Use of specific bis(biphenyl)triazine derivatives and mixtures thereof as UV absorbers Patent Application (2025)

U.S. patent application number 13/822014 was filed with the patent office on 2013-06-27 for use of specific bis(biphenyl)triazine derivatives and mixtures thereof as uv absorbers. This patent application is currently assigned to BASF SE. The applicant listed for this patent is Bernd Herzog, Barbara Wagner. Invention is credited to Bernd Herzog, Barbara Wagner.

Use of specific bis(biphenyl)triazine derivatives and mixturesthereof as UV absorbers

Abstract

Disclosed is the use of mixtures comprising at least 2structurally different bis(biphenyl)triazine derivatives of formula(1) wherein X is hydrogen; C.sub.1-C.sub.50alkyl which may beuninterrupted or interrupted by one or more oxygen atoms and/orsubstituted by one or more R.sub.8 groups;C.sub.3-C.sub.12-cycloalkyl which is substituted by R.sub.8;--CH((CH.sub.2).sub.p--R.sub.8)--CO--O--(CH.sub.2).sub.m--R.sub.9;--CH((CH.sub.2).sub.p--R.sub.8)--CO--(NR.sub.10)--(CH.sub.2).sub.m--R.sub-.9; --CO--O--(CH.sub.2).sub.p--R.sub.a;--CH.sub.2--CH(--O(CO)--R.sub.8)--R.sub.9;--CO--(NR.sub.10)--(Ch.sub.2).sub.p--R.sub.a; C.sub.6-C.sub.20aryl;allyl; C.sub.4-C.sub.50alkenyl which is uninterrupted or isinterrupted by one or more oxygen atoms; C.sub.3-C.sub.12cycloalkylwhich is uninterrupted or interrupted by one or more oxygen atoms;C.sub.3-C.sub.20alkynyl; C.sub.6-C.sub.12cycloalkynyl; R.sub.1 ishydrogen; unsubstituted or substituted unsubstituted or substitutedC.sub.3-C.sub.12cycloalkyl; unsubstituted or substitutedC.sub.6-C.sub.20aryl; unsubstituted or substitutedC.sub.2-C.sub.20alkenyl; OR.sub.7; OH; SR.sub.8; SOR.sub.7;SO.sub.2R.sub.7; SO.sub.2H; SO.sub.3M; or a radical of the formula(c); R.sub.2, R.sub.3, R.sub.4, R.sub.5 and R.sub.6 independentlyof one another are hydrogen; hydroxyl; --CN; substituted orunsubstituted C.sub.1-C.sub.20alkyl; unsubstituted or substitutedC.sub.3-C.sub.12-cycloalkyl; unsubstituted or substitutedC.sub.1-C.sub.18alkoxy; unsubstituted or substitutedC.sub.4-C.sub.20cycloalkoxy; C.sub.7-C.sub.20phenylalkyl; halogen;halo-C.sub.1-C.sub.5alkyl; sulfonyl; carboxyl; acylamino; acyloxy;C.sub.1-C.sub.12alkoxycarbonyl; aminocarbonyl; R.sub.7 issubstituted or unsubstituted C.sub.1-C.sub.18alkyl; unsubstitutedor substituted C.sub.3-C.sub.12-cycloalkyl; unsubstituted orsubstituted C.sub.6-C.sub.20aryl; unsubstituted or substitutedC.sub.2-C.sub.20alkenyl; or C.sub.7-C.sub.20phenylalkyl; M isalkali metal; R.sub.8 and R.sub.9 independently of one another areR.sub.x if attached to a carbon atom and are R.sub.y if attached toan oxygen atom; p is 0 to 20; m is 0 to 20; R.sub.x is hydrogen;hydroxyl; C.sub.1-C.sub.30alkyl; C.sub.3-C.sub.12cycloalkyl;C.sub.1-C.sub.30alkoxy; C.sub.3-C.sub.12cycloalkoxy;C.sub.3-C.sub.12-cycloalkyl or C.sub.3-C.sub.12cycloalkoxy which isinterrupted by one or more oxygen atoms; C.sub.6-C.sub.12aryl;hetero-C.sub.3-C.sub.12aryl; --OR.sub.z; NHR.sub.z; R.sub.z;CONR.sub.10R.sub.11; SO.sub.3H; SO.sub.3M; OSO.sub.3H.sub.2; allyl,C.sub.2-C.sub.30alkenyl; C.sub.4-C.sub.12-cycloalkenyl which isuninterrupted or interrupted by one or more oxygen atoms;C.sub.3-C.sub.20-alkynyl; or C.sub.6-C.sub.12cycloalkynyl; R.sub.yis hydrogen; C.sub.1-C.sub.30alkyl; C.sub.3-C.sub.12cycloalkylwhich is uninterrupted or interrupted by one or more oxygen atoms;C.sub.6-C.sub.12aryl; hetero-C.sub.3-C.sub.12aryl; R.sub.z; allyl,C.sub.2-C.sub.30alkenyl; C.sub.4-C.sub.12-cycloalkenyl which isuninterrupted or interrupted by one or more oxygen atoms;C.sub.3-C.sub.20-alkynyl; or C.sub.6-C.sub.12cycloalkynyl; R.sub.zis --COR.sub.10; --COOR.sub.10; --CON-R.sub.10R.sub.11;--CO--CH.dbd.CH.sub.2; --CO--C(CH.sub.3).dbd.CH.sub.2; R.sub.10 andR.sub.11 independently of one another are hydrogen;C.sub.1-C.sub.30alkyl; C.sub.1-C.sub.50alkyl which is interruptedby one or more oxygen atoms; C.sub.3-C.sub.12cycloalkyl which isuninterrupted or interrupted by one or more oxygen atoms;C.sub.2-C.sub.20alkenyl which is uninterrupted or is interrupted byone or more oxygen atoms; or C.sub.6-C.sub.12aryl; or R.sub.10 andR.sub.11 together form a five or six membered ring; as UV absorbersfor increasing the UVA protection factor of cosmetic ordermatological compositions. ##STR00001##

Related U.S. Patent Documents

Foreign Application Data

Claims

1. A method for increasing the UVA protection factor of cosmetic ordermatological compositions comprising adding thereto at least 2structurally different bis(biphenyl)triazine derivatives of formula##STR00031## wherein X is hydrogen; C.sub.1-C.sub.50alkyl which maybe uninterrupted or interrupted by one or more oxygen atoms and/orsubstituted by one or more R.sub.8 groups;C.sub.3-C.sub.12-cycloalkyl which is substituted by R.sub.8;--CH((CH.sub.2).sub.p-R.sub.8)--CO--O--(CH.sub.2).sub.m--R.sub.9;--CH((CH.sub.2).sub.p-R.sub.8)--CO--(NR.sub.10)--(CH.sub.2).sub.m--R.sub.-9; ##STR00032## --CO--(CH.sub.2).sub.p--R.sub.8;--CO--O--(CH.sub.2).sub.p--R.sub.8;--CH.sub.2--CH(--O(CO)--R.sub.8--R.sub.9;--CO--(NR.sub.10)--(CH.sub.2).sub.p--R.sub.8; C.sub.6-C.sub.20aryl;allyl; C.sub.4-C.sub.50alkenyl which is uninterrupted or isinterrupted by one or more oxygen atoms; C.sub.3-C.sub.12cycloalkylwhich is uninterrupted or interrupted by one or more oxygen atoms;C.sub.3-C.sub.20alkynyl; C.sub.6-C.sub.12cycloalkynyl; R.sub.1 ishydrogen; unsubstituted or substituted C.sub.1-C.sub.12alkyl;unsubstituted or substituted C.sub.3-C.sub.12cycloalkyl;unsubstituted or substituted C.sub.6-C.sub.20aryl; unsubstituted orsubstituted C.sub.2-C.sub.20alkenyl; OR.sub.7; OH; SR.sub.8;SOR.sub.T; SO.sub.2R.sub.7; SO.sub.3H; SO.sub.3M; or a radical ofthe formula ##STR00033## R.sub.2, R.sub.3, R.sub.4, R.sub.5 andR.sub.6 independently of one another are hydrogen; hydroxyl; --CN;substituted or unsubstituted C.sub.1-C.sub.20alkyl; unsubstitutedor substituted C.sub.3-C.sub.12-cycloalkyl; unsubstituted orsubstituted C.sub.1-C.sub.18alkoxy; unsubstituted or substitutedC.sub.4-C.sub.20cycloalkoxy; C.sub.7-C.sub.20phenylalkyl; halogen;halo-C.sub.1-C.sub.5alkyl; sulfonyl; carboxyl; acylamino; acyloxy;C.sub.1-C.sub.12alkoxycarbonyl; aminocarbonyl; R.sub.7 issubstituted or unsubstituted C.sub.1-C.sub.18alkyl; unsubstitutedor substituted C.sub.3-C.sub.12-cycloalkyl; unsubstituted orsubstituted C.sub.6-C.sub.20aryl; unsubstituted or substitutedC.sub.2-C.sub.20alkenyl; or C.sub.7-C.sub.20phenylalkyl; M isalkali metal; R.sub.8 and R.sub.9 independently of one another areR.sub.x if attached to a carbon atom and are R.sub.y if attached toan oxygen atom; p is 0 to 20; m is 0 to 20; R.sub.x is hydrogen;hydroxyl; C.sub.1-C.sub.30alkyl; C.sub.3-C.sub.12cycloalkyl;C.sub.1-C.sub.30alkoxy; C.sub.3-C.sub.12cycloalkoxy;C.sub.3-C.sub.12cycloalkyl or C.sub.3-C.sub.12cycloalkoxy which isinterrupted by one or more oxygen atoms; C.sub.6-C.sub.12aryl;hetero-C.sub.3-C.sub.12aryl; --OR.sub.z; NHR.sub.z; R.sub.z;CONR.sub.10R.sub.11; SO.sub.3H; SO.sub.3M; OSO.sub.3H.sub.2; allyl,C.sub.2-C.sub.30alkenyl; C.sub.4-C.sub.12-cycloalkenyl which isuninterrupted or interrupted by one or more oxygen atoms;C.sub.3-C.sub.20-alkynyl; or C.sub.6-C.sub.12cycloalkynyl; R.sub.yis hydrogen; C.sub.1-C.sub.30alkyl; C.sub.3-C.sub.12cycloalkylwhich is uninterrupted or interrupted by one or more oxygen atoms;C.sub.6-C.sub.12aryl; hetero-C.sub.3-C.sub.12aryl; R.sub.z; allyl,C.sub.2-C.sub.30alkenyl; C.sub.4-C.sub.12-cycloalkenyl which isuninterrupted or interrupted by one or more oxygen atoms;C.sub.3-C.sub.20-alkynyl; or C.sub.6-C.sub.12cycloalkynyl; R.sub.zis --COR.sub.10; --COOR.sub.10; --CONR.sub.10R.sub.11;--CO--CH.dbd.CH.sub.2; --CO--C(CH.sub.3).dbd.CH.sub.2; R.sub.10 andR.sub.11 independently of one another are hydrogen;C.sub.1-C.sub.30alkyl; C.sub.1-C.sub.50alkyl which is interruptedby one or more oxygen atoms; C.sub.3-C.sub.12cycloalkyl which isuninterrupted or interrupted by one or more oxygen atoms;C.sub.2-C.sub.20alkenyl which is uninterrupted or is interrupted byone or more oxygen atoms; or C.sub.6-C.sub.12aryl; or R.sub.10 andR.sub.11 together form a five or six membered ring; as UV absorbersfor increasing the UVA protection factor of cosmetic ordermatological compositions.

2. The method according to claim 1, wherein the biphenyl triazinederivatives correspond to formula ##STR00034## wherein X is definedas in claim (1).

3. The method according to claim 1 or 2, wherein X is hydrogen;C.sub.1-C.sub.30alkyl which may be interrupted by one or moreoxygen atoms and/or substituted by one or more R.sub.8 groups;C.sub.3-C.sub.12-cycloalkyl which is substituted by R.sub.8;--CH((CH.sub.2).sub.p--R.sub.8)--CO--O--(CH.sub.2).sub.m--R.sub.9;--CH((CH.sub.2).sub.p--R.sub.8)--CO--(NR.sub.10)--(CH.sub.2).sub.m-R.sub.-9; --CO--(CH.sub.2).sub.p--R.sub.8;--CO--O--(CH.sub.2).sub.p--R.sub.8;--CH.sub.2--CH(--O(CO--R.sub.8)--R.sub.9;--CO--(NR.sub.10)--(CH.sub.2).sub.p--R.sub.8;C.sub.2-C.sub.50alkenyl which is unsubstitued or is interrupted byone or more oxygen atoms; C.sub.3-C.sub.12cycloalkyl which isuninterrupted or interrupted by one or more oxygen atoms; R.sub.8,R.sub.9 and R.sub.10 are defined as in claim 1; p is a number from0 to 20; and m is a number from 0 to 20.

4. The method according to claim 1, wherein X is hydrogen;C.sub.1-C.sub.18alkyl which may be interrupted by one or moreoxygen atoms and/or substituted by hydroxy, C.sub.1-C.sub.12alkylor *--O--(CO)--R.sub.12; a radical of formula ##STR00035##phenoxy-C.sub.1-C.sub.5alkyl; phenyl-C.sub.1-C.sub.4alkyl; Y is--O--; or --NH--; R.sub.12 is C.sub.1-C.sub.18alkyl; R.sub.13 ishydrogen; or C.sub.1-C.sub.5alkyl; R.sub.14 is C.sub.1-C.sub.18alkyl, wich is optionally interrupted by --NH or --O--;C.sub.2-C.sub.18alkenyl; R.sub.8, R.sub.9 and R.sub.10 are definedas in claim 1; R.sub.12 is C.sub.1-C.sub.5alkyl; p is a number from0 to 20; and m is a number from 0 to 20.

5. (canceled)

Description

[0001] The present invention relates to the use of specificbis-biphenyl-triazine and mixtures thereof as UV absorbers insunscreens and/or cosmetic compositions.

[0002] It is well known that ultraviolet radiation (light) isharmful to human skin. Depending on the wavelength the UV radiationcauses different types of skin damage. UV-B radiation (about 290 nmto about 320 nm) is responsible for sunburn and can cause skincancer. UV-A radiation (about 320 nm to about 400 nm) contributesalso to sunburn and the induction of skin cancer. Moreover, UVAmainly produces free radicals/reactive oxygen species byinteraction with endogenous photosensitizers.

[0003] In general cosmetic preparations comprise an oil phase and awater phase. The UV filters in the water phase can be easily washedout by contact with water like e.g. swimming, bathing or whilesweating during sportive acitivities which will lead to a decreasein UV protection. The oil phase is more resistent to water contact,thus maintaining a film on the skin during water contact. The UVfilters present in the oil phase so ensure the UV protection of theskin and maintain the water resistency of a sunscreen. Thereforeoilsoluble UV absorbers are an integral part of a sunscreen. Herebythe UV absorber should be sufficiently soluble in a cosmetic oil toguarantee a certain amount of protection.

[0004] An important class of triazines represents the bisbiphenyltriazines. These compounds exhibit superior UVB and UVA absorbingproperties combined with high photopermanence what makes them idealcandidates as UV absorbers in sunscreens.

[0005] WO 96/28431 describes biphenyl-substituted triazines aslight stabilizers in cosmetic preparations (p. 40-42).

[0006] The bisbiphenyltriazines disclosed in this reference aremilled with a dispersant and used as micronized particles in thewater phase.

[0007] Surprisingly it was found that mixtures of specificbis(biphenyl)triazines show appreciable solubility properties incosmetic oils and as a consequence significantly increase the UVAand UVB protection factor of cosmetic or dermatologicalcompositions.

[0008] Therefore, the present invention relates to the use ofmixtures comprising at least two structurally differentbis(biphenyl)triazine derivatives of formula

##STR00002##

wherein [0009] X is hydrogen; C.sub.1-C.sub.50alkyl which may beuninterrupted or interrupted by one or more oxygen atoms and/orsubstituted by one or more R.sub.8 groups;C.sub.3-C.sub.12-cycloalkyl which is substituted by R.sub.8;--CH((CH.sub.2).sub.p--R.sub.8)--CO--O--(CH.sub.2).sub.m--R.sub.9;--CH((CH.sub.2).sub.p--R.sub.8)--CO--(NR.sub.10)--(CH.sub.2).sub.m--R.sub-.9;

##STR00003##

[0009] --CO--(CH.sub.2).sub.p--R.sub.8;--CO--O--(CH.sub.2).sub.p--R.sub.8;--CH.sub.2--CH(--O(CO)--R.sub.8)--R.sub.9;--CO--(NR.sub.10)--(CH.sub.2).sub.p--R.sub.8; C.sub.6-C.sub.20aryl;allyl; C.sub.4-C.sub.50alkenyl which is uninterrupted or isinterrupted by one or more oxygen atoms; C.sub.3-C.sub.12cycloalkylwhich is uninterrupted or interrupted by one or more oxygen atoms;C.sub.3-C.sub.20alkynyl; C.sub.6-C.sub.12cycloalkynyl; [0010]R.sub.1 is hydrogen; unsubstituted or substitutedC.sub.1-C.sub.12alkyl; unsubstituted or substitutedC.sub.3-C.sub.12cycloalkyl; unsubstituted or substitutedC.sub.6-C.sub.20aryl; unsubstituted or substitutedC.sub.2-C.sub.20alkenyl; OR.sub.7; OH; SR.sub.8; SOR.sub.7;SO.sub.2R.sub.7; SO.sub.3H; SO.sub.3M; or a radical of theformula

[0010] ##STR00004## [0011] R.sub.2, R.sub.3, R.sub.4, R.sub.5 andR.sub.6 independently of one another are hydrogen; hydroxyl; --CN;substituted or unsubstituted C.sub.1-C.sub.20alkyl; unsubstitutedor substituted C.sub.3-C.sub.12-cycloalkyl; unsubstituted orsubstituted C.sub.1-C.sub.18alkoxy; unsubstituted or substitutedC.sub.4-C.sub.20cycloalkoxy; C.sub.7-C.sub.20phenylalkyl; halogen;halo-C.sub.1-C.sub.5alkyl; sulfonyl; carboxyl; acylamino; acyloxy;C.sub.1-C.sub.12alkoxycarbonyl; aminocarbonyl; [0012] R.sub.7 issubstituted or unsubstituted C.sub.1-C.sub.18alkyl; unsubstitutedor substituted C.sub.3-C.sub.12-cycloalkyl; unsubstituted orsubstituted C.sub.6-C.sub.20aryl; unsubstituted or substitutedC.sub.2-C.sub.20alkenyl; or C.sub.7-C.sub.20phenylalkyl; [0013] Mis alkali metal; [0014] R.sub.8 and R.sub.9 independently of oneanother are R.sub.x if attached to a carbon atom and are R.sub.y ifattached to an oxygen atom; [0015] p is 0 to 20; [0016] m is 0 to20; [0017] R.sub.x is hydrogen; hydroxyl; C.sub.1-C.sub.30alkyl;C.sub.3-C.sub.12cycloalkyl; C.sub.1-C.sub.30alkoxy;C.sub.3-C.sub.12cycloalkoxy; C.sub.3-C.sub.12cycloalkyl orC.sub.3-C.sub.12cycloalkoxy which is interrupted by one or moreoxygen atoms; C.sub.6-C.sub.12aryl; hetero-C.sub.3-C.sub.12aryl;--OR.sub.z; NHR.sub.z; R.sub.z; CONR.sub.10R.sub.11; SO.sub.3H;SO.sub.3M; OSO.sub.3H.sub.2; allyl, C.sub.2-C.sub.30alkenyl;C.sub.4-C.sub.12-cycloalkenyl which is uninterrupted or interruptedby one or more oxygen atoms; C.sub.3-C.sub.20-alkynyl; orC.sub.6-C.sub.12cycloalkynyl; [0018] R.sub.y is hydrogen;C.sub.1-C.sub.30alkyl; C.sub.3-C.sub.12cycloalkyl which isuninterrupted or interrupted by one or more oxygen atoms;C.sub.6-C.sub.12aryl; hetero-C.sub.3-C.sub.12aryl; R.sub.z; allyl,C.sub.2-C.sub.30alkenyl; C.sub.4-C.sub.12-cycloalkenyl which isuninterrupted or interrupted by one or more oxygen atoms;C.sub.3-C.sub.20-alkynyl; or C.sub.6-C.sub.12cycloalkynyl; [0019]R.sub.z is --COR.sub.10; --COOR.sub.10; --CONR.sub.10R.sub.11;--CO--CH.dbd.CH.sub.2; --CO--C(CH.sub.3).dbd.CH.sub.2; [0020]R.sub.10 and R.sub.11 independently of one another are hydrogen;C.sub.1-C.sub.30alkyl; C.sub.1-C.sub.50alkyl which is interruptedby one or more oxygen atoms; C.sub.3-C.sub.12cycloalkyl which isuninterrupted or interrupted by one or more oxygen atoms;C.sub.2-C.sub.20alkenyl which is uninterrupted or is interrupted byone or more oxygen atoms; or C.sub.6-C.sub.12aryl; or [0021]R.sub.10 and R.sub.11 together form a five or six membered ring; asUV absorbers for increasing the UVA protection factor of cosmeticor dermatological compositions.

[0022] Alkyl is branched or unbranched alkyl, such as methyl,ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, t-butyl,2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl,1,3-dimethyl-butyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl,1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl,2-ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl,nonyl, decyl, undecyl, 1-methylundecyl, dodecyl,1,1,3,3,5,5-hexamethylhexyl, tridecyl, tetradecyl, pentadecyl,hexadecyl, heptadecyl or octadecyl.

[0023] C.sub.1-C.sub.20alkoxy comprises straight-chain or branchedradicals such as, for example, methoxy, ethoxy, propoxy, butoxy,pentyloxy, hexyloxy, heptyloxy, octyloxy, isooctyloxy, nonyloxy,undecyloxy, dodecyloxy, tetradecyloxy, pentadecyloxy, hexadecyloxy,heptadecyloxy, octadecyloxy, nonadecyloxy or eicosyloxy.

[0024] Phenylalkyl is alkyl which is substituted by phenyl.C.sub.7-C.sub.20phenylalkyl, for example, comprises benzyl,.alpha.-methylbenzyl, .alpha.,.alpha.-dimethylbenzyl, phenylethyl,phenylpropyl, phenylbutyl, phenylpentyl, phenylhexyl, phenylheptyl,phenyloctyl, phenylnonyl, phenyldecyl, phenyldodecyl orphenyltetradecyl.

[0025] Halogen is --F, --Cl, --Br or --I; preference is given to--F or --Cl, especially --Cl.

[0026] C.sub.4-C.sub.12cycloalkyl is for example cyclobutyl,cyclopentyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl,cycloundecyl, cyclodocecyl and, in particular cyclohexyl.

[0027] Suitable examples of C.sub.4-C.sub.12cycloalkyl interruptedby one or more oxygen atoms are tetrahydrofuryl, 1-oxa-4-cyclohexyland 1,3-dioxa-4-cyclohexyl.

[0028] Within the scope of the definitions given alkenyl includesallyl, isopropenyl, 2-butenyl, 3-butenyl, isobutenyl,n-penta-2,4-dienyl, 3-methyl-but-2-enyl, n-oct-2-enyl,n-dodec-2-enyl, iso-dodecenyl, n-dodec-2-enyl and n-octadec-4-enyl,inter alia.

[0029] C.sub.5-C.sub.12cycloalkenyl is for example2-cyclopenten-1-yl, 2,4-cyclopentadien-1-yl-, 2-cyclohexen-1-yl,2-cyclohepten-1-yl or 2-cycloocten-1-yl.

[0030] C.sub.4-C.sub.12cycloalkoxy is for example cyclobutyloxy,cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, cyclooctyloxy,cyclononyloxy, cyclodecyloxy, cycloundecyloxy, cyclododecyloxy,especially cyclohexyloxy.

[0031] Particular examples of C.sub.6-C.sub.12aryl are phenyl,naphthyl and biphenyl.

[0032] Hetero-C.sub.3-C.sub.12aryl is preferably pyridyl,pyrimidinyl, triazinyl, pyrrolyl, furyl, thiophenyl orquinolyl.

[0033] A cyclic radical formed by R.sub.11 and R.sub.12 togetherwith the phenyl radical is for example3,4-dimethylenedioxyphenyl.

[0034] Preferred bis(biphenyl)triazine derivatives are compounds offormula (1) wherein [0035] R.sub.1, R.sub.2, R.sub.3, R.sub.4,R.sub.5 and R.sub.6 are hydrogen; and [0036] X is defined as informula (1).

[0037] Even more preferred are compounds of formula (1), wherein[0038] X is hydrogen; C.sub.1-C.sub.30alkyl which may beinterrupted by one or more oxygen atoms and/or substituted by oneor more R.sub.8 groups; C.sub.3-C.sub.12-cycloalkyl which issubstituted by R.sub.8;--CH((CH.sub.2)p-R.sub.8)-CO--O-(CH.sub.2).sub.p-R.sub.9;--CH((CH.sub.2).sub.p-R.sub.8)-CO-(NR.sub.10)-(CH.sub.2).sub.m-R.sub.9;--CO--(CH.sub.2).sub.p-R.sub.8; --CO--O--(CH.sub.2).sub.p-R.sub.8;--CH.sub.2--CH(--O(CO)--R.sub.8)--R.sub.9;--CO--(NR.sub.10)-(CH.sub.2).sub.p-R.sub.8; C.sub.2-C.sub.50alkenylwhich is unsubstituted or is interrupted by one or more oxygenatoms; C.sub.3-C.sub.12cycloalkyl which is uninterrupted orinterrupted by one or more oxygen atoms; [0039] R.sub.8, R.sub.9and R.sub.10 are defined as in claim 1; [0040] p is a number from 0to 20; and [0041] m is a number from 0 to 20.

[0042] Most preferred are bis(biphenyl)triazine derivatives offormula (1), wherein [0043] X is hydrogen; C.sub.1-C.sub.18alkylwhich may be interrupted by one or more oxygen atoms and/orsubstituted by hydroxy, C.sub.1-C.sub.12alkyl or*--O--(CO)--R.sub.12; a radical of formula

##STR00005##

[0043] phenoxy-C.sub.1-C.sub.18alkyl; phenyl-C.sub.1-C.sub.4alkyl;[0044] Y is --O--; or --NH--; [0045] R.sub.12 isC.sub.1-C.sub.18alkyl; [0046] R.sub.13 is hydrogen; orC.sub.1-C.sub.5alkyl; [0047] R.sub.14 is C.sub.1-C.sub.18 alkyl,which is optionally interrupted by --NH or --O--;C.sub.2-C.sub.18alkenyl; [0048] R.sub.8, R.sub.9 and R.sub.10 aredefined as in claim formula (1); [0049] R.sub.12 isC.sub.1-C.sub.5alkyl; [0050] p is a number from 0 to 20; and [0051]m is a number from 0 to 20.

[0052] Most preferred are mixtures of two structurally differentbiphenyl triazines of formula (1).

[0053] Examples of bisbiphenyltriazine compounds as used in thepresent invention are listed in Table 1 below:

TABLE-US-00001 TABLE 1 Representatives of bisbiphenyltriazinesaccording to the present invention B-1 ##STR00006## B-2##STR00007## B-3 ##STR00008## B-4 ##STR00009## B-5 ##STR00010## B-6##STR00011## B-7 ##STR00012## B-8 ##STR00013## B-9 ##STR00014##B-10 ##STR00015## B-11 ##STR00016## B-12 ##STR00017## B-13##STR00018## B-14 ##STR00019## B-15 ##STR00020## B-16 ##STR00021##B-17 ##STR00022## B-18 ##STR00023## B-19 ##STR00024## B-20##STR00025## B-21 ##STR00026## B-22 ##STR00027## B-23##STR00028##

[0054] The bisbiphenyl triazines as used in the present inventioncan be prepared according to standard procedures by reacting abis(biphenyl)resorcinyl triazine of formula (1a) with a reactant ofgeneral formula (1 b) wherein LG is a leaving group like forexample halogen (in particular bromine, chlorine) or tosylate andthe other substituents are as defined above. The reactant is ingeneral an alkylating or acylating agent.

##STR00029##

[0055] Such standard procedures are for example described in the WO96/28431 or in GB 2 317 174 A.

[0056] Other preparation methods that can be used analogously forthe preparation of the compounds according to this invention aredescribed in EP-A-434608, WO 98/03489, EP 1 308 084, GB-2317893-A,EP-0826675-A1 or in WO 2004/090030 A1.

[0057] The mixtures of bis(biphenyl)triazine derivatives accordingto formula (1) may advantageously be used as actives in cosmeticpreparations which additionally comprise at cosmetically tolerablecarriers or adjuvants.

[0058] The cosmetic preparation may also comprise, in addition tothe mixtures of bis(biphenyl)triazine derivatives according toformula (1) one or more further UV protective agents of thefollowing substance classes: [0059] 1. p-aminobenzoic acidderivatives, for example 4-dimethylaminobenzoic acid 2-ethylhexylester; [0060] 2. salicylic acid derivatives, for example salicylicacid 2-ethylhexyl ester; [0061] 3. benzophenone derivatives, forexample 2-hydroxy-4-methoxybenzophenone and its 5-sulfonic acidderivative; [0062] 4. dibenzoylmethane derivatives, for example1-(4-tert-butylphenyl)-3-(4-methoxphenyl)-propane-1,3-dione; [0063]5. diphenylacrylates, for example 2-ethylhexyl2-cyano-3,3-diphenylacrylate, and 3-(benzofuranyl) 2-cyanoacrylate;[0064] 6. 3-imidazol-4-ylacrylic acid and esters; [0065] 7.benzofuran derivatives, especially 2-(p-aminophenyl)benzofuranderivatives, described in EP-A-582 189, U.S. Pat. No. 5,338,539,U.S. Pat. No. 5,518,713 and EP-A-613 893; [0066] 8. polymeric UVabsorbers, for example the benzylidene malonate derivativesdescribed in EP-A-709 080; [0067] 9. cinnamic acid derivatives, forexample the 4-methoxycinnamic acid 2-ethylhexyl ester and isoamylester or cinnamic acid derivatives disclosed in U.S. Pat. NO.5,601,811 and WO 97/00851; [0068] 10. camphor derivatives, forexample 3-(4'-methyl)benzylidene-bornan-2-one,3-benzylidenebornan-2-one, N-[2(and4)-2-oxyborn-3-ylidene-methyl)-benzyl]acrylamide polymer,3-(4'-trimethylammonium)-benzylidene-bornan-2-one methyl sulfate,3,3'-(1,4-phenylene-dimethine)-bis(7,7-dimethyl-2-oxo-bicyclo[2.2.1]hepta-ne-1-ethanesulfonic acid) and salts,3-(4'-sulfo)benzylidene-bornan-2-one and salts; camphorbenzalkoniummethosulfate; [0069] 11. hydroxyphenyltriazine compounds, forexample2-(4'-methoxyphenyl)-4,6-bis(2'-hydroxy-4'-n-octyloxyphenyl)-1,3,5-triazi-ne;2,4-bis{[4-(3-(2-propyloxy)-2-hydroxy-propyloxy)-2-hydroxy]-phenyl}-6--(4-methoxphenyl)-1,3,5-triazine;2,4-bis{[4-(2-ethyl-hexyloxy)-2-hydroxy]-phenyl}-6-[4-(2-methoxyethyl-car-boxyl)-phenylamino]-1,3,5-triazine;2,4-bis{[4-(tris(trimethylsilyloxy-silylpropyloxy)-2-hydroxy]-phenyl}-6-(-4-methoxyphenyl)-1,3,5-triazine;2,4-bis{[4-(2''-methylpropenyloxy)-2-hydroxy]-phenyl}-6-(4-methoxphenyl)--1,3,5-triazine;2,4-bis{[4-(1',1',1',3',5',5',5'-heptamethyltrisilyl-2''-methyl-propyloxy-)-2-hydroxy]-phenyl}-6-(4-methoxphenyl)-1,3,5-triazine;2,4-bis{[4-(3-(2-propyloxy)-2-hydroxy]-propyloxy)-2-hydroxyyphenyl}-6-[4--ethylcarboxy)-phenylamino]-1,3,5-triazine; [0070] 12. benzotriazolecompounds, for example2,2'-methylene-bis(6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)--phenol

[0070] ##STR00030## [0071] 13. trianilino-s-triazine derivatives,for example2,4,6-trianiline-(p-carbo-2'-ethyl-1'-oxy)-1,3,5-triazine and theUV absorbers disclosed in U.S. Pat. No. 5,332,568, EP-A-517 104,EP-A-507 691, WO 93/17002 and EP-A-570 838; [0072] 14.2-phenylbenzimidazole-5-sulfonic acid and salts thereof; [0073] 15.menthyl o-aminobenzoate; [0074] 16. TiO.sub.2 (variouslyencapsulated), ZnO and mica.

[0075] The UV absorbers described in "Sunscreens", Eds. N.J. Lowe,N. A. Shaath, Marcel Dekker, Inc., New York and Basle or inCosmetics & Toiletries (107), 50ff (1992) also can be used asadditional UV protective substances.

[0076] Special preference is given to the light-protective agentsindicated in the following Table:

TABLE-US-00002 INCI Chemical Name CAS No. 3-BENZYLIDENE CAMPHOR1,7,7-trimethyl-3-(phenylmethylene)- 15087-24-8bicyclo[2.2.1]heptan-2-one 4-METHYLBENZYLIDENE(+/-)-1,7,7-trimethyl-3-[(4-methylphenyl)- 36861-47-9 CAMPHORmethylene]bicyclo[2.2.1]heptan-2-one BENZOPHENONE-10(2-hydroxy-4-methoxyphenyl)-(4-methyl- 1641-17-4 phenyl)methanoneBENZOPHENONE-1 2,4-dihydroxybenzophenone 131-56-6 BENZOPHENONE-22,2',4,4'-tetrahydroxybenzophenone 131-55-5 BENZOPHENONE-32-hydroxy-4-methoxybenzophenone 131-57-7 BENZOPHENONE-42-hydroxy-4-methoxybenzophenone-5- 4065-45-6 sulfonic acidBENZOPHENONE-6 2,2'-dihydroxy-4,4'-dimethoxybenzophenone 131-54-4BENZOPHENONE-8 2,2'-dihydroxy-4-methoxybenzophenone 131-53-3BENZYLIDENE CAMPHOR alpha-(2-oxoborn-3-ylidene)-toluene-4-56039-58-8 SULFONIC ACID sulfonic acid and its salts BUTYL METHOXY-1-[4-(1,1-dimethylethyl)phenyl]-3-(4- 70356-09-1 DIBENZOYLMETHANEmethoxyphenyl)propane-1,3-dione CAMPHOR BENZALKONIUM methylN,N,N-trimethyl-4-[(4,7,7-trimethyl- METHOSULFATE3-oxobicyclo[2,2,1]hept-2-ylidene)methyl]- 52793-97- aniliniumsulfate CINOXATE 2-ethoxyethyl p-methoxycinnamate 104-28-9DEA-METHOXYCINNAMATE diethanolamine salt of p-methoxyhydrocinnamate56265-46-4 DIISOPROPYL METHYL CIN- 2-propenoic acid, 3-[2,4-bis(1-32580-71-5 NAMATE methylethyl)phenyl]-, methyl ester DIPROPYLENEGLYCOL SA- dipropylene glycol salicylate 7491-14-7 LICYLATE ETHYLDIHYDROXYPROPYL ethyl 4-bis(2-hydroxypropyl)-amino- 58882-17-0 PABAbenzoate ETHYL DIISOPROPYLCIN- ethyl3-[2,4-bis(1-methylethyl)phenyl]acrylate 32580-72-6 NAMATE ETHYLMETHOXYCINNAMATE ethyl p-methoxycinnamate 1929-30-2 GLYCERYLOCTANOATE DIMETHOXYCINNAMATE GLYCERYL PABA glyceryl1-(4-aminobenzoate) 136-44-7 HOMOSALATE3,3,5-trimethylcyclohexyl-2-hydroxy- 118-56-9 benzoate ISOAMYLp-METHOXY- isopentyl p-methoxycinnamate 71617-10-2 CINNAMATEISOPROPYL DIBENZOYL- 1-[4-(1-methylethyl)phenyl]-3-phenyl-63250-25-9 METHANE propane-1,3-dione ISOPROPYL METHOXYCIN-isopropyl p-methoxycinnamate 5466-76-2 NAMATE LAWSONE2-hydroxy-1,4-naphthoquinone 83-72-7 MENTHYL ANTHRANILATE menthylo-aminobenzoate 134-09-8 MENTHYL SALICYLATE menthyl salicylate89-46-3 OCTOCRYLENE 2-ethylhexyl 2-cyano-3,3-diphenyl acrylate6197-30-4 ETHYLHEXYL DIMETHYL 2-ethylhexyl4-(dimethylamino)benzoate 21245-02-3 PABA ETHYLHEXYL METHOXY-2-ethylhexyl 4-methoxycinnamate 5466-77-3 CINNAMATE ETHYLHEXYLSALICYLATE 2-ethylhexyl salicylate 118-60-5 ETHYLHEXYL TRIAZONEbenzoic acid, 4,4',4''-(1,3,5-triazine-2,4,6- 88122-99-0triyltriimino)tris-, tris(2-ethylhexyl) ester; 2,4,6-trianilino-(p-carbo-2'-ethylhexyl- 1'-oxy)-1,3,5-triazine PABA4-aminobenzoic acid 150-13-0 PEG-25 PABA benzoic acid, 4-amino-,ethyl ester, 113010-52-9 polymer with oxirane PENTYL DIMETHYL PABAamyl dimethyl PABA 14779-78-3 PHENYLBENZIMIDAZOLE2-phenyl-1H-benzimidazole-5-sulfonic 27503-81-7 SULFONIC ACID acidPOLYACRYLAMIDOMETHYL 113783-61-2 BENZYLIDENE CAMPHOR TEA-SALICYLATEtriethanolamine salicylate 2174-16-5 TEREPHTHALYLIDENE DI-3,3'-(1,4-phenylenedimethylene)bis[7,7-dimethyl- 90457-82-2 CAMPHORSULFONIC 2-oxo-bicyclo[2.2.1]heptane-1-methanesulfonic ACID acid]TITANIUM DIOXIDE titanium dioxide 13463-67-7 DIGALLOYL TRIOLEATEdigalloyl trioleate 17048-39-4 ZINC OXIDE zinc oxide 1314-13-2Methylene bis-benzotriazolyl2,2'-methylene-bis[6-(2H-benzotriazol-2-yl)-4- 103597-45-1tetramethylbutylphenol (1,1,3,3-tetramethylbutyl)-phenol]Bis-ethylhexyloxyphenol me-2,4-bis{[4-(2-ethylhexyloxy)-2-hydroxy]-phenyl}- 187393-00-6thoxyphenyltriazine 6-(4-methoxyphenyl)-(1,3,5)-triazineBISIMIDAZYLATE 1H-benzimidazole-4,6-disulfonic acid, 180898-37-72,2'-(1,4-phenylene)bis-, disodium salt DIETHYLHEXYL BUTAMIDObenzoic acid, 4,4'-[[6-[[4-[[(1,1-dimethylethyl)- 154702-15-5TRIAZONE amino]carbonyl]phenyl]amino]-1,3,5-triazine-2,4-diyl]diimino]bis-, bis(2-ethyl-hexyl) ester DROMETRIZOLETRISILOXANE phenol, 2-(2H-benzotriazol-2-yl)-4-methyl- 155633-54-86-[2-methyl-3-[1,3,3,3-tetramethyl-1-[(trimethyl-silyl)oxy]disiloxanyl]propyl]- BENZYLIDENE MALONATEalpha-(trimethylsilyl)-omega-(trimethyl-silyloxy)- 207574-74-1POLYSILOXANE poly[oxy(dimethyl)silylene]-co-[oxy(methyl)(2-{p-[2,2-bis(ethoxycarbonyl)vinyl]phenoxy}-1-methyleneethyl)silylene]-co-[oxy(methyl)(2-{p-[2,2-bis(ethoxycarbonyl)vinyl]phenoxy}prop-1- enyl)silylene]2-(4-diethylamino-2-hydroxybenzoyl)- 302776-68-7 benzoic hexylester

[0077] Each of the above-mentioned light-protective agents,especially the light-protective agents in the above Table indicatedas being preferred, can be used in admixture with the mixtures ofthe bis(biphenyl)triazine derivatives according to the invention.It will be understood in that connection that, in addition to themixtures of the bis(biphenyl)triazine derivatives of the presentinvention, it is also possible for more than one of the additionallight-protective agents to be used, for example, two, three, four,five or six further light-protective agents.

[0078] Other typical ingredients in such formulations arepreservatives, bactericides and bacteriostatic agents, perfumes,dyes, pigments, thickening agents, moisturizing agents, humectants,fats, oils, waxes or other typical ingredients of cosmetic andpersonal care formulations such as alcohols, poly-alcohols,polymers, electrolytes, organic solvents, silicon derivatives,emollients, emulsifiers or emulsifying surfactants, surfactants,dispersing agents, antioxidants, anti-irritants andanti-inflammatory agents etc.

[0079] The cosmetic compositions contain, for example, from 0.1 to30% by weight, preferably from 0.1 to 15% by weight and especiallyfrom 0.5 to 10% by weight, based on the total weight of thecomposition, of the mixtures of the bis(biphenyl)triazinederivatives of formula (1) and at least one cosmetically tolerableadjuvant.

[0080] The cosmetic compositions can be prepared by physicallymixing the mixtures of the bis(biphenyl)triazine derivatives offormula (1) with the adjuvant using customary methods, for exampleby simply stirring together the individual components, especiallyby making use of the dissolution properties of already knowncosmetic UV absorbers, for example OMC, salicylic acid isooctylester, inter alia. The UV absorber can be used, for example,without further treatment, or in the micronized state, or in theform of a powder.

[0081] The cosmetic compositions may be, for example, creams, gels,lotions, alcoholic and aqueous/alcoholic solutions, emulsions,wax/fat compositions, stick preparations, powders or ointments.

[0082] As water- and oil-containing emulsions (e.g. W/O, O/W, O/W/Oand W/O/W emulsions or microemulsions) the compositions contain,for example, from 0.1 to 30% by weight, preferably from 0.1 to 15%by weight and especially from 0.5 to 10% by weight, based on thetotal weight of the composition, of the mixture of thebis(biphenyl)triazine derivatives of formula (1), from 1 to 60% byweight, especially from 5 to 50% by weight and preferably from 10to 35% by weight, based on the total weight of the composition, ofat least one oil component, from 0 to 30% by weight, especiallyfrom 1 to 30% by weight and preferably from 4 to 20% by weight,based on the total weight of the composition, of at least oneemulsifier, from 10 to 90% by weight, especially from 30 to 90% byweight, based on the total weight of the composition, of water, andfrom 0 to 88.9% by weight, especially from 1 to 50% by weight, offurther cosmetically tolerable adjuvants.

[0083] As oil components of oil-containing compositions (e.g. oils,W/O, O/W, O/W/O and W/O/W emulsions or microemulsions) there comeinto consideration, for example, Guerbet alcohols based on fattyalcohols having from 6 to 18, preferably from 8 to 10, carbonatoms, esters of linear C.sub.6-C.sub.24 fatty acids with linearC.sub.3-C.sub.24 alcohols, esters of branchedC.sub.6-C.sub.13carboxylic acids with linear C.sub.6-C.sub.24 fattyalcohols, esters of linear C.sub.6-C.sub.24 fatty acids withbranched alcohols, especially 2-ethylhexanol, esters ofhydroxycarboxylic acids with linear or branched C.sub.6-C.sub.22fatty alcohols, especially dioctyl malates, esters of linear and/orbranched fatty acids with polyhydric alcohols (for examplepropylene glycol, dimer diol or trimer triol) and/or Guerbetalcohols, triglycerides based on C.sub.6-C.sub.10 fatty acids,liquid mono/di-/tri-glyceride mixtures based on C.sub.6-C.sub.18fatty acids, esters of C.sub.6-C.sub.24 fatty alcohols and/orGuerbet alcohols with aromatic carboxylic acids, especially benzoicacid, esters of C.sub.2-C.sub.12dicarboxylic acids with linear orbranched alcohols having from 1 to 22 carbon atoms or polyolshaving from 2 to 10 carbon atoms and from 2 to 6 hydroxy groups,vegetable oils (such as sunflower oil, olive oil, soybean oil,rapeseed oil, almond oil, jojoba oil, orange oil, wheat germ oil,peach kernel oil and the liquid components of coconut oil),branched primary alcohols, substituted cyclohexanes, linear andbranched C.sub.6-C.sub.22 fatty alcohol carbonates, Guerbetcarbonates, esters of benzoic acid with linear and/or branchedC.sub.6-C.sub.22alcohols (e.g. Finsoly.RTM. TN), linear orbranched, symmetric or asymmetric dialkyl ethers having a total offrom 12 to 36 carbon atoms, especially from 12 to 24 carbon atoms,for example di-n-octyl ether, di-n-decyl ether, di-n-nonyl ether,di-n-undecyl ether, di-n-dodecyl ether, n-hexyl n-octyl ether,n-octyl n-decyl ether, n-decyl n-undecyl ether, n-undecyl n-dodecylether, n-hexyl n-undecyl ether, di-tert-butyl ether, diisopentylether, di-3-ethyldecyl ether, tert-butyl n-octyl ether, isopentyln-octyl ether and 2-methyl pentyl-n-octyl ether; ring-openingproducts of epoxidised fatty acid esters with polyols, siliconeoils and/or aliphatic or naphthenic hydrocarbons. Also ofimportance are monoesters of fatty acids with alcohols having from3 to 24 carbon atoms. That group of substances comprises theesterification products of fatty acids having from 8 to 24 carbonatoms, for example caproic acid, caprylic acid, 2-ethylhexanoicacid, capric acid, lauric acid, isotridecanoic acid, myristic acid,palmitic acid, palmitoleic acid, stearic acid, isostearic acid,oleic acid, elaidic acid, petroselinic acid, linoleic acid,linolenic acid, elaeostearic acid, arachidic acid, gadoleic acid,behenic acid and erucic acid and technical-grade mixtures thereof(obtained, for example, in the pressure removal of natural fats andoils, in the reduction of aldehydes from Roelen's oxosynthesis orin the dimerisation of unsaturated fatty acids) with alcohols, forexample isopropyl alcohol, caproic alcohol, capryl alcohol,2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecylalcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol,stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidylalcohol, petroselinyl alcohol, linoyl alcohol, linolenyl alcohol,elaeostearyl alcohol, arachidyl alcohol, gadoleyl alcohol, behenylalcohol, erucyl alcohol and brassidyl alcohol and technical-grademixtures thereof (obtained, for example, in the high-pressurehydrogenation of technical-grade methyl esters based on fats andoils or aldehydes from Roelen's oxosynthesis and as monomerfractions in the dimerisation of unsaturated fatty alcohols). Ofspecial importance are isopropyl myristate, isononanoic acidC.sub.16-C.sub.18alkyl esters, stearic acid 2-ethylhexyl ester,cetyl oleate, glycerol tricaprylate, coconut fatty alcoholcaprinate/caprylate and n-butyl stearate. Further oil componentsthat can be used are dicarboxylic acid esters, such as di-n-butyladipate, di(2-ethylhexyl) adipate, di(2-ethylhexyl) succinate anddiisotridecyl acetate, and also diol esters, such as ethyleneglycol dioleate, ethylene glycol diisotridecanoate, propyleneglycol di(2-ethylhexanoate), propylene glycol diisostearate,propylene glycol dipelargonate, butanediol diisostearate andneopentyl glycol dicaprylate. Preferred mono- or poly-ols areethanol, isopropanol, propylene glycol, hexylene glycol, glyceroland sorbitol. It is also possible to use di- and/or tri-valentmetal salts (alkaline earth metal, Al.sup.3+ inter alia) of one ormore alkyl carboxylic acids.

[0084] The oil components can be used in an amount of, for example,from 1 to 60% by weight, especially from 5 to 50% by weight andpreferably from 10 to 35% by weight, based on the total weight ofthe composition.

[0085] Any conventionally usable emulsifier can be used for thecompositions.

[0086] As emulsifiers there come into consideration, for example,non-ionic surfactants from the following groups: [0087] additionproducts of from 2 to 30 mol of ethylene oxide and/or from 0 to 5mol of propylene oxide with linear fatty alcohols having from 8 to22 carbon atoms, with fatty acids having from 12 to 22 carbon atomsand with alkylphenols having from 8 to 15 carbon atoms in the alkylgroup, for example ceteareth-20 or ceteareth-12; [0088]C.sub.12-C.sub.22 fatty acid mono- and di-esters of additionproducts of from 1 to 30 mol of ethylene oxide with polyols havingfrom 3 to 6 carbon atoms, especially with glycerol; [0089] glycerolmono- and di-esters and sorbitan mono- and di-esters of saturatedand unsaturated fatty acids having from 6 to 22 carbon atoms andethylene oxide addition products thereof, for example glycerylstearates, glyceryl isostearates, glyceryl oleates, sorbitanoleates or sorbitan sesquioleates; [0090]C.sub.8-C.sub.22alkyl-mono- and -oligo-glycosides and ethoxylatedanalogues thereof, degrees of oligomerisation of from 1.1 to 5,especially from 1.2 to 1.4, being preferred, and glucose beingpreferred as the sugar component; [0091] addition products of from2 to 60 mol, especially from 15 to 60 mol, of ethylene oxide withcastor oil and/or hydrogenated castor oil; [0092] polyol esters andespecially polyglycerol esters, for example diisostearoylpolyglyceryl-3-diisostearates, polyglyceryl-3-diisostearates,triglyceryl diisostearates, polyglyceryl-2-sesquiisostearates orpolyglyceryl dimerates. Mixtures of compounds from a plurality ofthose substance classes are also suitable; [0093] partial estersbased on linear, branched, unsaturated or saturatedC.sub.6-C.sub.22 fatty acids, ricinoleic acid and also12-hydroxystearic acid and on glycerol, polyglycerol,pentaerythritol, dipentaerythritol, sugar alcohols (e.g. sorbitol),alkyl glucosides (e.g. methyl glucoside, butyl glucoside, laurylglucoside) and also polyglucosides (e.g. cellulose), for examplepolyglyceryl-2-dihydroxystearates or polyglyceryl-2-diricinoleates;[0094] mono-, di- and tri-alkylphosphates and also mono-, di-and/or tri-PEG-alkylphosphates and salts thereof; [0095] wool waxalcohols; [0096] one or more ethoxylated esters of naturalderivatives, for example polyethoxylated esters of hydrogenatedcastor oil; [0097] silicone oil emulsifiers, for example siliconepolyol; [0098] polysiloxane/polyalkyl/polyether copolymers andcorresponding derivatives, for example cetyl dimethicone copolyol;[0099] mixed esters of pentaerythritol, fatty acids, citric acidand fatty alcohol (see DE-A-1 165 574) and/or mixed esters of fattyacids having from 6 to 22 carbon atoms, methylglucose and polyols,preferably glycerol or polyglycerol, for examplepolyglyceryl-3-glucose distearates, polyglyceryl-3-glucosedioleates, methyl glucose dioleates or dicocoyl pentaerythryldistearyl citrates and also [0100] polyalkylene glycols.

[0101] The addition products of ethylene oxide and/or of propyleneoxide with fatty alcohols, fatty acids, alkylphenols, glycerolmono- and di-esters and also sorbitan mono- and di-esters of fattyacids, or with castor oil, are known, commercially availableproducts. They are usually homologue mixtures, the average degreeof alkoxylation of which corresponds to the ratio of the amounts ofethylene oxide and/or propylene oxide and substrate with which theaddition reaction is carried out. C.sub.12-C.sub.18 fatty acidmono- and di-esters of addition products of ethylene oxide withglycerol are known, for example, from DE-A-2 024 051 asfat-restoring substances for cosmetic preparations.

[0102] C.sub.8-C.sub.18Alkyl-mono- and -oligo-glycosides, theirpreparation and their use are known from the prior art. They areprepared especially by reacting glucose or oligosaccharides withprimary alcohols having from 8 to 18 carbon atoms. Suitableglycoside radicals include monoglycosides in which a cyclic sugarradical is glycosidically bonded to the fatty alcohol and alsooligomeric glycosides having a degree of oligomerisation of up topreferably about 8. The degree of oligomerisation is a statisticalaverage value based on a homologue distribution customary for suchtechnical-grade products.

[0103] It is also possible to use zwitterionic surfactants asemulsifiers. The term "zwitterionic surfactants" denotes especiallysurface-active compounds that carry at least one quaternaryammonium group and at least one carboxylate and/or sulfonate groupin the molecule. Zwitterionic surfactants that are especiallysuitable are the so-called betaines, such asN-alkyl-N,N-dimethylammonium glycinates, for examplecocoalkyldimethylammonium glycinate,N-acylaminopropyl-N,N-dimethylammonium glycinates, for examplecocoacylaminopropyldimethylammonium glycinate, and2-alkyl-3-carboxymethyl-3-hydroxyethylimidazolines each having from8 to 18 carbon atoms in the alkyl or acyl group and alsococoacylaminoethylhydroxyethylcarboxymethylglycinate. Specialpreference is given to the fatty acid amide derivative known by theCTFA name cocamidopropyl betaine. Likewise suitable as emulsifiersare ampholytic surfactants. Ampholytic surfactants are to beunderstood as meaning especially those which, in addition tocontaining a C.sub.8-C.sub.18-alkyl or -acyl group, contain atleast one free amino group and at least one --COOH or --SO.sub.3Hgroup in the molecule and are capable of forming internal salts.Examples of suitable ampholytic surfactants includeN-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids,N-alkyliminodipropionic acids,N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines,N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoaceticacids, each having approximately from 8 to 18 carbon atoms in thealkyl group.

[0104] Ampholytic surfactants to which special preference is givenare N-cocoalkylamino-propionate, cocoacylaminoethylaminopropionateand C.sub.12-C.sub.18acylsarcosine. In addition to the ampholyticemulsifiers there also come into consideration quaternaryemulsifiers, special preference being given to those of theesterquat type, preferably methyl-quaternised di-fatty acidtriethanolamine ester salts.

[0105] Non-ionic emulsifiers are preferred. Of the non-ionicemulsifiers mentioned, special preference is given to ethoxylatedfatty alcohols having from 8 to 22 carbon atoms and from 4 to 30 EOunits.

[0106] The emulsifiers may be used in an amount of, for example,from 1 to 30% by weight, especially from 4 to 20% by weight andpreferably from 5 to 10% by weight, based on the total weight ofthe composition. It is, however, also possible in principle todispense with the use of emulsifiers.

[0107] The compositions according to the invention, for examplecreams, gels, lotions, alcoholic and aqueous/alcoholic solutions,emulsions, wax/fat compositions, stick preparations, powders orointments, may in addition contain, as further adjuvants andadditives, mild surfactants, super-fatting agents, pearlescentwaxes, consistency regulators, thickeners, polymers, siliconecompounds, fats, waxes, stabilisers, biogenic active ingredients,deodorising active ingredients, anti-dandruff agents, film formers,swelling agents, further UV light-protective factors, antioxidants,hydrotropic agents, preservatives, insect repellents, self-tanningagents, solubilizers, perfume oils, colorants, bacteria-inhibitingagents and the like.

[0108] Substances suitable for use as super-fatting agents are, forexample, lanolin and lecithin and also polyethoxylated or acrylatedlanolin and lecithin derivatives, polyol fatty acid esters,monoglycerides and fatty acid alkanolamides, the lattersimultaneously acting as foam stabilisers.

[0109] Examples of suitable mild surfactants, that is to saysurfactants especially well tolerated by the skin, include fattyalcohol polyglycol ether sulfates, monoglyceride sulfates, mono-and/or di-alkyl sulfosuccinates, fatty acid isethionates, fattyacid sarcosinates, fatty acid taurides, fatty acid glutamates,.alpha.-olefin sulfonates, ether carboxylic acids, alkyloligoglucosides, fatty acid glucamides, alkylamidobetaines and/orprotein fatty acid condensation products, the latter preferablybeing based on wheat proteins.

[0110] As pearlescent waxes there come into consideration, forexample: alkylene glycol esters, especially ethylene glycoldistearate; fatty acid alkanolamides, especially coco fatty aciddiethanolamide; partial glycerides, especially stearic acidmonoglyceride; esters of polyvalent, unsubstituted orhydroxy-substituted carboxylic acids with fatty alcohols havingfrom 6 to 22 carbon atoms, especially long-chained esters oftartaric acid; fatty substances, for example fatty alcohols, fattyketones, fatty aldehydes, fatty ethers and fatty carbonates, whichin total have at least 24 carbon atoms, especially laurone anddistearyl ether; fatty acids, such as stearic acid, hydroxystearicacid or behenic acid, ring-opening products of olefin epoxideshaving from 12 to 22 carbon atoms with fatty alcohols having from12 to 22 carbon atoms and/or polyols having from 2 to 15 carbonatoms and from 2 to 10 hydroxy groups, and mixtures thereof.

[0111] As consistency regulators there come into considerationespecially fatty alcohols or hydroxy fatty alcohols having from 12to 22 carbon atoms and preferably from 16 to 18 carbon atoms, andin addition partial glycerides, fatty acids and hydroxy fattyacids. Preference is given to a combination of such substances withalkyl-oligoglucosides and/or fatty acid N-methylglucamides ofidentical chain length and/or polyglycerolpoly-12-hydroxystearates. Suitable thickeners include, for example,Aerosil types (hydrophilic silicic acids), polysaccharides,especially xanthan gum, guar-guar, agar-agar, alginates andTyloses, carboxymethyl cellulose and hydroxymethyl cellulose, alsorelatively high molecular weight polyethylene glycol mono- anddi-esters of fatty acids, polyacrylates (e.g. Carbopol.RTM. fromGoodrich or Synthalen.RTM. from Sigma), polyacrylamides, polyvinylalcohol and polyvinylpyrrolidone, surfactants, for exampleethoxylated fatty acid glycerides, esters of fatty acids withpolyols, for example pentaerythritol or trimethylolpropane, fattyalcohol ethoxylates with restricted homologue distribution andalkyl-oligoglucosides as well as electrolytes, such as sodiumchloride or ammonium chloride.

[0112] Suitable cationic polymers are, for example, cationiccellulose derivatives, for example a quaternised hydroxymethylcellulose obtainable under the name Polymer JR 400.RTM. fromAmerchol, cationic starch, copolymers of diallylammonium salts andacrylamides, quaternised vinylpyrrolidone/vinyl imidazole polymers,for example Luviquat.RTM. (BASF), condensation products ofpolyglycols and amines, quaternised collagen polypeptides, forexample lauryldimonium hydroxypropyl hydrolyzed collagen(Lamequat.RTM.L/Grunau), quaternised wheat polypeptides,polyethyleneimine, cationic silicone polymers, for exampleamidomethicones, copolymers of adipic acid anddimethylaminohydroxypropyldiethylenetriamine(Cartaretin.RTM./Sandoz), copolymers of acrylic acid withdimethyldiallylammonium chloride (Merquat.RTM. 550/Chemviron),polyaminopolyamides, as described, for example, in FR-A-2 252 840,and the crosslinked water-soluble polymers thereof, cationic chitinderivatives, for example quaternised chitosan, optionallydistributed as microcrystals; condensation products ofdihaloalkyls, for example dibromobutane, with bisdialkylamines, forexample bisdimethylamino-1,3-propane, cationic guar gum, forexample Jaguar.RTM. C-17, Jaguar.RTM. C-16 from Celanese,quaternised ammonium salt polymers, for example Mirapol.RTM. A-15,Mirapol.RTM. AD-1, Mirapol.RTM. AZ-1 from Miranol.

[0113] As anionic, zwitterionic, amphoteric and non-ionic polymersthere come into consideration, for example, vinyl acetate/crotonicacid copolymers, vinylpyrrolidone/vinyl acrylate copolymers, vinylacetate/butyl maleate/isobornyl acrylate copolymers, methyl vinylether/maleic anhydride copolymers and esters thereof, uncrosslinkedpolyacrylic acids and polyacrylic acids crosslinked with polyols,acrylamidopropyltrimethylammonium chloride/acrylate copolymers,octyl acrylamide/methyl methacrylate/tert-butylaminoethylmethacrylate/2-hydroxypropyl methacrylate copolymers,polyvinylpyrrolidone, vinylpyrrolidone/vinyl acetate copolymers,vinylpyrrolidone/dimethylaminoethyl methacrylate/vinyl caprolactamterpolymers and also optionally derivatised cellulose ethers andsilicones.

[0114] Suitable silicone compounds are, for example,dimethylpolysiloxanes, methylphenylpolysiloxanes, cyclic silicones,and also amino-, fatty acid-, alcohol-, polyether-, epoxy-,fluorine-, glycoside- and/or alkyl-modified silicone compounds,which at room temperature may be in either liquid or resinous form.Also suitable are simethicones, which are mixtures of dimethiconeshaving an average chain length of from 200 to 300 dimethylsiloxaneunits with hydrogenated silicates. A detailed survey by Todd et al.of suitable volatile silicones may in addition be found in Cosm.Toil. 91, 27 (1976).

[0115] Typical examples of fats are glycerides, and as waxes therecome into consideration, inter alia, beeswax, carnauba wax,candelilla wax, montan wax, paraffin wax, hydrogenated castor oilsand fatty acid esters or microwaxes solid at room temperatureoptionally in combination with hydrophilic waxes, e.g. cetylstearylalcohol or partial glycerides. Metal salts of fatty acids, forexample magnesium, aluminium and/or zinc stearate or ricinoleate,may be used as stabilisers.

[0116] Biogenic active ingredients are to be understood as meaning,for example, tocopherol, tocopherol acetate, tocopherol palmitate,ascorbic acid, deoxyribonucleic acid, retinol, bisabolol,allantoin, phytantriol, panthenol, AHA acids, amino acids,ceramides, pseudoceramides, essential oils, plant extracts andvitamin complexes.

[0117] As deodorising active ingredients there come intoconsideration, for example, antiperspirants, for example aluminiumchlorohydrates (see J. Soc. Cosm. Chem. 24, 281 (1973)). Under thetrade mark Locron.RTM. of Hoechst AG, Frankfurt (FRG), there isavailable commercially, for example, an aluminium chlorohydratecorresponding to formula Al.sub.2(OH).sub.5Cl.times.2.5 H.sub.2O,the use of which is especially preferred (see J. Pharm. Pharmacol.26, 531 (1975)). Besides the chlorohydrates, it is also possible touse aluminium hydroxyacetates and acidic aluminium/zirconium salts.Esterase inhibitors may be added as further deodorising activeingredients. Such inhibitors are preferably trialkyl citrates, suchas trimethyl citrate, tripropyl citrate, triisopropyl citrate,tributyl citrate and especially triethyl citrate (Hydagen.RTM. CAT,Henkel KGaA, Dusseldorf/FRG), which inhibit enzyme activity andhence reduce odour formation. Further substances that come intoconsideration as esterase inhibitors are sterol sulfates orphosphates, for example lanosterol, cholesterol, campesterol,stigmasterol and sitosterol sulfate or phosphate, dicarboxylicacids and esters thereof, for example glutaric acid, glutaric acidmonoethyl ester, glutaric acid diethyl ester, adipic acid, adipicacid monoethyl ester, adipic acid diethyl ester, malonic acid andmalonic acid diethyl ester and hydroxycarboxylic acids and estersthereof, for example citric acid, malic acid, tartaric acid ortartaric acid diethyl ester. Antibacterial active ingredients thatinfluence the microbial flora and kill, or inhibit the growth of,sweat-decomposing bacteria can likewise be present in thepreparations (especially in stick preparations). Examples includechitosan, phenoxyethanol and chlorhexidine gluconate.5-Chloro-2-(2,4-dichlorophenoxy)-phenol (Irgasan.RTM., CibaSpecialty Chemicals Inc.) has also proved especially effective.

[0118] As anti-dandruff agents there may be used, for example,climbazole, octopirox and zinc pyrithione. Customary film formersinclude, for example, chitosan, microcrystalline chitosan,quaternised chitosan, polyvinylpyrrolidone, vinylpyrrolidone/vinylacetate copolymers, polymers of quaternary cellulose derivativescontaining a high proportion of acrylic acid, collagen, hyaluronicacid and salts thereof and similar compounds. As swelling agentsfor aqueous phases there may be used montmorillonites, clay mineralsubstances, Pemulen and also alkyl-modified types of Carbopol(Goodrich). Further suitable polymers and swelling agents can befound in the review by R. Lochhead in Cosm. Toil. 108, 95(1993).

[0119] In addition to the primary light-protective substances it isalso possible to use secondary light-protective substances of theantioxidant kind which interrupt the photochemical reaction chaintriggered when UV radiation penetrates the skin or hair. Typicalexamples of such antioxidants are 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-carnosine, L-carnosine and derivativesthereof (e.g. anserine), carotinoids, carotenes (e.g..alpha.-carotene, .beta.-carotene, lycopene) and derivativesthereof, chlorogenic acid and derivatives thereof, lipoic acid andderivatives thereof (e.g. dihydrolipoic acid), aurothioglycose,propylthiouracil and other thiols (e.g. thioredoxin, glutathione,cysteine, cystine, cystamine and the glycosyl, N-acetyl, methyl,ethyl, propyl, amyl, butyl, lauryl, palmitoyl, oleyl,.gamma.-linoleyl, cholesteryl and glyceryl esters thereof) and alsosalts thereof, dilauryl thiodipropionate, distearylthiodipropionate, thiodipropionic acid and derivatives thereof(esters, ethers, peptides, lipids, nucleotides, nucleosides andsalts) and also sulfoximine compounds (e.g. buthioninesulfoximines, homocysteine sulfoximine, buthionine sulfones,penta-, hexa-, hepta-thionine sulfoximine) in very small tolerableamounts (e.g. from pmol to .mu.mol/kg), also (metal) chelatingagents (e.g. .alpha.-hydroxy fatty acids, palmitic acid, phyticacid, lactoferrin), .alpha.-hydroxy acids (e.g. citric acid, lacticacid, malic acid), humic acid, bile acid, bile extracts, bilirubin,biliverdin, EDTA, EGTA and derivatives thereof, unsaturated fattyacids and derivatives thereof (e.g. .gamma.-linolenic acid,linoleic acid, oleic acid), folic acid and derivatives thereof,ubiquinone and ubiquinol and derivatives thereof, vitamin C andderivatives (e.g. ascorbyl palmitate, magnesium ascorbyl phosphate,ascorbyl acetate), tocopherols and derivatives (e.g. vitamin Eacetate), vitamin A and derivatives (e.g. vitamin A palmitate) andalso coniferyl benzoate of benzoin resin, rutinic acid andderivatives thereof, .alpha.-glycosylrutin, ferulic acid,furfurylidene glucitol, carnosine, butyl hydroxytoluene, butylhydroxyanisole, resinous nordihydroguaiaretic acid,nordihydroguaiaretic acid, trihydroxybutyrophenone, uric acid andderivatives thereof, mannose and derivatives thereof, superoxidedismutase,N-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]sulfanilic acid(and salts thereof, for example the sodium salts), zinc andderivatives thereof (e.g. ZnO, ZnSO.sub.4), selenium andderivatives thereof (e.g. selenium methionine), stilbene andderivatives thereof (e.g. stilbene oxide, trans-stilbene oxide) andthe derivatives suitable according to the invention (salts, esters,ethers, sugars, nucleotides, nucleosides, peptides and lipids) ofthose mentioned active ingredients. HALS (="Hindered Amine LightStabilizers") compounds may also be mentioned. The amount ofantioxidants present is usually from 0.001 to 30% by weight,preferably from 0.01 to 3% by weight, based on the weight of the UVabsorber(s).

[0120] To improve the flow behavior it is also possible to employhydrotropic agents, for example ethanol, isopropyl alcohol orpolyols. The polyols that come into consideration for that purposehave preferably from 2 to 15 carbon atoms and at least two hydroxygroups.

[0121] The polyols may also contain further functional groups,especially amino groups, and/or may be modified with nitrogen.Typical examples are as follows: [0122] glycerol; [0123] alkyleneglycols, for example ethylene glycol, diethylene glycol, propyleneglycol, butylene glycol, hexylene glycol and also polyethyleneglycols having an average molecular weight of from 100 to 1000dalton; [0124] technical oligoglycerol mixtures having an intrinsicdegree of condensation of from 1.5 to 10, for example technicaldiglycerol mixtures having a diglycerol content of from 40 to 50%by weight; [0125] methylol compounds, such as, especially,trimethylolethane, trimethylolpropane, trimethylolbutane,pentaerythritol and dipentaerythritol; [0126] loweralkyl-glucosides, especially those having from 1 to 8 carbon atomsin the alkyl radical, for example methyl and butyl glucoside;[0127] sugar alcohols having from 5 to 12 carbon atoms, for examplesorbitol or mannitol; [0128] sugars having from 5 to 12 carbonatoms, for example glucose or saccharose; [0129] amino sugars, forexample glucamine; [0130] dialcohol amines, such as diethanolamineor 2-amino-1,3-propanediol.

[0131] Suitable preservatives include, for example, phenoxyethanol,formaldehyde solution, Parabens, pentanediol or sorbic acid and thefurther substance classes listed in Schedule 6, Parts A and B ofthe Cosmetics Regulations.

[0132] There may be mentioned as perfume oils mixtures of naturaland/or synthetic aromatic substances. Natural aromatic substancesare, for example, extracts from blossom (lilies, lavender, roses,jasmine, neroli, ylang-ylang), from stems and leaves (geranium,patchouli, petitgrain), from fruit (aniseed, coriander, carraway,juniper), from fruit peel (bergamot, lemons, oranges), from roots(mace, angelica, celery, cardamom, costus, iris, calmus), from wood(pinewood, sandalwood, guaiacum wood, cedarwood, rosewood), fromherbs and grasses (tarragon, lemon grass, sage, thyme), fromneedles and twigs (spruce, pine, Scots pine, mountain pine), fromresins and balsams (galbanum, elemi, benzoin, myrrh, olibanum,opoponax). Animal raw materials also come into consideration, forexample civet and castoreum. Typical synthetic aromatic substancesare, for example, products of the ester, ether, aldehyde, ketone,alcohol or hydrocarbon type.

[0133] Aromatic substance compounds of the ester type are, forexample, benzyl acetate, phenoxy-ethyl isobutyrate,p-tert-butylcyclohexyl acetate, linalyl acetate,dimethyl-benzylcarbinyl acetate, phenylethyl acetate, linalylbenzoate, benzyl formate, ethylmethylphenyl glycinate,allylcyclohexyl propionate, styrallyl propionate and benzylsalicylate. The ethers include, for example, benzyl ethyl ether;the aldehydes include, for example, the linear alkanals having from8 to 18 hydrocarbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial andbourgeonal; the ketones include, for example, the ionones,.alpha.-isomethylionone and methyl cedryl ketone; the alcoholsinclude, for example, anethol, citronellol, eugenol, isoeugenol,geraniol, linalool, phenyl ethyl alcohol and terpinol; and thehydrocarbons include mainly the terpenes and balsams. It ispreferable, however, to use mixtures of various aromatic substancesthat together produce an attractive scent. Ethereal oils ofrelatively low volatility, which are chiefly used as aromacomponents, are also suitable as perfume oils, e.g. sage oil,camomile oil, clove oil, melissa oil, oil of cinnamon leaves, limeblossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanumoil, labolanum oil and lavandin oil. Preference is given to the useof bergamot oil, dihydromyrcenol, lilial, lyral, citronellol,phenyl ethyl alcohol, .alpha.-hexyl cinnamaldehyde, geraniol,benzyl acetone, cyclamen aldehyde, linalool, boisambrene forte,ambroxan, indole, hedione, sandelice, lemon oil, tangerine oil,orange oil, allyl amyl glycolate, cyclovertal, lavandin oil,muscatel sage oil, .beta.-damascone, bourbon geranium oil,cyclohexyl salicylate, vertofix coeur, iso-E-Super, Fixolide NP,evernyl, iraldein gamma, phenylacetic acid, geranyl acetate, benzylacetate, rose oxide, romillat, irotyl and floramat alone or inadmixture with one another.

[0134] There may be used as colourants the substances that aresuitable and permitted for cosmetic purposes, as compiled, forexample, in the publication "Kosmetische Farbemittel" of theFarbstoffkommission der Deutschen Forschungsgemeinschaft, VerlagChemie, Weinheim, 1984, pages 81 to 106. The colourants are usuallyused in concentrations of from 0.001 to 0.1% by weight, based onthe total mixture.

[0135] Typical examples of bacteria-inhibiting agents arepreservatives that have a specific action against gram-positivebacteria, such as 2,4,4'-trichloro-2'-hydroxydiphenyl ether,chlorhexidine (1,6-di(4-chlorophenyl-biguanido)hexane) or TCC(3,4,4'-trichlorocarbanilide).

[0136] A large number of aromatic substances and ethereal oils alsohave antimicrobial properties. Typical examples are the activeingredients eugenol, menthol and thymol in clove oil, mint oil andthyme oil. A natural deodorising agent of interest is the terpenealcohol farnesol (3,7,11-trimethyl-2,6,10-dodecatrien-1-ol), whichis present in lime blossom oil. Glycerol monolaurate has alsoproved to be a bacteriostatic agent. The amount of the additionalbacteria-inhibiting agents present is usually from 0.1 to 2% byweight, based on the solids content of the preparations.

[0137] It is furthermore possible for the cosmetic compositions tocontain, as adjuvants, antifoams, such as silicones, structurants,such as maleic acid, solubilisers, such as ethylene glycol,propylene glycol, glycerol or diethylene glycol, opacifiers, suchas latex, styrene/PVP or styrene/acrylamide copolymers, complexingagents, such as EDTA, NTA, .beta.-alaninediacetic acid orphosphonic acids, propellants, such as propane/butane mixtures,N.sub.2O, dimethyl ether, CO.sub.2, N.sub.2 or air, so-calledcoupler and developer components as oxidation dye precursors,reducing agents, such as thioglycolic acid and derivatives thereof,thiolactic acid, cysteamine, thiomalic acid or.alpha.-mercaptoethanesulfonic acid, or oxidising agents, such ashydrogen peroxide, potassium bromate or sodium bromate.

[0138] There come into consideration as insect repellents, forexample, N,N-diethyl-m-toluamide, 1,2-pentanediol or insectrepellent 3535; suitable self-tanning agents are, for example,dihydroxyacetone, erythrulose or mixtures of dihydroxyacetone anderythrulose.

[0139] Cosmetic formulations according to the invention arecontained in a wide variety of cosmetic preparations. There comeinto consideration, for example, especially the followingpreparations: [0140] skin-care preparations, e.g. skin-washing andcleansing preparations in the form of tabletform or liquid soaps,synthetic detergents or washing pastes, [0141] bath preparations,e.g. liquid (foam baths, milks, shower preparations) or solid bathpreparations, e.g. bath cubes and bath salts; [0142] skin-carepreparations, e.g. skin emulsions, multi-emulsions or skin oils;[0143] cosmetic personal care preparations, e.g. facial make-up inthe form of day creams or powder creams, face powder (loose orpressed), rouge or cream make-up, eye-care preparations, e.g.eyeshadow preparations, mascara, eyeliner, eye creams or eye-fixcreams; lip-care preparations, e.g. lipsticks, lip gloss, lipcontour pencils, nail-care preparations, such as nail varnish, nailvarnish removers, nail hardeners or cuticle removers; [0144]foot-care preparations, e.g. foot baths, foot powders, foot creamsor foot balsams, special deodorants and antiperspirants orcallus-removing preparations; [0145] light-protective preparations,such as sun milks, lotions, creams or oils, sunblocks or tropicals,pre-tanning preparations or after-sun preparations; [0146]skin-tanning preparations, e.g. self-tanning creams; [0147]depigmenting preparations, e.g. preparations for bleaching the skinor skin-lightening preparations; [0148] insect-repellents, e.g.insect-repellent oils, lotions, sprays or sticks; [0149]deodorants, such as deodorant sprays, pump-action sprays, deodorantgels, sticks or roll-ons; [0150] antiperspirants, e.g.antiperspirant sticks, creams or roll-ons; [0151] preparations forcleansing and caring for blemished skin, e.g. synthetic detergents(solid or liquid), peeling or scrub preparations or peeling masks;[0152] hair-removal preparations in chemical form (depilation),e.g. hair-removing powders, liquid hair-removing preparations,cream- or paste-form hair-removing preparations, hair-removingpreparations in gel form or aerosol foams; [0153] shavingpreparations, e.g. shaving soap, foaming shaving creams,non-foaming shaving creams, foams and gels, preshave preparationsfor dry shaving, aftershaves or aftershave lotions; [0154]fragrance preparations, e.g. fragrances (eau de Cologne, eau detoilette, eau de parfum, parfum de toilette, perfume), perfume oilsor perfume creams; [0155] cosmetic hair-treatment preparations,e.g. hair-washing preparations in the form of shampoos andconditioners, hair-care preparations, e.g. pretreatmentpreparations, hair tonics, styling creams, styling gels, pomades,hair rinses, treatment packs, intensive hair treatments,hair-structuring preparations, e.g. hair-waving preparations forpermanent waves (hot wave, mild wave, cold wave),hair-straightening preparations, liquid hair-setting preparations,hair foams, hairsprays, bleaching preparations, e.g. hydrogenperoxide solutions, lightening shampoos, bleaching creams,bleaching powders, bleaching pastes or oils, temporary,semi-permanent or permanent hair colourants, preparationscontaining self-oxidising dyes, or natural hair colourants, such ashenna or camomile.

[0156] The final formulations listed may exist in a wide variety ofpresentation forms, for example: [0157] in the form of liquidpreparations as a W/O, O/W, O/W/O, W/O/W or PIT emulsion and allkinds of microemulsions, [0158] in the form of a gel, [0159] in theform of an oil, a cream, milk or lotion, [0160] in the form of apowder, a lacquer, a tablet or make-up, [0161] in the form of astick, [0162] in the form of a spray (spray with propellent gas orpump-action spray) or an aerosol, [0163] in the form of a foam, or[0164] in the form of a paste.

[0165] Of special importance as cosmetic compositions for the skinare light-protective preparations, such as sun milks, lotions,creams, oils, sunblocks or tropicals, pretanning preparations orafter-sun preparations, also skin-tanning preparations, for exampleself-tanning creams. Of particular interest are sun protectioncreams, sun protection lotions, sun protection oils, sun protectionmilk and sun protection preparations in the form of a spray.

[0166] Of special importance as cosmetic compositions for the hairare the above-mentioned preparations for hair treatment, especiallyhair-washing preparations in the form of shampoos, hairconditioners, hair-care preparations, e.g. pretreatmentpreparations, hair tonics, styling creams, styling gels, pomades,hair rinses, treatment packs, intensive hair treatments,hair-straightening preparations, liquid hair-setting preparations,hair foams and hairsprays. Of special interest are hair-washingpreparations in the form of shampoos.

[0167] A shampoo has, for example, the following composition: from0.01 to 5% by weight of a UV absorber according to the invention,12.0% by weight of sodium laureth-2-sulfate, 4.0% by weight ofcocamidopropyl betaine, 3.0% by weight of sodium chloride, andwater ad 100%.

[0168] For example, especially the following hair-cosmeticformulations may be used: [0169] a.sub.1) spontaneously emulsifyingstock formulation, consisting of the UV absorber according to theinvention, PEG-6-C.sub.10oxoalcohol and sorbitan sesquioleate, towhich water and any desired quaternary ammonium compound, forexample 4% minkamidopropyl-dimethyl-2-hydroxyethylammonium chlorideor Quaternium 80 is added; [0170] a.sub.2) spontaneouslyemulsifying stock formulation consisting of the UV absorberaccording to the invention, tributyl citrate and PEG-20-sorbitanmonooleate, to which water and any desired quaternary ammoniumcompound, for example 4%minkamidopropyl-dimethyl-2-hydroxyethylammonium chloride orQuaternium 80 is added; [0171] b) Quat-doped solutions of the UVabsorber according to the invention in butyltriglycol and tributylcitrate; [0172] c) mixtures or solutions of the UV absorberaccording to the invention with n-alkylpyrrolidone.

[0173] The present invention describes a process for thepreparation of mixtures comprising bis(biphenyl)triazine and theiruse as high performance UV absorbers.

[0174] Preferably a mixture of BBTs or of one or more BBTs withother organic UV absorbers is used constituting a solid solution oran amorphous mixture.

[0175] Many processes describe the preparation of solid mixturesand solutions and are found in the literature which might be allapplicable also to the process of preparing solid bisbiphenyltriazine mixtures.

[0176] The preparation of solid mixtures can be classified intovapour, liquid and solid phase processes. Vapour phase processesseem to be unsuitable for the preparation of organic mixtures dueto thermal degradation of the organic constituents duringprocessing.

[0177] The solid mixtures and solutions of bis(biphenyl)triazinederivatives according to the present invention are preferablyprepared according to either liquid or solid phase processes.

[0178] The solid phase process involves a mechanical productionmethod. Such a mechanical preparation method is characterized by amechanical stimulation (eg high-speed ball milling) for activatingthe surface of the precursors sufficiently to induce the formationof the solid mixture and/or solution. In the process of milling,however, it is difficult to control to obtain a consistent productand expensive milling equipment for manufacturing are required.

[0179] Additionally, the mechanochemical synthesis requires a longreaction time.

[0180] Most preferably the liquid phase process is used for theproduction of bis(biphenyl)triazine solid mixtures and/orsolutions. With this method uniform micro-particles can be preparedand applied to mass production.

[0181] The preparation of mixtures of bisbiphenyl triazines is alsopossible by applying a mixture of different reactants of thegeneral formula (1b) in the production process.

[0182] The mixtures exhibit superior solubility properties comparedto prior art.

[0183] It is known that solid mixtures and in particular solidsolutions of two or more constituents exhibit excellent propertieswhich might be superior to the properties of the pure, unmixedcomponents.

[0184] Preparation Examples of Bis(biphenyl) triazine Mixtures

[0185] Preparation of Mixture (M-1):

[0186] 1 Part of bis(biphenyl) triazine B-2 and 3 parts ofbis(biphenyl)triazine B-3 are dissolved in 40 parts of hot2-butanone. The solvent is then stripped off under vacuum and theresulting residue is grinded to a yellowish powder (meltingpoint=62-68.degree. C.).

[0187] Preparation of Mixture (M-2):

[0188] 15 Parts of bis(biphenyl) triazine B-2 and 85 parts ofbis(biphenyl)triazine B-3 are dissolved in 1800 parts of hot2-butanone. The solvent is then stripped off under vacuum and theresulting residue is grinded to a yellowish powder (meltingpoint=57-65.degree. C.).

[0189] Preparation of Mixture (M-3):

[0190] 1 Part of bis(biphenyl) triazine B-2 and 9 parts ofbis(biphenyl)triazine B-3 are dissolved in 40 parts of hot2-butanone. The solvent is then stripped off under vacuum and theresulting residue is grinded to a yellowish powder (meltingpoint=64-72.degree. C.).

[0191] Preparation of Mixture (M-4):

[0192] 5 Parts of bis(biphenyl) triazine B-2 and 95 parts ofbis(biphenyl)triazine B-3 are dissolved in 1800 parts of hot2-butanone. The solvent is then stripped off under vacuum and theresulting residue is grinded to a yellowish powder (meltingpoint=62-68.degree. C.).

[0193] Preparation of Mixture (M-5):

[0194] 1 Part of bis(biphenyl) triazine B-2 and 1 part ofbis(biphenyl)triazine B-3 are dissolved in 40 parts of hot2-butanone. The solvent is then stripped off under vacuum and theresulting residue is grinded to a yellowish powder (meltingpoint=129.2.degree. C.).

[0195] Preparation of Mixture (M-6):

[0196] 1 Part of bis(biphenyl) triazine B-2 and 4 parts ofbis(biphenyl)triazine B-3 are dissolved in 40 parts of hot2-butanone. The solvent is then stripped off under vacuum and theresulting residue is grinded to a yellowish powder (meltingpoint=62.3.degree. C.).

[0197] Preparation of Mixture (M-7):

[0198] 1 Part of bis(biphenyl) triazine B-6 and 1 part ofbis(biphenyl)triazine B-3 are dissolved in 40 parts of hot2-butanone. The solvent is then stripped off under vacuum and theresulting residue is grinded to a yellowish powder (meltingpoint=137.4.degree. C.).

[0199] Preparation of Mixture (M-8):

[0200] 1 Part of bis(biphenyl) triazine B-6 and 4 parts ofbis(biphenyl)triazine B-3 are dissolved in 40 parts of hot2-butanone. The solvent is then stripped off under vacuum and theresulting residue is grinded to a yellowish powder (meltingpoint=74.degree. C.).

[0201] Preparation of Mixture (M-9):

[0202] 1 Part of bis(biphenyl) triazine B-9 and 4 parts ofbis(biphenyl)triazine B-3 are dissolved in 40 parts of hot2-butanone. The solvent is then stripped off under vacuum and theresulting residue is grinded to a yellowish powder (meltingpoint=69-76.degree. C.).

[0203] Preparation of Mixture (M-10):

[0204] 1 Part of bis(biphenyl) triazine B-2, 1 part ofbis(biphenyl)triazine B-6 and 2 parts of bis(biphenyl)triazine B-3are dissolved in 100 parts of hot 2-butanone. The solvent is thenstripped off under vacuum and the resulting residue is grinded to ayellowish powder.

[0205] Preparation of Mixture (M-11):

[0206] 1 Part of bis(biphenyl) triazine B-4, 1 part ofbis(biphenyl)triazine B-6 and 2 parts of bis(biphenyl)triazine B-3are dissolved in 100 parts of hot 2-butanone. The solvent is thenstripped off under vacuum and the resulting residue is grinded to ayellowish powder.

[0207] Preparation of Mixture (M-12):

[0208] 2 Parts of bis(biphenyl) triazine B-6, 3 parts ofbis(biphenyl)triazine B-2 and 5 parts of bis(biphenyl)triazine B-3are dissolved in 100 parts of hot 2-butanone. The solvent is thenstripped off under vacuum and the resulting residue is grinded to ayellowish powder.

[0209] Preparation of Mixture (M-13):

[0210] 1 Part of bis(biphenyl) triazine B-6, 3 parts ofbis(biphenyl)triazine B-2 and 6 parts of bis(biphenyl)triazine B-3are dissolved in 100 parts of hot 2-butanone. The solvent is thenstripped off under vacuum and the resulting residue is grinded to ayellowish powder.

[0211] Preparation of Mixture (M-14):

[0212] 12,35 g of2-(2,4-dihydroxyphenyl)-4,6-bisbiphenyl-1,3,5-triazine,corresponding to formula B-1, and 4,22 g of potassium carbonate aresuspended in 18 g of ethylcellosolve. The mixture is heated to80.degree. C., and 0.35 g of 1-bromo-2-methylpropane are addeddropwise. After stirring the mixture at 110.degree. C. for 1 hour,0.42 g of 1-bromohexane, 0.49 g of 1-bromo-octane and 6.04 g of3-(bromomethyl)-heptane are added dropwise. The mixture is stirredat 110.degree. C. for 2 hours. On cooling the mixture, a product isprecipitated. The mixture is filtered and the residue isrecrystallized to give 11.65 g of a bis(biphenyl) triazine mixturecontaining 1 part of B-6, 1 part of B-2, 1 part of B-21 and 7 partsof B-3 (melting point=87-105.degree. C.).

[0213] Preparation of Mixture (M-15):

[0214] 12,34 g of2-(2,4-dihydroxyphenyl)-4,6-bisbiphenyl-1,3,5-triazine,corresponding to formula B-1, and 4,22 g of potassium carbonate aresuspended in 18 g of ethylcellosolve. The mixture is heated to75.degree. C., and 0.35 g of 1-bromo-2-methylpropane, 0.42 g of2-bromopentane and 0.47 g of methyl-2-bromobutyrate are addeddropwise. After stirring the mixture at 110.degree. C. for 3 hours,6.04 g of 3-(bromomethyl)-heptane are added dropwise. The mixtureis stirred at 110.degree. C. for 16 hours. On cooling the mixture,a product is precipitated. The mixture is filtered and the residueis recrystallized to give 14.81 g of a bis(biphenyl) triazinemixture containing 1 part of B-4, 1 part of B-9, 1 part of B-6 and7 parts of B-3 (melting point=76-85.degree. C.).

[0215] Preparation of Mixture (M-16):

[0216] 1 Part of bis(biphenyl) triazine B-4, 1 part ofbis(biphenyl)triazine B-2 and 3 parts of bis(biphenyl)triazine B-3are dissolved in 100 parts of hot petroleum benzene. On cooling themixture, a product is precipitated. The mixture is filtered, washedwith methanol and the resulting residue is grinded to a yellowishpowder.

[0217] Preparation of Mixture (M-17):

[0218] 1 Part of bis(biphenyl) triazine B-4, 4 parts ofbis(biphenyl)triazine B-2 and 15 parts of bis(biphenyl)triazine B-3are dissolved in 100 parts of hot petroleum benzene. On cooling themixture, a product is precipitated. The mixture is filtered, washedwith methanol and the resulting residue is grinded to a yellowishpowder.

[0219] Preparation of Mixture (M-18):

[0220] 1 Part of bis(biphenyl) triazine B-4, 2 parts ofbis(biphenyl)triazine B-2 and 7 parts of bis(biphenyl)triazine B-3are dissolved in 100 parts of hot petroleum benzene. On cooling themixture, a product is precipitated. The mixture is filtered, washedwith methanol and the resulting residue is grinded to a yellowishpowder.

[0221] Solubility

[0222] Measurement of Solubility

TABLE-US-00003 Solubility in Capric/ Caprylic Triglyceride Comp.No. [w- %] (M-1) 5.0 (M-2) 2.3 (M-3) 2.4 (M-4) 1.7 (M-5) 1.8 (M-6)5.2 (M-7) 3.9 (M-12) 7.1 (M-13) 11.90 (M-14) 10.21 (M-15) 7.27(M-16) 13.31 (M-17) 7.41 (M-18) 16.57

[0223] The solubility data of the bisbiphenyl triazine mixturesM-1, M-2, M-3, M-4, M-5, M-6, M-7,

[0224] M-8, M-9, M-10, M-11, M-12, M-13, M-14, M-15, M-16, M-17 andM-18 according to the instant invention show a proper solubility.The bisbiphenyl triazine mixtures M-13, M-14, M-16 and M-18 possessextraordinary high solubility in the cosmetic oil capric/caprylictriglyceride in comparison to the commercial triazine derivativesEthylhexyl triazone (3%) and Tinosorb S (6%) corresponding to thestate-of-the-art.

[0225] Photostability

[0226] Measurement of Photostability of Highly Diluted UV AbsorberSolutions

[0227] The method used for assessment of photostability is based onthe irradiation of a highly diluted solution of the UV-filter. Theanalysis after certain doses of irradiation is performed byUV-spectroscopy. The concentration of the UV-absorber in ethanol isadjusted to values between 1.10.sup.-5 and 1.10.sup.-6 mol/l, suchthat the absorbance of the solution in cuvette of 1 cm opticalpathlength is equal or smaller than 0.2. The mutual protection offilter molecules can be excluded under such conditions.

[0228] FIG. 1 shows the experimental set-up for the irradiation ofthe samples:

[0229] Prior to irradiation of a sample the UVB-intensity at thesample position is measured with a UV-radiometer (RM-12, Dr. GrobelElectronic GmbH). This radiometer is calibrated by comparison witha measurement of the spectral output of the metal halide lamp(including light guide and cut-off filter) using awavelength-resolved radiometer (Gamma C11). Therefore therelationship of the reading of the RM-12 radiometer and thecorresponding spectral output of the lamp is known, and thewavelength-resolved intensities by measuring the UVB-intensity canbe determined.

[0230] By changing the distance between the end of the light guideand the cuvette, the UVB-intensity can be varied in the range of100 .mu.W/cm.sup.2 and 4500 .mu.W/cm.sup.2.

[0231] For sample irradiation the highest possible intensity isused (4.5 mW/cm.sup.2 UVB-intensity measured with the Macam 103radiometer). The irradiation time is varied from 0 to 180 min. Thedose the sample has received after 180 minutes corresponds to 60MED. During irradiation the sample is stirred. After certainintervals of irradiation, the samples are analysed in aUV-spectrometer (Perkin Elmer, Lambda 16).

[0232] From the absorbance values at each dose of irradiation theconcentration may be calculated using Lambert-Beer's law. In orderto get the half-life of the substance, a first order kinetic modelis fitted to the experimental data. Since the UV-spectrum of thelamp and the UV-spectrum of the COLIPA standard sun are known, onecan calculate the respective half-life of the UV-absorber underconditions of COLIPA standard sun irradiation [Bernd Herzog, StefanMuller, Myriam Sohn, Uli Osterwalder, "New Insight and Predictionof Photostablity of Sunscreens", SOFW Journal 133, 26-36(2007)].

[0233] The investigated half-time values and recovery afterirradiation (10 MED) of some specific benzotropolones are listed inthe table below:

TABLE-US-00004 Comp. No. Half time [h] Recovery after 10 MED [%](M-1) 279.1 99.4 (M-2) 655.5 99.7 (M-3) 505.1 99.7 (M-4) 535.7 99.7(M-10) 274.5 99.4

[0234] The mixtures M-1, M-2, M-3, M-4 and M-10 according to thepresent invention show high photostability and more than 99% of thebis(biphenyl) triazine derivatives are in all cases recovered afterirradiation of 10 MED.

[0235] UV Shielding Properties

[0236] The UV shielding properties of the bisbiphenyl triazinederivatives are investigated by measuring their UV spectra inethanol.

[0237] In the cases of M-14, M-15, M-16, M-17 and M-18 the UVspectra are measured in tetrahydrofuran.

[0238] In the following table the investigated absorption maxima(.quadrature..sub.max) together with the correspondingA.sup.1%.sub.1 cm values are listed:

TABLE-US-00005 Absorption maximum Comp. No. .lamda..sub.maxA.sup.1%.sub.1 cm Mixture (M-5) 317 1228 Mixture (M-6) 317 1147Mixture (M-8) 317 1204 Mixture (M-9) 317 1201 Mixture (M-1) 3171247 Mixture (M-2) 316 1238 Mixture (M-3) 317 1222 Mixture (M-4)316 1189 Mixture (M-7) 318 1363 Mixture (M-10) 317 1221 Mixture(M-11) 317 1255 Mixture (M-12) 317 1097 Mixture (M-13) 317 1199Mixture (M-14) 319 1192 Mixture (M-15) 319 1097 Mixture (M-16) 3201065 Mixture (M-17) 319 1151 Mixture (M-18) 320 1118

[0239] The bis(biphenyl) triazine mixtures according to the presentinvention possess high shielding properties in the UV region asindicated by high A.sup.1%.sub.1 cm values, which are in all caseshigher than 1000.

[0240] Measurement of Photostability of UV Absorber Solutions atRealistic Concentrations

[0241] To this purpose, 2% of the Triazine UV absorber mixture wasdissolved in Caprylic/Capric Triglyceride (Tegosoft CT).Afterwards, 1 mg/cm.sup.2 of this solution was spread on aroughened Polymethylmetacrylate (PMMA) plate with a surfaceroughness of 6 .mu.m (Helioscience, Marseille). The absorbance ofthis sample plate was then measured employing an Optometrics SPF290S Analyzer, and using a PMMA plate treated with pure glycerol asa reference. The measurement was repeated after irradiation of thesample plate by 10 and 20 minimal erythemal doses (MED),respectively, using an Atlas CPS+ solar simulator device["Photostability of UV-Absorber Systems in Sunscreens", BerndHerzog, Monika Wehrle, Katja Quass, Photochemistry andPhotobiology, Symposium in Print: Pahrmaceutical Photochemistry,85, 869-878 (2009)]. A further solution was then prepared,containing 2% of the triazine UV absorber plus 2% of Butyl MethoxyDibenzoyl Methane (BMDBM), and assessed in the same way asdescribed before for the solution of the single triazine UVabsorber. For the assessment of the photostability, the change atthe wavelength at maximum absorbance was taken.

[0242] Application Example No. A1

[0243] Photostability of mixture M-16 (2% in Tegosoft CT on PMMAplate, without BMDBM) in terms of recovery of absorbance

TABLE-US-00006 Wavelength of maximum of overall absorbance spectrum0 MED 10 MED 20 MED 315 nm 100% 104% 94%

[0244] Application Example No. A2

[0245] Photostability of mixture M-16 (2% in Tegosoft CT on PMMAplate, with 2% BMDBM) in terms of recovery of absorbance

TABLE-US-00007 Wavelength of maximum of overall absorbance spectrum0 MED 10 MED 20 MED 335 nm 100% 84% 76%

[0246] Application Example No. A2, but different evaluationwavelength

[0247] Photostability of mixture M-16 (2% in Tegosoft CT on PMMAplate, with 2% BMDBM) in terms of recovery of absorbance

TABLE-US-00008 Wavelength of maximum absorbance of BMDBM 0 MED 10MED 20 MED 360 nm 100% 76% 64%

[0248] The absorbance of the mixture M-16 at 360 nm is only onthird of its maximum absorbance at 315 nm when measured alone. Theabsorbance of M-16 together with BMDBM at 360 nm is about 90% ofthe maximum absorbance at 335 nm.

[0249] The absorbance of BMDBM at its maximum wavelength 360 nmdrops dramatically to 13%, when assessed alone (see next table). Inthe presence of M-16, the absorbance at 360 nm drops only to 64%(see last table). This indicates, that M-16 is a stabilizer ofBMDBM.

[0250] Photostability of state of the art UV absorbers (2% inTegosoft CT on PMMA plate in terms of recovery of absorbance

TABLE-US-00009 UV dose EHT EHMC BEMT DHHB BMDBM 0 MED 100% 100%100% 100% 100% 10 MED 83% 83% 96% 93% 34% 20 MED 71% 71% 87% 80%13% EHT = Ethylhexyl Triazone EHMC = Ethylhexyl MethoxycinnamateBEMT = Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine DHHB =Diethylamino Hydroxybenzoyl Hexyl Benzoate BMDBM = Butyl MethoxyDibenzoyl Methane

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