyl-l-indanylidene)-4,4-dimethyl-3-oxo-pentanonitrile (Figure Removed) The procedure was analogous to that in Example 1 starting from 5-methoxy-3,3,6-trimethyl-1-indanone. Yield: 60% of theory; E1/1 850 (λmax 359 nm). Example 7 2-[(5-Methoxy-3,3-dimethyl-(2-methyl-3-(l,3,3,3-tetramethyl-l-(trimethyl-silyloxy)-disiloxanyl)-propyl)-indanylidene)]-4,4-dimethyl-3-oxo-pentanonitrile (Figure Removed) a) 2-(5-Methoxy-3,3-dimethyl-6-hydroxy-l-indanylidene)-4,4-dimethyl-3-oxo-pentanonitrile (Figure Removed) 5-Methoxy-3,3-dimethyl-6-hydroxy-l-indanone is reacted according to Example 1. Yield: 50% of theory. b) 2-(5-Methoxy-3,3-dimethyl-6-(2-methyl-propenyloxy)-l-indanylidene)-4,4-dimethyl-3 -oxo-pentanonitri le (Figure Removed) 136g (0.43 mol) of the compound under a) are added together with 95 g of potassium carbonate to 470 g of N-methylpyrrolidinone, heated to 70°C and 42 g (0.46 mol) of methallyl chloride are added thereto over the course of 30 min. The mixture is heated for a further 3 h at 70°C, then cooled to room temperature, and the product is extracted with ethyl acetate. Yield: 45% of theory. 90g (130mmol) of the compound under b), 29g (130mmol) of 1,1,1,3,5,5,5-hepta-methyltrisiloxane are kept at 80°C in the presence of catalytic amounts of divinyltetramethylplatinum complex in 90 g of toluene and a nitrogen atmosphere for 20 h. After the solvent has been distilled off, the residue is distilled over a Kugelrohr, giving 50 g (70% of theory) of the desired product as a yellow oil; E1/1 400 (λmax 373 nm). Example 8 2-(6-Acetoxy-3,3-dimethyl-5-methoxy-l-indanylidene)-4,4-dimethyl-3-oxo-pentano-nitrile (Figure Removed) 54 g (0.17 mol) of the compound under a) are reacted with 13 g (0.17 mol) of acetyl chloride in N-methylpyrrolidinone at 40°C over the course of 5 h. Yield: 98% of theory. E1/1 420/280 (λmax 355/302 nm). Example 9 2-(3,3-Dimethyl-5-tert-butyl-l-indanylidene)-3-(l'-methylcyclohexyl)-3-oxo-propiononitrile (Figure Removed) 3,3-Dimethyl-5-tert-butyl-l-indanone are reacted with 3-(l'-methylcyclohexyl)-3-oxo-propiononitrile analogously to Example 1. Yield: 40% of theory. E1/1 580 (λmax 355 nm). Example 10 2-(3,3,5-Trimethyl-l-indanylidene)-3-phenyl-3-oxo-propiononitrile (Figure Removed) 3,3,5-Trimethyl-l-indanone are reacted with benzoylacetonitrile analogously to Example 1. Yield: 50% of theory. E1/1 600 (λmax 350 nm). Formulation Example 1 Sunscreen soft cream (O/W), in-vitro SPF 3, water resistant (Table Removed) Preparation method Part A: Heat to about 85°C. Part B: Weigh in raw materials without Carbopol. Disperse Carbopol therein using Ultra Turrax. Heat to about 85°C. Add B to A. Part C: Immediately add to A/B and then homogenize while hot (Ultra Turrax). Leave to cool with stirring. Part D: Add and stir in. (Table Removed) Formulation Example 2 Sunscreen lotion (O/W), in-vitro SPF 20 (Table Removed) Preparation method Part A: Heat to about 85°C. Part B: Weigh in raw materials without Carbopol. Disperse Carbopol therein using Ultra Turrax. Heat to about 85°C. Add B to A. Part C: Immediately add to A/B and then homogenize while hot (Ultra Turrax). Leave to cool with stirring. Part D: Add and stir in. (Table Removed) Formulation Example 3 Sunscreen milk (0/W), in-vitro SPF 6 (Table Removed) Preparation method Part A: Heat to 80-85°C. Part B: Heat to 80-85°C, add part B to part A with stirring. Part C: Disperse Carbopol into the water and neutralize with NaOH, with stirring. Add part C at about 60°C with stirring. Allow to cool to RT. Part D: Add and stir. (Table Removed) Formulation Example 4 Sunscreen lotion (O/W), in-vitro SPF 21 (Table Removed) Preparation method Part A:Heat to 80-85°C. Part B: Heat to 80-85°C, add part B to part A with stirring. Part C: Disperse Carbopol into the water and neutralize with NaOH, with stirring. Add part C at about 60°C with stirring. Allow to cool to RT. Part D: Add and stir. (Table Removed) Formulation Example 5 Sunscreen lotion (O/W), in-vitro SPF 11 (Table Removed) Preparation method Part A: Dissolve UV absorber according to formula I in the oils or liquid UV filters (heating to about 70°C). Allow to cool to about 30°C, add the remaining constituents apart from Carbopol and Pemulen and mix at room temperature (stir for about 5 minutes). Stir in Carbopol and Pemulen. Part B: Dissolve Solbrols in phenoxyethanol with heating. Mix with water and glycerol, add to part A with stirring. Stir for about 60 minutes. Part C: Add to A/B, homogenize using the Ultra Turrax. (Table Removed) Formulation Example 6 Sunscreen cream (W/O), in-vitro SPF 4, water resistant (Table Removed) Preparation method Part A: Heat to about 85°C. Part B:Heat to about 85°C (without zinc oxide; disperse zinc oxide therein using the Ultra Turrax). Add B to A. Allow to cool with stirring, then homogenize. (Table Removed) Formulation Example 7 Sunscreen softcream (W/O), in-vitro SPF 40 (Table Removed) Preparation method Part A: Heat to about 85°C. Part B:Heat to about 85°C (without zinc oxide; disperse zinc oxide therein using the Ultra Turrax). Add B to A. Allow to cool with stirring. Part C: Add and then homogenize (Table Removed) Formulation Example 8 Sunscreen milk (W/O) (Table Removed) Preparation method Part A: Heat to about 85°C. Part B: Heat to about 85°C. Add B to A. Allow to cool with stirring. Part C: Add and then homogenize. Formulation Example 9 Daycare cream with UV protection (Table Removed) Preparation method Part A:Heatto80°C. Part B: Heat to 80°C Add to part A with stirring. Part C: Disperse Carbopol in water and neutralize with sodium hydroxide solution. Add to part A/B at about 55°C. Part D: Add at RT and homogenize. Formulation Example 10 Sunscreen spray (Table Removed) Preparation method Part A: Dissolve Lara Care A-200 into the other constituents of part A with stirring. Part B: Weigh in all raw materials (without Pemulen) and dissolve the crystalline substances with heating. Disperse Pemulen therein. Add part B to part A then homogenize for 1 minute. Add part C+D and homogenize again for 1-2 minutes using the Ultra Turrax. Formulation Example 11 (Table Removed) Preparation method Part A: Disperse Carbopol in water and neutralize with sodium hydroxide solution. Part B: Add to part A with stirring. Part C: Dissolve cristalline constituents in the other raw materials of part C with warming (max.40°C) and add to part A/B. Stir well and then homogenize. (Homozenta). Formulation Example 12 Hair Conditioner with UV filters (Table Removed) Preparation method PartA:Heatto80°C. Part B: Heat to 80°C. Add to part A with stirring. Part C: Add at 40°C and cool to RT. Formulation Example 13 (Table Removed) Preparation method PartA:Heatto80-85°C. Part B: Heat to 80-85°C, add part B to part A with stirring. Part C: Disperse Carbopol into the water and neutralize with NaOH with stirring. Add part C at about 60°C with stirring. WE CLAIM; 1. Indanylidene compounds of the formula (Formula Removed) in which R1 and R2 are hydrogen; R3 and R4 are methyl; R5 to R7, independently of one another, are hydrogen, C1-C20-alkyl, C 1-C20-alkoxy, acetoxy, or Me-Si(OSiMe3)2-CH2CH(CH3)CH2-O-, with the proviso that R6 and R7 are not both methoxy, when R5 is hydrogen; additionally two substituents of R5 to R7 on adjacent carbon atoms can together form a 1,4-dioxalan ring. R8 is hydrogen; X is cyano; n is 1; R9 to R11 are methyl. 2. An indanylidene compound as claimed in claim 1 and selected from the following: a. 2-(3,3,5,6-tetramethyl-l-indanylidene)-4,4-dimethyl-3-oxo-pentanonitrile (Formula Removed) b. 2-(3,3,5-trimethyl-l-indanylidene)-4,4-diinethyl-3-oxo-pentanonitrile (Formula Removed) c. 2-(3,3,6-trimethyl-l-indanylidene)-4,4-dimethyl-3-oxo-pentanonitrile (Formula Removed) d. 2-(5-methoxy-3,3,4,6-tetramethyl-l-indanylidene)-4,4-dimethyl-3- oxo-pentanonitrile (Formula Removed) e 2-(5-methoxy-3,3,6-trimethyl-l-indanylidene)-4,4-dimethyl-3-oxo-pentanonitrile (Formula Removed) f. 2-(5-n-butoxy-3,3,4-trimethyl-1 -indanylidene)-4,4-dimethyl-3-oxo-pentanonitrile (Formula Removed) g. 2-(3,3-dimethyl-5-methoxy-1 -indanylidene)-4,4-dimethyl-3-oxo-pentanonitrile (Formula Removed) h. 2-(5-n-butoxy-3,3,6-trirnethyl-l-indanylidene)-4,4-dimethyl-3-oxo-pentanonitrile (Formula Removed) i. 2-(5-t-butyl-3,3-dimethyl-l-indanylidene)-4,4-dimethyl-3-oxo-pentanonitrile (Formula Removed) j. 2-(5,6-ethylenedioxo-3,3-dimethyl-l-indanylidene)-4,4-dimethyl-3-oxo-pentanonitrile (Formula Removed) k. 2-[3,3-dimethyl-5-methoxy-6-(2-methyl-3-(l>3,3,3-tetramethyl-l-(trimethyl-silyloxy)-disiloxanyl)-propyloxy)-indanylidene]-4,4-dimethyl-3-oxo-pentanonitrile (Formula Removed) 1. 2-(6-acetO3cy-3,3-dimethyl-5-niethoxy- l-indanylidene)-4,4-dimethyl-3-oxo-pentanonitrile (Formula Removed) 3. A cosmetic composition for protecting skin and hair, comprising a total amount of 0.1 to 30% by weight of one or more indanyliden compounds as claimed in claim 1 based on the total weight of the composition and one or more compounds selected from the group consisting of (i) water-soluble UV filter substance in an amount of 0.1-10% by weight based on the total weight of the composition and (ii) oil-soluble UV filter substance in an amount of 0.1-10% by weight based on the total weight of the composition. 4. The cosmetic composition for protecting skin and hair, as claimed in claim 3 wherein the composition comprises one or more indanyliden compounds selected from the following: a. 2-(3,3,5,6-tetramethyl-1 -indanylidene)-4,4-dimethyl-3-oxo- pentanonitrile (Formula Removed) b. 2-(3,3,5-trimethyl-l-indanylidene)-4,4-dimethyl-3-oxo-pentanonitrile (Formula Removed) c. 2-(3,3,6-trimethyl- l-indanylidene)-4,4-dimethyl-3-oxo-pentanonitrile (Formula Removed) d. 2-(5-methoxy-3,3,4,6-tetramethyl-1 -indanylidene)-4,4-dimethyl-3-oxo- pentanonitrile (Formula Removed) e. 2-(5-methoxy-3,3,6-trimethyl-1 -indanylidene)-4,4-dimethyl-3-oxo-pentanonitrile (Formula Removed) f. 2-(5-n-butoxy-3,3,4-trimethyl-1 -indanylidene) -4,4-dimethyl-3-oxo- pentanonitrile (Formula Removed) g. 2-(3,3-dimethyl-5-inethoxy-1 -indanylidene)-4,4-dimethyl-3-oxo- pentanonitrile (Formula Removed) h. 2-(5-n-butoxy-3,3,6-trimethyl-1 -indanylidene)-4,4-dimethyl-3-oxo-pentanonitrile (Formula Removed) i. 2-(5-t-butyl-3,3-dimethyl-1 -indanylidene)-4,4-dimethyl-3-oxo-pentanonitrile (Formula Removed) j. 2-(5,6-ethylenedioxo-3,3-dimethyl-1 -indanylidene)-4,4-dimethyl-3-oxo-pentanonitrile (Formula Removed) k. 2-[3,3-dimethyl-5-methoxy-6-(2-met±iyl-3-(l,3,3,3-tetramethyl-l-(trimethyl-silyloxy)-disiloxanyl)-propyloxy)-indanylidene]-4,4-diinethyl-3-oxo-pentanonitrile (Formula Removed) 1. 2-(6-acetoxy-3,3-dimethyl-5-methoxy-1 -indanylidene)-4,4-dimethyl-3-oxo-pentanonitrile (Formula Removed) 5. The cosmetic composition as claimed in Claim 3, wherein it comprises at least one tanning agent and/or artificial self-tanning agent for the skin. 6. The cosmetic composition as claimed in Claim 3, wherein it comprises, in addition to the compounds of the formula I according to the invention it contains, one or more other UV filter substance from the group consisting of ethylhexylmethoxy cinnamate, 2-ethylhexyl-2-cyano-3,3- diphenyl acrylate, 2-phenylbenzimidazolesulphonic acid, methylbenzylidene campher, 4-t-butyl-4'-methoxy-dibenzoylmethane, phenylene-bis- benzimidazyl-tetrasulphonic acid disodium salt, terephthalylidene- dibomanesulphonic acid and salts thereof, 2-(2H-benzotriazol-2-yl)-4- methyl-6-(2-methyl-3( 1,3,3,3-tetramethyl-1 -(trimethylsilyl)-oxy)- disiloxyanyl)-propyl)phenol, benzylidene malonate polysiloxane, 2,2'- methylene-bis- (6- (2 H-benzotriazol-2 -yl) -4- (1,1,3,3-tetramethylbutyl) - phenol), 2,4-bis[{(4-(2-ethyl-hexyloxy-2-hydroxy}-phenyl]-6-(4-methoxy- phenyl)-l,3,5-triazine, 4,4',4"-(l,3,5-triazine-2,4,6-triyltriimino)-tris-benzoic acid tris(2-ethylhexyl ester), 4,4'-[(6-[4-(l,l-dimethyl)-aminocarbonyl)- phenylamino]-1,3,5-triazine-2,4-diyl)diimino]-bis-(benzoic acid-2-ethylhexyl ester), zinc oxide and titanium dioxide. 7. The cosmetic composition as claimed in Claim 3, wherein it comprises UV filter substance and additionally coated or noncoated pigments or nanopigments of metal oxides. 8. The cosmetic composition as claimed in Claim 3, wherein it comprises UV filter substance and additionally finely divided pigments such that a UV broad-band protection performance with a critical wavelength λcrit.> 380 nm results therefrom.

Full Text

Novel indanvlidene compounds
The invention relates to novel indanylidene compounds, to a process for their preparation and to their use as UVA filters.
Indanylidene compounds which have UV-absorbing properties are already known from EP-A 823 418. However, the indanylidene compounds previously described in EP-A 823 418 have a photostability which is too low for the application.
Novel indanylidene compounds of the formula
(Formula Removed)
in which
R1 to R4, independently of one another are hydrogen, C1-C20-alkyl or C5-C10-cyclo-alkyl, with the proviso that two substituents on adjacent carbon atoms can together also be an optionally substituted C1-C4-alkylene group;
may also, independently of one another, be C2-C20-alkyl, in which at least one methylene group may be replaced by oxygen, C3-C20-alkenyl, C3-C20-alkinyl or a group S,
where S may be a silane, an oligosiloxane or a polysiloxane group; -
R5 to R8, independently of one another, are hydrogen, C1-C20-alkyl or C5-C10-cyclo-alkyl or C1-C20-alkoxy, C5-C10-cycloalkoxy, hydroxyl, acetoxy, acetamino, carboxyl, carbalkoxy or carbamoyl,
additionally two substituents of R5 to R8 on adjacent carbon atoms can together form a 5-7-membered ring which contains up to three heteroatoms, in particular oxygen or nitrogen, where the ring atoms may be substituted by exocyclically double-bonded oxygen (keto group),
also, in the case of alkoxy, may, independently of one another, be C2-C20-alkyl in which at least one methylene group may be replaced by oxygen, C3-C20-alkenyl, C3-C20-alkinyl or a group S,
where S may be a silane, an oligosiloxane or a polysiloxane group;
X is cyano, CON(R)2 or CO2R, where R is hydrogen or C1-C8-alkyl;
n is 1 or 0;
R9 to R11, in cases where n=l, may be hydrogen, C1-C20-alkyl or C5-C10-cycloalkyl, aryl or heteroaryl,
additionally two substituents of R9 to R1' can, together with the B-atom form a 3-7-membered ring which may contain up to three heteroatoms, in particular oxygen or nitrogen,
also, in cases where n=0, R9 and R10, together with the 13-atom, are an aryl or heteroaryl radical.
have been found.
The novel indanylidene compounds represent a surprising selection from the indanylidene compounds known from EP-A 823 418. They have a significantly higher photostability than the compounds mentioned in EP-A 823 418 and high compatibility with other UV filters, such as, for example, isooctyl p-methoxy-cinnamate.
Preference is given to indanylidene compounds of the formula
(Formula Removed)
Particular preference is given to indanylidene compounds of the formula
(Formula Removed)
Specifically, the following preferred indanylidene compounds may be mentioned: 2-(5,6-Dimethoxy-3,3-dimethyl-l-indanylidene)-4,4-dimethyl-3-oxo-pentanonitrile, 2-(5-methoxy-3,3,4,6-tetramethyl-l-indanylidene)-4,4-dimethyl-3-oxo-pentano-nitrile, 2-(3,3,5,6-tetramethyl-1 -indanylidene)-4,4-dimethyl-3-oxo-pentanonitrile, 2-(3,3,6-trimethyl-l-indanylidene)-4,4-dimethyl-3-oxo-pentanonitrile, 2-(5,6-eth-
ylenedioxo-3,3-dimethyl-l-indanylidene)-4,4-dimethyl-3-oxo-pentanonitrile, 2-(5-methoxy-3,3,6-trimethyl-l-indanylidene)-4,4-dimethyl-3-oxo-pentanonitrile, 2-[(5-methoxy-3,3-dimethyl-(2-methyl-3-( 1,3,3,3-tetramethyl-1 -(trimethyl-silyloxy)-disiloxanyl)-propyl)-indanylidene)]-4,4-dimethyl-3-oxo-pentanonitrile and 2-(6-acetoxy-3,3-dimethyl-5-methoxy-l-indanylidene)-4,4-dimethyl-3-oxo-pentanonitrile.
The indanylidene compounds according to the invention can be prepared by (Knoevenagel) condensation of compounds of the formula
(Formula Removed)
where
1 O
R to R have the meanings given above, with compounds of the formula
(Formula Removed)
where
R9 to R11 and X have the meanings given above.
The indanones used here can be prepared by Friedel-Crafts Reactions of (substituted) acrylic esters with (substituted) aromatics or, in the case of hydroxyl substituents, by
Fries rearrangement of corresponding phenyl esters (F.-H. Marquardt, Helv. Chim. Actai59, 1476(1965)).
The preparation of the indanylidene compounds according to the invention can, for example, be carried out as follows:
The abovementioned indanones are condensed with equimolar amounts of pivaloyl-acetonitrile with the catalysis of ammonium acetate according to the conditions of a Knoevenagel condensation.
The preparation can be illustrated by the reaction scheme below:
(Formula Removed)
The indanylidene compounds according to the invention can be used as UV absorbers, e.g. in cosmetic compositions, in particular for protecting against acute skin damage (sunburn) and also chronic skin damage (premature skin ageing), particularly in sunscreen compositions, daily care products and hair care products, but also for improving the photostability of technical products, such as paints, surface coatings, plastics, textiles, packaging materials and rubbers.
The indanylidene compounds according to the invention can be used individually or in a mixture in the corresponding preparations; it is also possible to use them in combination with UV absorbers of other classes of substance, and also with the latter in any desired mixtures with one another. For example, the following UV absorbers may be mentioned:
• p-aminobenzoic acid
• ethyl p-aminobenzoate (25 mol) ethoxylated
• 2-ethylhexyl p-dimethylaminobenoate
• ethyl p-aminobenzoate (2 mol) N-propoxylated
• glycerol p-aminobenzoate
• homomethyl salicylate (homosalate) (Neo Heliopan®HMS)
• ethylhexyl salicylate (Neo Heliopan®OS)
• triethanolamine salicylate
• 4-isopropylbenzyl salicylate
• menthyl anthranilate (Neo Heliopan®MA)
• ethyl diisopropylcinnamate
• 2-ethylhexyl p-methoxycinnamate (Neo Heliopan®AV)
• methyl diisopropylcinnamate
• isoamyl p-methoxycinnamate (Neo Heliopan®E 1000)
• p-methoxycinnamate acid diethanolamine salt
• isopropyl p-methoxycinnamate
• 2-ethylhexyl 2-cyano-3,3-diphenyl acrylate (Neo Heliopan®303)
• ethyl 2-cyano-3,3'-diphenyl acrylate
• 2-phenylbenzimidazolesulphonic acid and salts (Neo Heliopan®hydro)
• 3-(4l-trimethylammonium)-benzylidene-boman-2-one methylsulphate
• terephthalylidene-dibornanesulphonic acid and salts (Mexoryl®SX)
• 4-t-butyl-4'-methoxy-dibenzoylmethane (Avobenzon) / (Neo Heliopan®357)
• J3-imidazole-4(5)-acrylic acid (Urocanic acid)
• 2-hydroxy-4-methoxybenzophenone (Neo Heliopan®BB)
• 2-hydroxy-4-methoxybenzophenone-5-sulphonic acid
• dihydroxy-4-methoxybenzophenone
• 2,4-dihydroxybenzophenone
• tetrahydroxybenzophenone
• 2,2'-dihydroxy-4,4'-dimethoxybenzophenone
• 2 -hydroxy-4-n-octoxybenzophenone
• 2-hydroxy-4-methoxy-4'-methylbenzophenone
• 3-(4'-sulpho)benzylidene-boman-2-one and salts
• 3-(4'-methylbenzylidene)-d,l-camphor (Neo Heliopan"MBC)
• 3-benzylidene-d,l-camphor
• 4-isopropyldibenzoylmethane
• 2,4,6-trianilino-(p-carbo-2'-ethylhexyl-1 '-oxy)-1,3,5-triazine
• phenylene-bis-benzimidazyl-tetrasulphonic acid disodium salt (Neo Heliopan®AP)
• 2,2'-(l,4-phenylene)-bis-(lH-benzimidazole-4,6-disulphonic acid), monosodium salt
• N-[(2 and 4)-[2-(oxoborn-3-ylidene)methyl]benzyl]-acrylamide-polymer
• phenol, 2-(2H-benzotriazol-2-yl)-4-methyl-6-(2-methyl-3(l,3,3,3-tetramethyl-l-
(trimethylsilyl)-oxy)-disiloxyanyl)-propyl), (Mexoryl®XL)
• bis-(2-ethylhexyl) 4,4'-[(6-[4-( 1,1 -dimethyl)-aminocarbonyl)-phenylamino]-1,3,5-
triazine-2,4-diyl)diimino]-bis-(benzoate) (Uvasorb®HEB)
• 2,2'-methylene-bis-(6-(2H-benztriazol-2-yl)-4-l,l,3,3-tetramethylbutyl)-phenol),
(Tinosorb®M)
• 2,4-bis-[4-(2-ethylhexyloxy)-2-hydroxyphenyl]-1,3,5-triazine
• benzylidene malonate-polysiloxane (Parsol®SLX)
• glycerylethyl hexanoate-dimethoxycinnamate
• disodium 2,2'-dihydroxy-4,4'-dimethoxy-5,5'-disulpho-benzophenone
• dipropylene glycol salicylate
• sodium hydroxymethoxybenzophenonesulphonate
• tris (2-ethylhexyl) 4,4',4-(l,3,5-triazine-2,4,6-triyltriimino)-tris-benzoate
(Uvinul®T150)
• 2,4-bis-[{(4-(2-ethyl-hexyloxy)-2-hydroxy}-phenyl]-6-(4-methoxyphenyl)-1,3,5-
triazine, (Tinosorb®S)
• 2,4-bis-[{(4-(3-sulphonato)-2-hydroxy-propyloxy)-2-hydroxy}-phenyl]-6-(4-
methoxyphenyl)-l,3,5-triazine sodium salt
• 2,4-bis-[ {(3-(2-propyloxy)-2-hydroxy-propyloxy)-2-hydroxy} -phenyl]-6-(4-
methoxy-phenyl)-! ,3,5-triazine
• 2,4-bis-[{4-(2-ethyl-hexyloxy)-2-hydroxy}-phenyl]-6-[4-(2-methoxyethyl-
carbonyl)-phenylamino]-l,3,5-triazine
• 2,4-bis-[{4-(3-(2-propyloxy)-2-hydroxy-propyloxy)-2-hydroxy}-phenyl]-6-[4-(2-
ethylcarboxyl)-phenylamino] -1,3,5 -triazine
• 2,4-bis-[{4-(2-ethyl-hexyloxy)-2-hydroxy}-phenyl]-6-(l-methyl-pyrrol-2-yl-)-
1,3,5-triazine
• 2,4-bis-[{4-tris-(trimethylsiloxy-silylpropyloxy)-2-hydroxy}-phenyl]-6-(4-meth-
oxyphenyl)-1,3,5-triazine
• 2,4-bis-[{4-(2"-methylpropenyloxy)-2-hydroxy}-phenyl]-6-(4-methoxyphenyl)-
1,3,5-triazine
• 2,4-bis-[{4-(l',l',l',3'5',5',5'-heptamethylsiloxy-2"-methyl-propyloxy)-2-
hydroxy}-phenyl]-6-(4-methoxyphenyl)-l,3,5-triazine
Particularly suitable UV absorbers are:
• p-aminobenzoic acid
• 3-(4'-trimethylammonium)-benzylidene-boman-2-one methylsulphate
• homomethyl salicylate (Neo Heliopan®HMS)
• 2-hydroxy-4-methoxy-benzophenone (Neo Heliopan®BB)
• 2-phenylbenzimidazolesulphonic acid (Neo Heliopan®Hydro)
• terephthalylidenedibornanesulphonic acid and salts (Mexoryl®SX)
• 4-tert-butyl-4'-methoxydibenzoylmethane (Neo Heliopan®357)
• 3-(4'-sulpho)benzylidene-bornan-2-one and salts
• 2-ethylhexyl 2-cyano-3,3-diphenylacrylate (Neo Heliopan®303)
• N-[(2 and 4)-[2-(oxoborn-3-ylidene)methyl]benzyl]-acrylamide polymer
• 2-ethylhexyl p-methoxycinnamate (Neo Heliopan®AV)
• ethyl p-aminobenzoate (25 mol) ethoxylated
• isoamyl p-methoxycinnamate (Neo Heliopan®E1000)
• 2,4,6-trianilmo-(p-carbo-2'-ethylhexyl-r-oxy)-l,3,5-triazine(Uvinul®T150)
• phenol, 2-(2H-benzotriazol-2-yl)-4-methyl-6-(2-methyl-3(l,3,3,3-tetramethyl-l-
(trimethylsilyl)-oxy)-disiloxyanyl)-propyl), (Mexoryl®XL)
• bis-(2-ethylhexyl) 4,4'-[(6-[4-(l,l-dimethyl)-aminocarbonyl)-phenylamino]-
1,3,5-triazine-2,4-diyl)-diimino]-bis-(benzoate), (UvasorbHEB)
• 3-(4'-methylbenzylidene)-d,l-camphor (Neo Helipan®MBC)
• 3-benzylidenecamphor
• 2-ethylhexyl salicylate (Neo Helipan®OS)
• 2-ethylhexyl 4-dimethylaminobenzoate (Padimate O)
• hydroxy-4-methoxybenzophenone-5-sulphonic acid and Na salt
• 2,2'-methylene-bis-(6-(2H-benztriazol-2-yl)-4-l,l,3,3-tetramethylbutyl)-phenol),
(Tinosorb®M)
• phenylene-bis-benzimidazyltetrasulphonic acid disodium salt (Neo Heliopan®AP)
• 2,4-bis-[{(4-(2-ethyl-hexyloxy)-2-hydroxy}-phenyl]-6-(4-methoxyphenyl)-l,3,5-
triazine, (Tinosorb®S)
• benzylidene malonate-polysiloxane (Parsol®SLX)
• menthyl anthranilate (Neo Heliopan®MA)
It may also be advantageous to use polymer-bonded or polymeric UV absorbers in preparations according to the present invention, in particular those described in WO-A-92/20690. The combination of the indanylidene compounds according to the invention with finely divided inorganic and organic pigments, such as, for example, titanium dioxide, zinc oxide and iron oxide and Tinosorb®M, in sunscreen and daily care products with UV protection is likewise possible.
The list of UV filters given which can be used for the purposes of the present invention is not of course intended to be limiting.
The total amount of all (mono- and polysulphonated) water-soluble UV filter substances in the finished cosmetic or dermatological preparations, for example of phenylene-bis-benzimidazyl-tetrasulphonic acid disodium salt or salts thereof and/or the corresponding disulphonic acid or salts thereof and/or 2-phenylbenzimidazole-5-sulphonic acid and salts thereof and/or 2-hydroxy-4-methoxybenzophenone-5-
sulphonic acid and salts thereof and/or 4-(2-oxo-3-bornylidenemethyl)-benzenesulphonic acid and salts thereof and/or 2-methyl-5-(2-oxo-3-bornylidene-methyl)-benzenesulphonic acid and salts thereof and/or benzene-l,4-di-(2-oxo-3-bomylidenemethyl)-10-sulphonic acid and salts thereof, is advantageously chosen from the range from 0.1 to 10.0% by weight, preferably 0.5 to 6.0% by weight, based on the total weight of the preparations, if the presence of these substances is desired.
The total amount of oil-soluble UV filter substances in the finished cosmetic or dermatological preparations, for example of tris(2-ethylhexyl) 4,4',4"-(l,3,5-triazine-2,4,6-triyltriimino)-tris-benzoate and/or 4-tert-butyl-4'-methoxy-dibenzoyl-methane and/or 4-methylbenzylidenecamphor and/or octyldimethyl-p-aminobenzoic acid and/or Mexoryl®XL and/or Uvasorb®HEB and/or Tinosorb®S and/or benzo-phenone-3 and/or Parsol®SLX and/or Neo Heliopan®MA is advantageously chosen from the range from 0.1 to 10.0% by weight, preferably 0.5 to 6.0% by weight, based on the total weight of the preparations, if the presence of these substances is desired.
The total amount of 2-ethylhexyl p-methoxycinnamate and/or isoamyl p-methoxy-cinnamate in the finished cosmetic or dermatological preparations is advantageously chosen from the range from 0.1 to 15.0% by weight, preferably 0.5 to 7.5% by weight, based on the total weight of the preparations, if the presence of these substances is desired.
The total amount of ethylhexyl 2-cyano-3,3-diphenylacrylate in the finished cosmetic or dermatological preparations is, if the presence of this substance is desired, advantageously chosen from the range from 0.1 to 15.0%, preferably 0.5 to 10.0% by weight, based on the total weight of the preparations.
The total amount of one or more salicylic acid derivatives in the finished cosmetic or dermatological preparations is advantageously chosen from the range from 0.1 to 15.0% by weight, preferably 0.5 to 10.0% by weight, based on the total weight of the preparations. If ethylhexyl salicylate is chosen, it is advantageous to choose its total
amount from the range from 0.1 to 5.0% by weight. If homomenthyl salicylate is chosen, it is advantageous to choose its total amount from range from 0.1 to 10.0% by weight.
The indanylidene compounds according to the invention are also suitable to a particular degree for photostabilizing UV absorbers with low UV photostability. The photostabilization of the very photo-unstable compounds of the dibenzoylmethane, e.g. tert-butyl-4'-methoxydibenzoylmethane, is particularly successful.
A further photostable UV filter combination is achieved using 0.1 to 10% by weight, preferably 1 to 10% by weight, of ethylhexyl p-methoxycinnamate or isoamyl p-methoxy cinnamate with 0.1 to 10% by weight, preferably 1 to 6% by weight, of the compound of the formula I, preferably in the ratio 1:1.
The combinations of p-methoxycinnamic esters and dibenzoylmethane derivatives and compounds of the formula I can be formulated to be photostable by using, for example, 0.1 to 5% by weight, preferably 1 to 3% by weight, of 4-tert-butyl-4'-meth-oxydibenzoylmethane, 0.1 to 10% by weight, preferably 1 to 7.5% by weight of ethylhexyl p-methoxycinnamate or isoamyl p-methoxycinnamate and at least 0.2% by weight, preferably 1 to 6% by weight, of the compounds of the formula I, preferably in the ratio 1 part of dibenzoylmethane derivative, 2 parts p-methoxycinnamic ester and 2 parts of the indanylidene compounds according to the invention.
hi addition, it is advantageous to add one or more very photostable UV absorbers to this three-way combination, such as, for example, methylbenzylidenecamphor, 2-eth-ylhexyl 2-cyano-3,3'-diphenylacrylate, octyltriazone, Uvasorb®HEB, Tinosorb®S, Tinosorb®M, ethylhexyl salicylate, homomenthyl salicylate, and phenylene-bisimidazolesulphonic acid or phenylene-bis-benzimidazole-tetrasulphonic acid disodium salt, Mexoryl®SX, Mexoryl®XL or Parsol®SLX.
In addition, in cosmetic preparations, a synergistic increase in the sun protection factor is surprisingly achieved using indanylidene derivatives of the formula I in combination with other UV filters. Examples of a synergistic increase in the sun protection factor are cosmetic emulsions which comprise both a compound of the formula I and also ethylhexyl methoxycinnamate or octocrylene, or a combination of a compound of the formula I with ethylhexyl methoxycinnamate and 2-phenyl-benzimidazolesulphonic acid, or ethylhexyl methoxycinnamate and methyl-benzylidenecamphor, or ethylhexyl methoxycinnamate and 4-t-butyl-4'-methoxy-dibenzoylmethane, or Neo Heliopan® AP and ethylhexyl methoxycinnamate, or a combination of a compound of the formula I with octocrylene, methyl-benzylidenecamphor and zinc oxide. Combinations of a compound of the formula I with dibenzoylmethanes, methylbenzylidenecamphor, 2-phenylbenzimidazole-sulphonic acid, Neo Heliopan®AP, Mexoryl®SX, Mexoryl®XL, Parsol®SLX, Tinosorb®S, Tinosorb®M, Uvinul®T150, Uvasorb® HEB, and microfine pigments, zinc oxide and titanium oxide, also have synergistic increases in the sun protection factors. Said UV filter combinations are listed by way of example and are not to be understood as being limited to the abovementioned combinations. Thus, it is possible to use combinations of all UV absorbers already mentioned as particularly suitable on pages 8/9, and UV filters approved in the subsequent publications with compounds of the formula I or the abovementioned combinations, individually or in any desired mixtures.
USA: Food and Drug Administration (FDA). Publication in monograph for
Sunscreen Drug Products for Over-The-Counter Human Use.
Europe: EC Directive 76/768 of the Council for adapting the legal provisions
of the member states regarding cosmetic compositions to technical progress. Publications in the Official Journal of European Communities.
Japan: Publication of the Cosmetics Directive of the Ministry of Health and
Welfare (MHW).
Germany: Publication in the Verordnung iiber kosmetische Mittel [Directive concerning cosmetic compositions] according to the Lebensmittel-und Bedarfsgegenstande-Gesetz (LMBG) [Act relating to Foods and Commodities].
Australia: Registration by Therapeutic Goods Administration (TGA) and publication in the Australian Register of Therapeutic Goods (ARTG).
These combinations usually achieve a synergistic increase in the UV sun protection factor.
The combination of compounds of the formula I with UV-A absorbers, particularly UV-A-II absorbers, gives broad protection against UV-A radiation (320-400 nm). In particular, a combination of compounds of the formula I with Neo Heliopan®AP (UV-AII absorber) is to be mentioned for broad UV-A protection performance. Further UV-A filters which are used in combination with compounds of the formula I alone or in combination of compounds of the formula I and Neo Heliopan®AP are Mexoryl®SX, Mexoryl®XL, Tinosorb®M Tinosorb®S, benzophenone-3, benzophenone-4, Neo Heliopan®357, Neo Heliopan®MA.
For optimum broad-band protection against UV-A and UV-B radiation, the
abovementioned combinations are to be combined with all UV-B filters and mixtures
of these filters (cf. list on pages 6-9). Preferably suitable are Neo Heliopan®AV,
Neo Heliopan®E 1000, Neo Heliopan®Hydro, Neo Heliopan®MBC,
Neo Heliopan®303, Neo Heliopan®OS, Neo Heliopan®HMS, Uvinul®T150, Uvasorb®HEB, ethylhexyl dimethylaminobenzoate.
Combining compounds of the formula I with Neo Heliopan®AP and a UV-B filter, e.g. ethylhexyl methoxycinnamate or UV-B filter mixtures, and coated or uncoated finely disperse metal oxides, such as, for example, zinc oxide, titanium dioxide, achieves UV broad-band protection performance with a critical wavelength λcnt of > 380 nm (cf. Diffey in Int. J. Cosm. Science 16,47 (1994)).
Furthermore, the indanylidene compounds according to the invention can be combined alone or with other UV absorbers used for the protection of technical products.
Examples of such UV absorbers are compounds from the series of benzotriazoles, benzophenones, triazines, cinnamic esters and oxalanilides.
The indanylidene compounds according to the invention are crystalline and have to be dissolved sufficiently in cosmetic preparations to avoid the problem of recrystallization following a prolonged storage period. A sufficient amount of the oil components customarily used in cosmetic preparations, liquid oil-soluble UV absorbers or alcohols, e.g. ethanol, isopropanol or 1-butanol, is necessary to avoid re-crystallization. Particular preference is given to the use of the following oil components and/or UV absorbers for achieving adequate solubility of combinations of the indanylidene compounds according to the invention:
ethylhexylmethoxycinnamate, isoamyl methoxycinnamate, octocrylene, ethylhexyl salicylate, homosalate, menthyl anthranilate, padimate O, diisopropyl adipate, C12-15-alkyl benzoate (Witconol TN), butylene glycol dicaprylate/dicaprate (Miglyol 8810), cocoglycerides (Myritol 331), caprylic/capric triglycerides (Miglyol 812), cetearyl isononanate (Cetiol SN), PVP/hexadecene copolymer (Unimer U151), adipic acid/diethylene glycol/isononanoic acid copolymer (Lexorez 100), propylene glycol dicaprylate/dicaprate (Myritol PC), hexyl laurate (Cetiol A), dicapryl ether (Cetiol OE), diethylhexyl naphthalate (Hallbrite®TQ), butyloctyl salicylate (Hallbrite®BHB), dibutyl adipate (Cetiol B), triethyl citrate (hydagen CAT), propylene glycol dibenzoate (Finsolv PG 22), tributyl citrate, dioctyl malate
(Ceraphyl 45), dipropylen glycol dibenzoate (Benzoflex 245), acetyltributyl citrate (Citroflex A-4), acetyltriethyl citrate (Citroflex A-2). The list of said oils which can be used for the purposes of the present invention is not of course intended to be limiting.
The use amount of all oil components in cosmetic emulsions with compounds of the formula I is 0.5 to 30% by weight, preferably 2 to 15% by weight. All said oil components and liquid oil-soluble UV filters are excellent solvents for all crystalline oil-soluble UV absorbers.
It is a serious drawback if UV absorbers leave behind marks which can not be washed out of items of clothing. In particular it is known that the UV-A absorber tert-butylmethoxydibenzoylmethane produces marks on textiles which cannot be washed out. The indanylidene compounds according to the invention do not have this drawback since a mark formed on textiles can be very readily washed out.
Sunscreen products should be water-resistant in order that sufficient UV protection is ensured for the user, in particular children, while swimming or bathing. Combinations of the indanylidene compounds according to the invention satisfy these requirements to a particularly good degree. In an O/W emulsion containing 3% by weight of a combination of the indanylidene compounds according to the invention, 97% substantivity of the UV absorber was measured following washing, and in a W/O emulsion, 95%. Furthermore, the water resistance of sun protection products containing water-soluble, mono- or polysulphonated UV filters, such as, for example, Neo Heliopan®AP, Mexoryl®SX, benzophenone-4, Neo Heliopan®Hydro and the oil-soluble UV absorbers listed on pages 6-9 can be significantly increased as a result of combination with compounds of the formula I.
It may also be of considerable advantage to combine the UV absorbers mentioned according to the invention with chelating substances, as are listed, for example, in
EP-A496434, EP-A313305 and WO-94/04128, or with polyaspartic acid and ethylenediamine-tetramethyl-phosphonic acid salts.
Cosmetic and dermatological formulations for the purposes of the invention comprise one or more customary UV-A, UV-B and/or broad-band filters as individual substances or in any mixtures with one another, in the lipid phase and/or in the aqueous phase. They are satisfactory products in every respect which are surprisingly characterized by high UV-A protection performance and high sun protection factor.
The invention further provides for the use of the UV absorbers according to the invention in combination with conventional UV absorbers for enhancing the protection against harmful UV radiation beyond the extent of the protection achieved using the same amounts of conventional or of UV filters according to the invention on their own (synergistic effect).
The total amount of UV filter substances (UV-A, UV-B and/ or broad-band filters) in the finished cosmetic or dermatological preparations, whether as individual substance or in any mixtures with one another, is advantageously chosen from the range from 0.1 to 30% by weight, preferably 0.1 to 10.0% by weight, in particular 0.5 to 5.0% by weight, based on the total weight of the preparations.
In addition, cosmetic and dermatological preparations according to the invention advantageously, but not obligatorily, comprise inorganic pigments based on finely disperse metal oxides and/or other metal compounds which are insoluble or sparingly soluble in water, in particular the oxides of titanium (TiO2), zinc (ZnO), iron (e.g. Fe2O3), zirconium (ZrO2), silicon (SiO2), manganese (e.g. MnO), aluminium (A12O3), cerium (e.g. Ce2O3), mixed oxides of the corresponding metals, and mixtures of such oxides. These pigments are X-ray-amorphous or non-X-ray-amorphous. Particular preference is given to pigments based on TiO2. X-ray-amorphous oxide pigments are metal oxides or semimetal oxides which reveal no or no recognizable crystalline structure in X-ray diffraction experiments. Such
pigments are often obtainable by flame reaction, for example by reacting a metal or semimetal halide with hydrogen and air (or pure oxygen) in a flame.
In cosmetic, dermatological or pharmaceutical formulations, X-ray-amorphous oxide pigments are used as thickeners and thixotropic agents, flow auxiliaries for emulsion and dispersion stabilization and as carrier substance (for example for increasing the volume of finely divided powders). X-ray-amorphous oxide pigments which are known and often used in cosmetic or dermatological galenics are, for example, high-purity silicon oxide. Preference is given to high-purity, X-ray-amorphous silicon dioxide pigments with a particle size in the range from 5 to 40 nm and an active surface area (BET) in the range from 50 to 400 m2/g, preferably 150 to 300 m2/g, where the particles are to be regarded as spherical particles of very uniform dimension. Macroscopically, the silicon dioxide pigments are recognizable as loose, white powders. Silicon dioxide pigments are sold commercially under the name Aerosil® (CAS-No. 7631-85-9) or Carb-O-Sil
Advantageous Aerosil® grades are, for example, Aerosil®OX50, Aerosil® 130, Aerosil®!50, Aerosil®200, Aerosil®300, Aerosil®380, Aerosil®MQX 80, Aerosil® MOX 170, AerosifCOK 84, Aerosil® R 202, Aerosil®R 805, Aerosil®R 812, Aerosil®R 972, Aerosil®R 974, Aerosil®R976.
According to the invention, cosmetic or dermatological light protection preparations comprise 0.1 to 20% by weight, advantageously 0.5 to 10% by weight, very particularly 1 to 5% by weight, of X-ray-amorphous oxide pigments.
The non-X-ray-amorphous inorganic pigments are, according to the invention, advantageously in hydrophobic form, i.e. have been surface-treated to repel water. This surface treatment may involve providing the pigments with a thin hydrophobic layer by processes known per se. Such a process involves, for example, producing the hydrophobic surface layer by a reaction according to
n TiO2 + m (RO)3Si-R' → n TiO2 (surf.)
where n and m are stoichiometric parameters to be used as desired, and R and R' are the desired organic radicals. Hydrophobicized pigments prepared analogously to DE-A 33 14 742, for example, are advantageous.
For example, mention may be made of TiO2 pigments, as are sold under the trade name T805 from Degussa. Preference is also given to TiO2/Fe2O3 mixed oxides, as are supplied, for example, under the trade name T817, also from Degussa.
The total amount of inorganic pigments, in particular hydrophobic inorganic micro-pigments, in the finished cosmetic or dermatological preparations is advantageously chosen from the range from 0.1 to 30% by weight, preferably 0.1 to 10.0% by weight, in particular 0.5 to 6.0% by weight, based on the total weight of the preparations.
The cosmetic and/or dermatological formulations according to the invention can have the customary composition and can be used for cosmetic and/or dermatological sun protection, and also for the treatment, care and cleansing of the skin and/or of the hair and as a make-up product in decorative cosmetics. Accordingly, the preparations according to the invention can, depending on their formulation, be used, for example, as skin protection cream, cleansing milk, sunscreen lotion, nourishing cream, day cream or night cream, etc. In some instances, it is possible and advantageous to use the preparations according to the invention as bases for pharmaceutical formulations. Preference is given, in particular, to those cosmetic and dermatological preparations in the form of a skin care or make-up product. Typical embodiments are creams, gels, lotions, alcoholic and aqueous/alcoholic solutions, emulsions or stick preparations. These compositions may also comprise, as further auxiliaries and additives, mild surfactants, co-emulsifiers, superfatting agents, pearlescent waxes, bodying agents, thickeners, polymers, silicone compounds, fats, waxes, stabilizers, biogenic active ingredients, deodorant active ingredients, antidandruff agents, film formers, swelling agents, hydrotropic agents, preservatives, insect repellants, tanning agents, artificial
self-tanning agents (e.g. dihydroxyacetone), stabilizers, perfume oils, dyes, antimicrobial agents and the like.
For use, the cosmetic and dermatological preparations according to the invention are applied to the skin and/or the hair in a sufficient amount in the manner customary for cosmetics.
Particular preference is given to those cosmetic and dermatological preparations in the form of a cosmetic composition for the protection of the skin and hair. Advantageously, in addition to UV-A, UV-B and/or broad-band filters used according to the invention, these can comprise at least one inorganic pigment, preferably an inorganic micropigment.
The cosmetic and dermatological preparations according to the invention can
comprise cosmetic auxiliaries, as are customarily used in such preparations, e.g. pre
servatives, bactericides, perfumes, antifoams, dyes, pigments which have a colouring
action, thickeners, moisturizers and/or humectants, fats, oils, waxes or other
customary constituents of a cosmetic or dermatological formulation, such as alcohols,
polyols, polymers, foam stabilizers, electrolytes, organic solvents or silicone
derivatives. Suitable nonionic emulsifiers or dispersants are the group formed by
polyglyceryl-2 dipolyhydroxystearate (Dehymuls®PGPH), polyglyceryl-3
diisostearate (Lameform®TGI), polyglyceryl-4 isostearate (Isolan®GI 34),
polyglyceryl-3 oleate, diisostearyl polyglyceryl-3 diisostearate (Isolan®PDI),
polyglyceryl-3 methylglucose distearate (Tego Carey®450), polyglyceryl-3 beeswax
(Cera Bellina®), polyglyceryl-4 caprate (polyglycerol caprate T2010/90),
polyglyceryl-3 cetyl ether (Chimexane®NL), polyglyceryl-3 distearate
(Cremophor®GS 32), polyglyceryl-2 stearate (Hostacerin®DGMS) and polyglyceryl polyricineoleate (Admul®WOL 1403), and mixtures thereof.
The amounts of cosmetic or dermatological auxiliaries and carrier substances and perfume which can be used in each case can be determined easily by the person
skilled in the art by simple trial and error, depending on the nature of the product in question.
An additional content of antioxidants is generally preferred. According to the invention, favourable antioxidants which can be used are all antioxidants customary or suitable for cosmetic and/or dermatological applications.
The antioxidants are advantageously chosen from the group consisting of amino acids (e.g. glycine, histidine, tyrosine, tryptophan) and derivatives thereof, imidazoles (e.g. urocanic acid) and derivatives thereof, peptides, such as D,L-carnosine, D-camosine, L-camosine and derivatives thereof (e.g. anserine), carotenoids, carotenes (e.g. α-carotene, ß-carotene, lycopene) and derivatives thereof, chlorogenic acid and derivatives thereof, lipoic acid and derivatives thereof (e.g. dihydrolipoic acid), aurothioglucose, propylthiouracil and other thiols (e.g. thioredoxin, glutathione, cysteine, cystine, cystamine and the glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl, γ-linoleyl, cholesteryl and glyceryl esters thereof) and salts thereof, dilauryl thiodipropionate, distearyl thiodipropionate, thiodipropionic acid and derivatives thereof (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts), and sulphoximine compounds (e.g. buthionine sulphoximines, homocysteine sulphoximine, buthionine sulphones, penta-, hexa-, heptathionine sulphoximine) in very low tolerated doses (e.g. pmol to umol/kg), and also (metal) chelating agents (e.g. α-hydroxy fatty acds, palmitic acid, phytic acid, lactoferrin), α-hydroxy acids (e.g. citric acid, lactic acid, maleic acid), humic acid, bile acid, bile extracts, bilirubin, biliverdin, EDTA, EGTA and derivatives thereof, unsaturated fatty acids and derivatives thereof (e.g. γ-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, Mg ascorbyl phosphate, ascorbyl acetate), tocopherols and derivates (e.g. vitamin E acetate), vitamin A and derivatives (vitamin A palmitate), and coniferyl benzoate of benzoin resin, rutinic acid and derivatives thereof, α-glycosylrutin, ferulic acid, furfurylideneglucitol, camosine, butylhydroxytoluene, butylhydroxyanisol,
nordihydroguaiacic acid, nordihydroguaiaretic acid, trihydroxybutyrophenone, uric acid and derivatives thereof, mannose and derivatives thereof, zinc and derivatives thereof (e.g. ZnO, ZnSO4), selenium and derivatives thereof (e.g. selenomethionine), stilbenes and derivatives thereof (e.g. stilbene oxide, trans-stilbene oxide) and the derivatives (salts, esters, ethers, sugars, nucleotides, nucleosides, peptides and lipids) of said active ingredients suitable according to the invention.
The amount of the abovementioned antioxidants (one or more compounds) in the preparations is preferably 0.001 to 30% by weight, particularly preferably 0.05 to 20% by weight, in particular 1 to 10% by weight, based on the total weight of the preparation.
If vitamin E and/or derivatives thereof represent the antioxidant(s), it is advantageous to choose their respective concentrations from the range from 0.001 to 10% by weight, based on the total weight of the formulation.
If vitamin A or vitamin A derivatives, or carotenes or derivatives thereof represent the antioxidant(s), it is advantageous to choose their respective concentrations from the range from 0.001 to 10% by weight, based on the total weight of the formulation.
The lipid phase can advantageously be chosen from the following group of substances:
mineral oils, mineral waxes;
oils, such as triglycerides of capric or of caprylic acid, and also natural oils,
such as, for example, castor oil;
fats, waxes and other natural and synthetic fatty substances, preferably esters
of fatty acids with alcohols of low carbon number, e.g. with isopropanol,
propylene glycol or glycerol, or esters of fatty alcohols with alkanoic acids of
low carbon number or with fatty acids;
alkyl benzoate;
silicone oils, such as dimethylpolysiloxane, diethylpolysiloxane, diphenyl-polysiloxane, and mixed forms thereof..
The oil phases of the emulsions, oleogels and hydrodispersions or lipodispersions for the purposes of the present invention are advantageously chosen from the group of esters of saturated and/or unsaturated, branched and/or unbranched alkanecarboxylic acids having a chain length of from 3 to 30 carbon atoms and saturated and/or unsaturated, branched and/or unbranched alcohols having a chain length of from 3 to 30 carbon atoms, from the group of esters of aromatic carboxylic acids and saturated and/or unsaturated, branched and/or unbranched alcohols having a chain length of from 3 to 30 carbon atom. Such ester oils can then advantageously be chosen from the group isopropyl myristate, isopropyl palmitate, isopropyl stearate, isopropyl oleate, n-butyl stearate, n-hexyl laurate, n-decyl oleate, isooctyl stearate, isononyl stearate, isononyl isononanate, 2-ethylhexyl palmitate, ethylhexyl laurate, 2-hexyl-decyl stearate, 2-octyldodecyl palmitate, oleyl oleate, oleyl erucate, erucyl oleate and synthetic, semisynthetic and natural mixtures of such esters, e.g. jojoba oil.
In addition, the oil phase can advantageously be chosen from the group of branched and unbranched hydrocarbons and hydrocarbon waxes, silicone oils, dialkyl ethers, the group of saturated or unsaturated, branched or unbranched alcohols, and fatty acid triglycerides, namely the triglycerol esters saturated and/or unsaturated, branched and/or unbranched alkanecarboxylic acids having a chain length of from 8 to 24, in particular 12 to 18, carbon atoms. The fatty acid triglycerides can, for example, advantageously be chosen from the group of synthetic, semisynthetic and natural oils, e.g. olive oil, sunflower oil, soybean oil, peanut oil, rapeseed oil, almond oil, palm oil, coconut oil, palm kernel oil and the like.
Any mixtures of such oil and wax components are also to be used advantageously for the purposes of the present invention. It may also be advantageous in some instances to use waxes, for example cetyl palmitate, as the sole lipid component of the oil phase.
The oil phase is advantageously chosen from the group 2-ethylhexyl isostearate, octyldodecanol, isotridecyl isononanoate, isoeicosane, 2-ethylhexyl cocoate, C12-15-alkyl benzoate, caprylic/capric triglyceride, dicapryl ether.
Particularly advantageous mixtures are those of the C12-15-alkyl benzoate and 2-ethylhexyl isostearate, those of C12-15-alkyl benzoate and isotridecyl isononanoate, those of the C12-15-alkyl benzoate, 2-ethylhexyl isostearate and isotridecyl isononanoate.
The oil phase can also advantageously have a content of cyclic or linear silicone oils or consist entirely of such oils, although it is preferable to use an additional content of their oil phase components apart from the silicone oil or silicone oils.
Cyclomethicone (octamethylcyclotetrasiloxane) is advantageously used as silicone oil to be used according to the invention. However, other silicone oils can also be used advantageously for the purposes of the present invention, for example hexameth-ylcyclotrisiloxane, polydimethylsiloxane, poly(methylphenylsiloxane).
Also particularly advantageous are mixtures of cyclomethicone and isotridecyl isononanoate, and of cyclomethicone and 2-ethylhexyl isostearate.
The aqueous phase of the preparations according to the invention optionally advantageously comprises alcohols, diols or polyols (lower alkyl), and ethers thereof, preferably ethanol, isopropanol, propylene glycol, glycerol, ethylene glycol-monoethyl or monobutyl ether, propylene glycol monomethyl, -monoethyl or monobutyl ether, diethylene glycol monomethyl or -monoethyl ether and analogous products, and also alcohols (lower alkyl), e.g. ethanol, 1,2-propanediol, glycerol, and, in particular, one or more thickeners which can advantageously be chosen from the group consisting of silicon dioxide, aluminium silicates, polysaccharides and derivatives thereof, e.g. hyaluronic acid, xanthan gum, hydroxypropylmethyl-cellulose, particularly advantageously from the group of polyacrylates, preferably a
polyacrylate from the group of so-called Carbopols, for example Carbopol grades 980, 981, 1382, 2984, 5984, in each case individually or in combination.
A comprehensive description of the raw materials and active ingredients used in cosmetic compositions is given in DE-A 199 19 630.
It could not have been foreseen that the indanylidene compounds according to the invention represent an excellent selection compared with the compounds known from EP-A823418.
Examples:
Photostability
By way of example, comparative measurements between the compounds of category A and the compounds of category B and the combination with other standard commercial UV filters such as OMC (= octyl methoxycinnamate) or BMDM (= tert-butylmethoxydibenzoylmethane) are listed below. The substances of category B demonstrate the improvement over the substances of category A. The irradiation was carried out in a Suntester from Heraeus at an irradiation intensity of 765 W/m2 (based on Global sensor). The values give the concentration decrease of the UV filters in percentage following irradiation (dose in J/cm2).
Formulation according to formulation Example 1
(Table Removed)
Tab.l
Formulation according to formulation Example 12
(Table Removed)
Tab.2
Formulation according to formulation
Comparison Example 12 Example 4 Example 4
without A or B without OMC
(Table Removed)
Tab.3
Compounds in Tables 1-3:
(Table Removed)
Example 1
2-(5,6-Dimethoxy-3,3-dimethyl-l-indanylidene)-4,4-dimethyl-3-oxo-pentanonitrile
(Figure Removed)
44 g (0.2 mol) of 5,6-dimethoxy-3,3-dimethyl-l-indanone, 25 g (0.2 mol) of pivaloylacetonitrile, 32 g of propionic acid and 17 g of ammonium acetate are mixed in 80 g of xylene and heated at 120°C for 7 hours. After the system has been cooled to room temperature and the organic phase has been washed, the xylene is distilled off, and the crude product which remains is recrystallized in methanol. Yield: 50% theory; E1/1 730 (λmax 373 nm).
Example 2
2-(5-Methoxy-3,3,4,6-tetramethyl-l-indanylidene)-4,4-dimethyl-3-oxo-pentanonitrile
(Figure Removed)
The procedure was analogous to that in Example 1 starting from 5-methoxy-3,3,4,6-tetramethyl-1-indanone. Yield: 50% of theory; E1/1 588 (λmax 340 nm).
Example 3
2-(3,3,5,6-tetramethyl-l-indanylidene)-4,4-dimethyl-3-oxo-pentanonitrile
(Figure Removed)
The procedure was analogous to that in Example 1 starting from 3,3,5,6-tetramethyl-1-indanone. Yield: 55% of theory; El/1 630 (λmax 342 nm).
Example 4
2-(3,3,6-trimethyl-l-indanylidene)-4,4-dimethyl-3-oxo-pentanonitrile
(Figure Removed)
The procedure was analogous to that in Example 1 starting from 3,3,6-trimethyl-l-indanone. Yield: 45% of theory; E1/1 528/505 (λmax 335/316 nm).
Example 5
2-(5,6-Ethylenedioxo-3,3-dimethyl-l-indanylidene)-4,4-dimethyl-3-oxo-pentano-nitrile
(Figure Removed)
The procedure was analogous to that in Example 1 starting from 5,6-ethylenedioxo-3,3-dimethyl-l-indanone. Yield: 55% of theory; E1/1 640 (λmax 369 nm).
Example 6
2-(5-Methoxy-3,3,6-trimethyl-l-indanylidene)-4,4-dimethyl-3-oxo-pentanonitrile
(Figure Removed)
The procedure was analogous to that in Example 1 starting from 5-methoxy-3,3,6-trimethyl-1-indanone. Yield: 60% of theory; E1/1 850 (λmax 359 nm).
Example 7
2-[(5-Methoxy-3,3-dimethyl-(2-methyl-3-(l,3,3,3-tetramethyl-l-(trimethyl-silyloxy)-disiloxanyl)-propyl)-indanylidene)]-4,4-dimethyl-3-oxo-pentanonitrile
(Figure Removed)
a) 2-(5-Methoxy-3,3-dimethyl-6-hydroxy-l-indanylidene)-4,4-dimethyl-3-oxo-pentanonitrile
(Figure Removed)
5-Methoxy-3,3-dimethyl-6-hydroxy-l-indanone is reacted according to Example 1. Yield: 50% of theory.
b) 2-(5-Methoxy-3,3-dimethyl-6-(2-methyl-propenyloxy)-l-indanylidene)-4,4-dimethyl-3 -oxo-pentanonitri le
(Figure Removed)
136g (0.43 mol) of the compound under a) are added together with 95 g of potassium carbonate to 470 g of N-methylpyrrolidinone, heated to 70°C and 42 g (0.46 mol) of methallyl chloride are added thereto over the course of 30 min. The mixture is heated for a further 3 h at 70°C, then cooled to room temperature, and the product is extracted with ethyl acetate. Yield: 45% of theory.
90g (130mmol) of the compound under b), 29g (130mmol) of 1,1,1,3,5,5,5-hepta-methyltrisiloxane are kept at 80°C in the presence of catalytic amounts of divinyltetramethylplatinum complex in 90 g of toluene and a nitrogen atmosphere for 20 h. After the solvent has been distilled off, the residue is distilled over a Kugelrohr, giving 50 g (70% of theory) of the desired product as a yellow oil; E1/1 400 (λmax 373 nm).
Example 8
2-(6-Acetoxy-3,3-dimethyl-5-methoxy-l-indanylidene)-4,4-dimethyl-3-oxo-pentano-nitrile
(Figure Removed)
54 g (0.17 mol) of the compound under a) are reacted with 13 g (0.17 mol) of acetyl
chloride in N-methylpyrrolidinone at 40°C over the course of 5 h. Yield: 98% of
theory.
E1/1 420/280 (λmax 355/302 nm).
Example 9
2-(3,3-Dimethyl-5-tert-butyl-l-indanylidene)-3-(l'-methylcyclohexyl)-3-oxo-propiononitrile
(Figure Removed)
3,3-Dimethyl-5-tert-butyl-l-indanone are reacted with 3-(l'-methylcyclohexyl)-3-oxo-propiononitrile analogously to Example 1. Yield: 40% of theory. E1/1 580 (λmax 355 nm).
Example 10
2-(3,3,5-Trimethyl-l-indanylidene)-3-phenyl-3-oxo-propiononitrile
(Figure Removed)
3,3,5-Trimethyl-l-indanone are reacted with benzoylacetonitrile analogously to
Example 1.
Yield: 50% of theory.
E1/1 600 (λmax 350 nm).
Formulation Example 1
Sunscreen soft cream (O/W), in-vitro SPF 3, water resistant
(Table Removed)
Preparation method
Part A: Heat to about 85°C.
Part B: Weigh in raw materials without Carbopol. Disperse Carbopol therein using
Ultra Turrax. Heat to about 85°C. Add B to A. Part C: Immediately add to A/B and then homogenize while hot (Ultra Turrax). Leave
to cool with stirring. Part D: Add and stir in.
(Table Removed)
Formulation Example 2
Sunscreen lotion (O/W), in-vitro SPF 20
(Table Removed)
Preparation method
Part A: Heat to about 85°C.
Part B: Weigh in raw materials without Carbopol. Disperse Carbopol therein using
Ultra Turrax. Heat to about 85°C. Add B to A. Part C: Immediately add to A/B and then homogenize while hot (Ultra Turrax). Leave
to cool with stirring. Part D: Add and stir in.
(Table Removed)
Formulation Example 3
Sunscreen milk (0/W), in-vitro SPF 6
(Table Removed)
Preparation method
Part A: Heat to 80-85°C.
Part B: Heat to 80-85°C, add part B to part A with stirring.
Part C: Disperse Carbopol into the water and neutralize with NaOH, with stirring.
Add part C at about 60°C with stirring. Allow to cool to RT.
Part D: Add and stir.
(Table Removed)
Formulation Example 4
Sunscreen lotion (O/W), in-vitro SPF 21
(Table Removed)
Preparation method
Part A:Heat to 80-85°C.
Part B: Heat to 80-85°C, add part B to part A with stirring.
Part C: Disperse Carbopol into the water and neutralize with NaOH, with stirring.
Add part C at about 60°C with stirring. Allow to cool to RT. Part D: Add and stir.
(Table Removed)
Formulation Example 5
Sunscreen lotion (O/W), in-vitro SPF 11
(Table Removed)
Preparation method
Part A: Dissolve UV absorber according to formula I in the oils or liquid UV filters
(heating to about 70°C). Allow to cool to about 30°C, add the remaining
constituents apart from Carbopol and Pemulen and mix at room temperature
(stir for about 5 minutes). Stir in Carbopol and Pemulen. Part B: Dissolve Solbrols in phenoxyethanol with heating. Mix with water and
glycerol, add to part A with stirring. Stir for about 60 minutes. Part C: Add to A/B, homogenize using the Ultra Turrax.
(Table Removed)
Formulation Example 6
Sunscreen cream (W/O), in-vitro SPF 4, water resistant
(Table Removed)
Preparation method
Part A: Heat to about 85°C.
Part B:Heat to about 85°C (without zinc oxide; disperse zinc oxide therein using the
Ultra Turrax).
Add B to A.
Allow to cool with stirring, then homogenize.
(Table Removed)
Formulation Example 7
Sunscreen softcream (W/O), in-vitro SPF 40
(Table Removed)
Preparation method
Part A: Heat to about 85°C.
Part B:Heat to about 85°C (without zinc oxide; disperse zinc oxide therein using the
Ultra Turrax).
Add B to A.
Allow to cool with stirring. Part C: Add and then homogenize
(Table Removed)
Formulation Example 8
Sunscreen milk (W/O)
(Table Removed)
Preparation method
Part A: Heat to about 85°C.
Part B: Heat to about 85°C. Add B to A. Allow to cool with stirring.
Part C: Add and then homogenize.
Formulation Example 9
Daycare cream with UV protection
(Table Removed)
Preparation method
Part A:Heatto80°C.
Part B: Heat to 80°C Add to part A with stirring.
Part C: Disperse Carbopol in water and neutralize with sodium hydroxide solution.
Add to part A/B at about 55°C. Part D: Add at RT and homogenize.
Formulation Example 10
Sunscreen spray
(Table Removed)
Preparation method
Part A: Dissolve Lara Care A-200 into the other constituents of part A with stirring. Part B: Weigh in all raw materials (without Pemulen) and dissolve the crystalline
substances with heating. Disperse Pemulen therein. Add part B to part A then
homogenize for 1 minute. Add part C+D and homogenize again for 1-2 minutes using the Ultra Turrax.
Formulation Example 11
(Table Removed)
Preparation method
Part A: Disperse Carbopol in water and neutralize with sodium hydroxide solution.
Part B: Add to part A with stirring.
Part C: Dissolve cristalline constituents in the other raw materials of part C with
warming (max.40°C) and add to part A/B. Stir well and then homogenize.
(Homozenta).
Formulation Example 12
Hair Conditioner with UV filters
(Table Removed)
Preparation method
PartA:Heatto80°C.
Part B: Heat to 80°C. Add to part A with stirring. Part C: Add at 40°C and cool to RT.
Formulation Example 13
(Table Removed)
Preparation method
PartA:Heatto80-85°C.
Part B: Heat to 80-85°C, add part B to part A with stirring.
Part C: Disperse Carbopol into the water and neutralize with NaOH with stirring. Add part C at about 60°C with stirring.

WE CLAIM;
1. Indanylidene compounds of the formula
(Formula Removed)
in which
R1 and R2 are hydrogen;
R3 and R4 are methyl;
R5 to R7, independently of one another, are hydrogen, C1-C20-alkyl, C 1-C20-alkoxy, acetoxy, or Me-Si(OSiMe3)2-CH2CH(CH3)CH2-O-, with the proviso that R6 and R7 are not both methoxy, when R5 is hydrogen;
additionally two substituents of R5 to R7 on adjacent carbon atoms can together form a 1,4-dioxalan ring.
R8 is hydrogen;
X is cyano;
n is 1;
R9 to R11 are methyl.
2. An indanylidene compound as claimed in claim 1 and selected from
the following:
a. 2-(3,3,5,6-tetramethyl-l-indanylidene)-4,4-dimethyl-3-oxo-pentanonitrile
(Formula Removed)
b. 2-(3,3,5-trimethyl-l-indanylidene)-4,4-diinethyl-3-oxo-pentanonitrile
(Formula Removed)
c. 2-(3,3,6-trimethyl-l-indanylidene)-4,4-dimethyl-3-oxo-pentanonitrile
(Formula Removed)
d. 2-(5-methoxy-3,3,4,6-tetramethyl-l-indanylidene)-4,4-dimethyl-3-
oxo-pentanonitrile
(Formula Removed)
e 2-(5-methoxy-3,3,6-trimethyl-l-indanylidene)-4,4-dimethyl-3-oxo-pentanonitrile
(Formula Removed)
f. 2-(5-n-butoxy-3,3,4-trimethyl-1 -indanylidene)-4,4-dimethyl-3-oxo-pentanonitrile
(Formula Removed)
g. 2-(3,3-dimethyl-5-methoxy-1 -indanylidene)-4,4-dimethyl-3-oxo-pentanonitrile
(Formula Removed)
h. 2-(5-n-butoxy-3,3,6-trirnethyl-l-indanylidene)-4,4-dimethyl-3-oxo-pentanonitrile
(Formula Removed)
i. 2-(5-t-butyl-3,3-dimethyl-l-indanylidene)-4,4-dimethyl-3-oxo-pentanonitrile
(Formula Removed)
j. 2-(5,6-ethylenedioxo-3,3-dimethyl-l-indanylidene)-4,4-dimethyl-3-oxo-pentanonitrile
(Formula Removed)
k. 2-[3,3-dimethyl-5-methoxy-6-(2-methyl-3-(l>3,3,3-tetramethyl-l-(trimethyl-silyloxy)-disiloxanyl)-propyloxy)-indanylidene]-4,4-dimethyl-3-oxo-pentanonitrile
(Formula Removed)
1. 2-(6-acetO3cy-3,3-dimethyl-5-niethoxy- l-indanylidene)-4,4-dimethyl-3-oxo-pentanonitrile
(Formula Removed)
3. A cosmetic composition for protecting skin and hair, comprising a total amount of 0.1 to 30% by weight of one or more indanyliden compounds as claimed in claim 1 based on the total weight of the composition and one or more compounds selected from the group consisting of
(i) water-soluble UV filter substance in an amount of 0.1-10% by weight based on the total weight of the composition
and
(ii) oil-soluble UV filter substance in an amount of 0.1-10% by weight based on the total weight of the composition.
4. The cosmetic composition for protecting skin and hair, as claimed in claim 3 wherein the composition comprises one or more indanyliden compounds selected from the following:
a. 2-(3,3,5,6-tetramethyl-1 -indanylidene)-4,4-dimethyl-3-oxo-
pentanonitrile
(Formula Removed)
b. 2-(3,3,5-trimethyl-l-indanylidene)-4,4-dimethyl-3-oxo-pentanonitrile
(Formula Removed)
c. 2-(3,3,6-trimethyl- l-indanylidene)-4,4-dimethyl-3-oxo-pentanonitrile
(Formula Removed)
d. 2-(5-methoxy-3,3,4,6-tetramethyl-1 -indanylidene)-4,4-dimethyl-3-oxo-
pentanonitrile
(Formula Removed)
e. 2-(5-methoxy-3,3,6-trimethyl-1 -indanylidene)-4,4-dimethyl-3-oxo-pentanonitrile
(Formula Removed)
f. 2-(5-n-butoxy-3,3,4-trimethyl-1 -indanylidene) -4,4-dimethyl-3-oxo-
pentanonitrile
(Formula Removed)
g. 2-(3,3-dimethyl-5-inethoxy-1 -indanylidene)-4,4-dimethyl-3-oxo-
pentanonitrile
(Formula Removed)
h. 2-(5-n-butoxy-3,3,6-trimethyl-1 -indanylidene)-4,4-dimethyl-3-oxo-pentanonitrile
(Formula Removed)
i. 2-(5-t-butyl-3,3-dimethyl-1 -indanylidene)-4,4-dimethyl-3-oxo-pentanonitrile
(Formula Removed)
j. 2-(5,6-ethylenedioxo-3,3-dimethyl-1 -indanylidene)-4,4-dimethyl-3-oxo-pentanonitrile
(Formula Removed)
k. 2-[3,3-dimethyl-5-methoxy-6-(2-met±iyl-3-(l,3,3,3-tetramethyl-l-(trimethyl-silyloxy)-disiloxanyl)-propyloxy)-indanylidene]-4,4-diinethyl-3-oxo-pentanonitrile
(Formula Removed)
1. 2-(6-acetoxy-3,3-dimethyl-5-methoxy-1 -indanylidene)-4,4-dimethyl-3-oxo-pentanonitrile
(Formula Removed)
5. The cosmetic composition as claimed in Claim 3, wherein it
comprises at least one tanning agent and/or artificial self-tanning agent for
the skin.
6. The cosmetic composition as claimed in Claim 3, wherein it
comprises, in addition to the compounds of the formula I according to the
invention it contains, one or more other UV filter substance from the group
consisting of ethylhexylmethoxy cinnamate, 2-ethylhexyl-2-cyano-3,3-
diphenyl acrylate, 2-phenylbenzimidazolesulphonic acid, methylbenzylidene
campher, 4-t-butyl-4'-methoxy-dibenzoylmethane, phenylene-bis-
benzimidazyl-tetrasulphonic acid disodium salt, terephthalylidene-
dibomanesulphonic acid and salts thereof, 2-(2H-benzotriazol-2-yl)-4-
methyl-6-(2-methyl-3( 1,3,3,3-tetramethyl-1 -(trimethylsilyl)-oxy)-
disiloxyanyl)-propyl)phenol, benzylidene malonate polysiloxane, 2,2'-
methylene-bis- (6- (2 H-benzotriazol-2 -yl) -4- (1,1,3,3-tetramethylbutyl) -
phenol), 2,4-bis[{(4-(2-ethyl-hexyloxy-2-hydroxy}-phenyl]-6-(4-methoxy-
phenyl)-l,3,5-triazine, 4,4',4"-(l,3,5-triazine-2,4,6-triyltriimino)-tris-benzoic
acid tris(2-ethylhexyl ester), 4,4'-[(6-[4-(l,l-dimethyl)-aminocarbonyl)-
phenylamino]-1,3,5-triazine-2,4-diyl)diimino]-bis-(benzoic acid-2-ethylhexyl
ester), zinc oxide and titanium dioxide.

7. The cosmetic composition as claimed in Claim 3, wherein it
comprises UV filter substance and additionally coated or noncoated
pigments or nanopigments of metal oxides.
8. The cosmetic composition as claimed in Claim 3, wherein it
comprises UV filter substance and additionally finely divided pigments such
that a UV broad-band protection performance with a critical wavelength
λcrit.> 380 nm results therefrom.

Documents:

857-delnp-2003-abstract.pdf

857-delnp-2003-claims.pdf

857-delnp-2003-complete specification (granted).pdf

857-DELNP-2003-Correspondence-Others-(23-09-2009).pdf

857-delnp-2003-correspondence-others.pdf

857-delnp-2003-correspondence-po.pdf

857-delnp-2003-description (complete).pdf

857-delnp-2003-form-1.pdf

857-delnp-2003-form-13.pdf

857-delnp-2003-form-18.pdf

857-delnp-2003-form-2.pdf

857-DELNP-2003-Form-3-(23-09-2009).pdf

857-delnp-2003-form-3.pdf

857-delnp-2003-form-5.pdf

857-delnp-2003-form-6.pdf

857-delnp-2003-gpa.pdf

857-delnp-2003-pct-210.pdf

857-delnp-2003-pct-304.pdf

857-delnp-2003-pct-308.pdf

857-delnp-2003-pct-409.pdf

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Patent Number

237349

Indian Patent Application Number

857/DELNP/2003

PG Journal Number

52/2009

Publication Date

25-Dec-2009

Grant Date

16-Dec-2009

Date of Filing

03-Jun-2003

Name of Patentee

SYMRISE GMBH & CO. KG

Applicant Address

MUHLENFELDSTRASSE 1, 37603 HOLZMINDEN, GERMANY.

Inventors:

#	Inventor's Name	Inventor's Address
1	OSKAR KOCH	LISSASBONSTR. 36, D-37079 GOTTINGEN, GERMANY.
2	ERICH DILK	MEIERNBERG, 10, D-37603 HOLZMINDEN, GERMANY.
3	ROLAND LANGNER	JAHNSTR. 9, D-37639 BEVERN, GERMANY.
4	WILLIAM JOHNCOCK	RICHARD-ARNTZ-STR. 16, D-37671 HOXTER, GERMANY.

PCT International Classification Number

C07C 255/40

PCT International Application Number

PCT/EP02/12516

PCT International Filing date

2001-10-30

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	100 55 940.9	2000-11-10	Germany