GB2438047A - Triazine derivatives as UV filters for cosmetic compositions - Google Patents

Triazine derivatives as UV filters for cosmetic compositions Download PDF

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GB2438047A
GB2438047A GB0708326A GB0708326A GB2438047A GB 2438047 A GB2438047 A GB 2438047A GB 0708326 A GB0708326 A GB 0708326A GB 0708326 A GB0708326 A GB 0708326A GB 2438047 A GB2438047 A GB 2438047A
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acid
comb
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hydrogen
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Thomas Ehlis
Elek Borsos
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BASF Schweiz AG
Ciba SC Holding AG
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Ciba Spezialitaetenchemie Holding AG
Ciba SC Holding AG
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00Medicinal preparations containing organic active ingredients
    • A61K31/33Heterocyclic compounds
    • A61K31/395Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins
    • A61K31/53Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins having six-membered rings with three nitrogens as the only ring hetero atoms, e.g. chlorazanil, melamine
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04Dispersions; Emulsions
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/494Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom
    • A61K8/4966Triazines or their condensed derivatives
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/58Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing atoms other than carbon, hydrogen, halogen, oxygen, nitrogen, sulfur or phosphorus
    • A61K8/585Organosilicon compounds
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/04Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D251/00Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/26Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
    • C07D251/40Nitrogen atoms
    • C07D251/48Two nitrogen atoms
    • C07D251/52Two nitrogen atoms with an oxygen or sulfur atom attached to the third ring carbon atom
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D251/00Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/26Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
    • C07D251/40Nitrogen atoms
    • C07D251/54Three nitrogen atoms
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D251/00Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/26Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
    • C07D251/40Nitrogen atoms
    • C07D251/54Three nitrogen atoms
    • C07D251/70Other substituted melamines
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02Silicon compounds
    • C07F7/08Compounds having one or more C—Si linkages
    • C07F7/0803Compounds with Si-C or Si-Si linkages
    • C07F7/081Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
    • C07F7/0812Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02Silicon compounds
    • C07F7/08Compounds having one or more C—Si linkages
    • C07F7/18Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804Compounds having Si-O-C linkages

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
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  • Birds (AREA)
  • Dermatology (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Dispersion Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Cosmetics (AREA)

Abstract

Triazine derivatives of formula: <EMI ID=1.1 HE=40 WI=74 LX=687 LY=725 TI=CF> <PC>wherein X1 is a bivalent radical of formula (1a) -NR9-A-NR9-, <EMI ID=1.2 HE=12 WI=19 LX=1453 LY=1151 TI=CF> <PC>(1b) or (1c) -O-A-O-; A and A' are unsubstituted or substituted, straight-chain or branched C1-C12alkylene (which is optionally interrupted by C5-C12cycloalkylene, N, O or S), C5-C12cycloalkylene, biphenylene, C6-C10arylene, or C5-C10 arylene-(C1-C12alkylene); R1 is a radical of formula (1d) -C(O)OR5, (1e) -S(O)2OR5, (1f) C(O)R5, (1g) C(O)NR5R6 or (1h) C(O)-X2-W1; R2 and R3 are hydrogen, C1-C12alkyl, OR7, NR7R8, C6-C10aryl: X2 is O or NH; W1 is C1-C20alkyl, or a group Sp-Sil; Sp is a straight-chain or branched saturated or single or multiple unsaturated C3-C12 hydrocarbon; Sil is a silane, an oligosiloxane or a polysiloxane moiety: and R4-R9 are hydrogen, C1-C10alkyl, or C3-C12cycloalkyl: are useful as UV filters. Processes for the preparation of these compounds, the preparation of micronized particles of these compounds, cosmetic compositions (particularly sunscreens) comprising them and UV absorber dispersions comprising them are also outlined.

Description

<p>Triazine derivatives The present invention relates to specific triazine
derivatives, preparation of these compounds, the preparation of micronized particles of the new tirazine derivatives and cosmetic compositions comprising these triazine derivatives.</p>
<p>The triazine derivatives correspond to formula R4fj\ RNJ)-N N-( \Z7R3 (1) R2 N)-x---( N R2, wherein N N N -i R1 R( R4 R4 R2 R2</p>
<p>A / \</p>
<p>X1 is a bivalent radical of formula (la) -NR9-A-NR9-; (ib) * N "N * ; or * ** * S S A' * *.* * (1 C) *_O..A..O..* *:..1o A and A' independently from each other are unsubstituted or substituted, straight-chain or branched C1-C12alkylene, which is optionally interrupted by C5-C12cycloalkylene, N, 0 or S; C5-C12cycloalkylene; biphenylene; C6-C10arylene; or C5-C1oarylene-(C1-C12alkylene); o 0 R1 is a radical of formula (id) ; (le) *-S0 (if) O-R5 R5 R5 (ig) *_ or(1h) R2 and R3 independently from each other are hydrogen; C1-C12alkyl; OR7; NR7R8; C6-C10aryl; X2 is0,orNH; W1 is C1-C20alkyl; or a group Sp-Sil; Sp is a straight-chain or branched saturated or single or multiple unsaturated C3-C12 hydrocarbon; Sil is a silane; an oligosiloxane; or a polysiloxaries moiety; and R4, R5 R6, R7, R8 and R9 independently from each other are hydrogen; C1-C12alkyl; or C3-C12cycloalkyl.</p>
<p>C1-C1alkyl is for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2'-dimethylpropyl, cyclopentyl cyclohexyl, n-hexyl, n-octyl, 1,1,3,3'-tetramethylbutyl or 2-ethylhexyl, nonyl, decyl, undecyl or dodecyl.</p>
<p>C6-C10aryl is for example naphthyl or preferably phenyl.</p>
<p>C1-C12alkylene is for example methylene, ethylene, propylene, isopropylene, n-butylene, sec-butylene, tert-butylene, n-pentylene, 2-pentylene 3-pentylene, 2,2'-dimethylpropylene, cyclopentylene, cyclohexytene, n-hexylene, n-octylene, 1,1',3,3'-tetramethylbutylene, 2-s. ethylhexytene, nonylene, decylene or dodecylene.</p>
<p>Alkylene may be straight-chain, branched, or, from C5alkyl upwards, monocyclic or polycyclic, and may be interrupted by hetero atoms, such as such as 0, S, -CO-, N, NH, NR 550 * :. -oco--C0(0R)-, -C0NR-, -(R)NC(0)-; for example C1-C10atkylene may be a bivalent radical such as: -CH2CH2-0-CH2CH2-0-CH2CH2--CH2CH2-0-CH2CH2-, -CH2CH2-0-CH2-, :20 -CH2-0-CH2-, -CH2CH2-CH2CH2-0-CH2-CH2-, -CH2CH2-CH(N(CH3)2)-CH2-CH2-, CH2-NH2-CH2-CH2, -CH2CH2-NH-CH2CH2-, -CH2CH2-NCH3-CH2CH2-, -C0-CH2-, -CH200-, -CH2CH2-NHCO-CH2CH2-, -CH2CH2-CONH-CH3-CH2CH2-, -CH2CH2-NCH3CO-CH2CH2-, -CH2CH2-CONCH3-CH3-CH2CH2-, -CH2-NHCO-CH2CH2-, -CH2CH2-NHCO-CH2-, -CH2CH2-CONH-CH2-or -CH2-CONH-CH2CH2-. R is hydrogen or C1-C12aIkyl.</p>
<p>C5-C10cycloatkylene is for example cyclopentylene, cyclohexytene, cycloheptylene or cyclooctylene.</p>
<p>C6-C10arylene is for example naphthylene like or -8' or preferably phenylene.</p>
<p>Preferred are compounds of formula (1)wherein o II R1 is a radical of formula (Id) ; or (ig) ; wherein O-R5 R R5 and R6 independently from each other are hydrogen; or C1-C5alkyl; and more preferably, wherein R is C1-C5alkyl; or hydrogen; and R6 is hydrogen.</p>
<p>In formula (1) X1 is preferably a radical of formula (ib), wherein A and A' are C1-C4alkylene; or wherein X1 is preferably a radical of formula (la), wherein : ... A is C1-C5alkylene; or phenylene; and R9 is hydrogen. * SI</p>
<p>Most preferably in formula (1) S..</p>
<p>X1 is selected from -NH-(CH2)2-NH-; ; ; and Most preferred are compounds of formula (1), wherein R2, R3 and R.4 are hydrogen.</p>
<p>Preferred are also compounds of formula (1), wherein Si! is the group S1R10R11R12, wherein R10, R,1 and R12 each independently are C1-C6alkyl; C1-C6alkoxy; or phenyl; or an oligosiloxane of formula -SiMem(OSiMe3)n; or an oligosiloxane of the formulae Me rMe 1 Me rMe 1 Me Me (ii) Me_i_O_j_i_O-1__i_* ; (1k) Me Si-O Si-O-Si--Me J i Me [Me Me u * Me or IMe JMe 1 Me (ii) 0 SHO Si-O-Si-Me; LMe ju * Me wherein Me is methyl; m isO;1;or2; n isl;2;or3; S. S m+nare3;and S **S *SS* * * U isOto6. **SS * *S</p>
<p>* * *4f * iu Very most preferred are compounds of formula * R-r%--N H\__, wherein *. . (2) "" N-( * . S * S. N' \>-x.-.(' R1-1-----N> N N=< R1 is a radical of formula (id) ._-_/< ; (Ig) ; or (lh) )L.. , 0-R5 N-R5 * R6 /\ X1 is radical of formula (la) -NR9-A-NR9-; (lc) *-Q-A-Q-* and -N N-A, W1, X2 and R9 are defined as in formula (1); and R5 and R6 independently from each other are hydrogen; or C1-C4alkyI.</p>
<p>Preferred are compounds of formula (2), wherein R1 is a radical of formula (id) *__ -or (ig) o R5 N-R5' R6 X1 is selected from -NH-(CH2)2-NH-; l H and</p>
<p>I</p>
<p>H and</p>
<p>R5 and R6 independently from each other are hydrogen; or C1-C4alkyl.</p>
<p>Examples of compounds of formula (1) are listed in the Table below:</p>
<p>Table 1:</p>
<p>* 4 ______ * *S* **** R * S *4S5 * * * T N=(('R1 * ** *** a * N" ">-Xj-----<\ N **. a</p>
<p>R)=N NQ S. S * ** * S. R1 Comround Li of formula (3) -CO(O)-C2H5 *_N N-(4) -CO(O)-C2H5 -NH-(CH2)2-NH- (5) -CO(O)-C2H5 (6) -CO-NH2 /___\ -* (7) -CO-NH2 -NH-(CH2)2-NH- (8) -CO(O)-C2H5 I H N,</p>
<p>H</p>
<p>Table 1:</p>
<p>R</p>
<p>NGR I N' R)=N R1</p>
<p>ComDound of formula (9) Si....</p>
<p>0 /SI..*Q I -o * Oi S* (10) 7 SL..</p>
<p>0,Si-_0 S... *</p>
<p>* S S _________ ____________________ ____________________________________________ S *.</p>
<p>S.. 5 (11) ..... 7 0 Si0 Si-....</p>
<p>S _o Si</p>
<p>H 5S S * S S</p>
<p>* (12) *</p>
<p>H</p>
<p>0 ________________________________________ (13) -C0(O)-CH3 /\ *_N N-* \-/ (14) 0 _________________________________________ (15) o H N.... *-..1</p>
<p>0 _________________________________________ (16) 0 _________________________________________</p>
<p>Table 1:</p>
<p>R</p>
<p> N N-( N))-X--(\ ,N</p>
<p>N N</p>
<p>-H H R1</p>
<p>Compound of formula (17) 0 _______________________ S *** ____________ SSSS (18)</p>
<p> N H</p>
<p>S S S... 0 H</p>
<p>S S..</p>
<p>* (19) *. . * * I * * * *. (20) (21)</p>
<p>s_N N-(22)</p>
<p>H</p>
<p>H</p>
<p>(23) *</p>
<p>H</p>
<p>Table 1:</p>
<p>R N<</p>
<p>I N' ,N N-< R>=N R1 ComDound -xl of formula ____________________ * (24) C * S * *** S...</p>
<p>______ ____________________</p>
<p>**. (25)</p>
<p>N</p>
<p>* * 0 *</p>
<p>S *..</p>
<p>(26) \/ Si-..0 I Si-..... * . .</p>
<p>* *5 * (27) N Si-...</p>
<p>0 Si....0 H * -o (28) \/ N\-H 0 I SL. H N.. (29)</p>
<p>H</p>
<p>Si-..... * 0 Si0</p>
<p>H tNH</p>
<p>(30) \/.-..-Si-.....</p>
<p>0 Si-0</p>
<p>N ri</p>
<p>Table 1:</p>
<p>R</p>
<p>-</p>
<p>R)=N -c R1 Compound R1 of formula * (31) Si..... H -IYQ-i{ Si...0 *.* S...</p>
<p>* (32) Vs( S* * S** * I S..</p>
<p>/ .-.. - (33) Si-. H * .. Si..</p>
<p>H</p>
<p>(34) \/ ,.-Si..0 (35) 0 Si..0 I (36) o</p>
<p>H</p>
<p>-10 -</p>
<p>Table 1:</p>
<p>R</p>
<p>N=(KR1 T N' ,N R)=N N-(ç R1 ________ xl Compound of formula (37) -o Si S. I S..</p>
<p>(38) SI-o Si-0 *. S</p>
<p>SI</p>
<p>*. . H I S.. ______________ _______________________________ ____________________________________________________________________ (39) -</p>
<p>S Si...</p>
<p> N</p>
<p>o Si.0 H * )N -o</p>
<p>S S Si</p>
<p>* S. * H (40) Si....</p>
<p>o Si.0 )N -o Si * H</p>
<p>H</p>
<p>(41) SI-o Si.0 )..- -o H Si * H (42) SI--o s,.</p>
<p>)-N-7-..' -o Si</p>
<p>H I</p>
<p>(43) Si-....</p>
<p>o Si.0 -o Si * H -11 -</p>
<p>Table 1:</p>
<p>R O-rj</p>
<p>-</p>
<p>N N' -R)N R1</p>
<p>Compound R1 of formula F Si-..., (44) / o Si.-01 * H</p>
<p>S * H S * S *sS</p>
<p>(45) \/ *-S( H o Si.-0</p>
<p>H *.</p>
<p>S</p>
<p>H S.S *</p>
<p>* (46) Si.....</p>
<p>/ ...-.-* o Si.-0 )LN-O</p>
<p>H * *.</p>
<p>S I S * (47) .-.-,.. .- SI-.- o Si.-0 -* H I (48) Si-....</p>
<p>/ N N N o Si.-01 H H</p>
<p>H</p>
<p>(49) \/ . oo* Si....</p>
<p>o Si.-0 * LNI0 * H I / ..-.-(50) Si Si-_0 *</p>
<p>________________________________________________ I -12-</p>
<p>Table 1: R1</p>
<p>N' >-x-----,N R>N Nc R1 Compound of formula (51) S 5.5 (52) S. S S.. 5 0 S.. ____________________________________________________________________ * (53) ** .</p>
<p>SS * *5 (54)</p>
<p>o /SlO N Si</p>
<p>H</p>
<p>(55) -CO(O)-CH3 NH(CH2)2NH</p>
<p>NH (56) * (57)</p>
<p>0 )ç-o Si</p>
<p>____________________________________________________________ I</p>
<p>-13 -</p>
<p>Table 1:</p>
<p>R)N N-ç Compound of formula (58) *NH *: *.. _____________ ____________________________ _____________________________________________________________ *::. (59) (60) *NH The compounds of formula (1) are prepared by methods known from the prior art, as disclosed for example in Journal of the Institution of Chemists (inida), 6(5), p. 197 (1984); or in Journal of the Institution of Chemists (inida), 57(6), p. 233 (1985); or in EP 818 450.</p>
<p>The method generally comprises reacting 2 moles of a halogentriazine of formula (1 m), preferably chlorotriazine, with 1 mole of the compound of formula (in) to give the compound of formula (1) according to the follwing reaction scheme: -14-</p>
<p>R R R R4_f\</p>
<p>R'! s_-N R' s-N N-_( R3 R N + 1 H-X-H R N -X---' N R</p>
<p> NR</p>
<p>(im) (in) (1) wherein R1, R2, R3, R4 and X1 are defined as in formula (1).</p>
<p>The reaction is preferably carried out in dipolar aprotic solvents, like dimetylfomamide, di- :. methylsulfoxide, sulfolane, N-methyl-pyrrolidone; hydrocarbons like xylene or toluene, tetra-line, petroleum, mesytilene or benzene; hydrogenated halocarbons like chlorobenzene or dichlorobenzene; or without a solvent using an excess of a base like tetraalylamines; or without any solvent and a base in a "melt process". *. 10</p>
<p>The reaction temperature is preferably from 20 to 280, preferably 30 to 200, and most *.. preferably from 4Oto 150 C.</p>
<p>Preferred bases used in the present process are trialkylamines like triethylamine, ethyl-iso-propylamirie, heterocyclic amines like DABCO or DBU, or inorganic bases like NH2CO3 or NaHCO3.</p>
<p>The compounds of the formula (1) according to the present invention are particularly suitable as UV filters, i.e. for protecting ultraviolet-sensitive organic materials, in particular the skin and hair of humans and animals, from the harmful effects of UV radiation. These compounds are therefore suitable as sunscreens in cosmetic, pharmaceutical and veterinary medical preparations. These compounds can be used both in dissolved form and in the micronized state.</p>
<p>The compounds of the formula (1) according to the present invention are particularly suitable as UV filters, i.e. for protecting ultraviolet-sensitive organic materials, in particular the skin and hair of humans and animals, from the harmful effects of UV radiation. These compounds are therefore suitable as sunscreens in cosmetic, pharmaceutical and veterinary medical preparations. These compounds can be used both in dissolved form and in the micronized state.</p>
<p>The UV absorbers of formula (1) according to the present invention, depending on the definition of X1 and R1 can be used either in the dissolved state (soluble organic filters, solubelized organic filters) or in the micronised state (nanoscalar organic filters, particulate organic filters, UV-absorber pigments).</p>
<p>Any known process suitable for the preparation of microparticles can be used for the pre-paration of the micronised UV absorbers, for example: -wet-milling (low viscous micronisation process for pumpable dispersions), with a hard grinding medium, for example zirconium silicate balls in a ball mill and a protective :.,. surfactant or a protective polymer in water or in a suitable organic solvent; -wet-kneading (high viscous micronisation process non pump-able pastes) using a : * 15 continuous or discontinuous (batch) kneader. For a wet-kneading process a solvent (water or cosmetically acceptable oils), a grinding-aid (surfactant, emulsifier) and a * polymeric grinding aid may be used.</p>
<p>*:*. -spray-drying from a suitable solvent, for example aqueous suspensions or suspensions containing organic solvents, or true solutions in water, ethanol, dichioroethane, toluene or N-methylpyrrolidone etc..</p>
<p>-by the expansion according to the RESS process (apid xpansion of upercritical Solutions) of supercritical fluids (e.g. GO2) in which the UV filter or filters is/are dissolved, or the expansion of fluid carbon dioxide together with a solution of one or more UV filters in a suitable organic solvent; -by reprecipitation from suitable solvents, including supercritical fluids (GASR process = Gas Anti-Solvent Recrystallisation / PCA process = recipitation with ompressed Anti-solvents).</p>
<p>As milling apparatus for the preparation of the micronised organic UV absorbers there may be used, for example, a jet mill, ball mill, vibratory mill or hammer mill, preferably a high-speed mixing mill. Even more preferablyused are modern ball mills; manufactures of these mill-types are for example Netzsch (LMZ-mill), Drais (DCP-viscoflow or cosmo), Bühler AG (centrifugal mills) or Bachhofer. The grinding is preferably carried out with a grinding aid.</p>
<p>-16 -As kneading apparatus for the preparation of the micronised organic UV absorbers examples are typically sigma-hook batch kneaders but also serial batch kneaders (IKA-Werke) or continuous kneaders (Contiuna from Werner und Pfleiderer).</p>
<p>Useful low molecular weight grinding aids for all the above micronizing processes are sur-factants and emulsifies as disclosed below in the chapters "emulsifiers" and "surfactants" and "fatty alcohols".</p>
<p>Useful polymeric grinding aids for water dispersion are cosmetically acceptable water soluble polymers with Mn> 500 g/mol for example acrylates (Salcare types), modified or non-modified polysaccharides, polyglucosides or xanthan gum. Furthermore an alkylated vinylpyrrolidone polymer, a vinylpyrrolidone/vinyl acetate copolymer, an acyl glutamate, an alkyl polyglucoside, ceteareth-25 or a phospholipid may be used. Oil dispersions may contain *. cosmetically acceptable waxy polymers or natural waxes as polymeric grinding aid in order to adjust viscosity during and after processing. Examples of other useful polymeric grinding aids are dieclosed below in the chapter "polymers".</p>
<p>Useful solvents for the grinding process are water, brine, (poly-)ethylenglycol, glycerine or * . cosmetically acceptable oils. Other useful sovents are disclosed below in the chapters "esters of fatty acids", "natural and synthetic triglycerides including glyceryl esters and derivatives", "perlescent waxes", "hydrocarbon oils" and "silicories or siloxanes".</p>
<p>The micronised UV absorbers so obtained usually have an average particle size from 0.02 to 2, preferably from 0.03 to 1.5, and more especially from 0.05 to 1.0 micrometer.</p>
<p>A further object of the present invention is a UV absorber dispersion, comprising (a) a micronised UV absorber of formula (1), each of them having a particle size from 0,02 to 2 jim, and (b) a suitable dispersing agent.</p>
<p>The UV absorbers according to the present invention can also be used as dry substrates in powder form. For that purpose the UV absorbers are subjected to known grinding methods, such as vacuum atomization, countercurrent spray-drying etc.. Such powders have a particle size from 0.1 micrometer to 2 micrometer. In order to avoid the occurrence of agglomeration, -17-the UV absorbers may be coated with a surface-active compound prior to the pulverization process, for example with an anionic, non-ionic or amphoteric surfactant, e.g. a phospholipid or a known polymer, such as PVP, an acrylate etc..</p>
<p>The UV absorbers according to the present invention can also be used in specific carriers for cosmetics, for example in solid lipid nanoparticles (SLN) or in inert sol-gel microcapsules wherein the UV absorbers are encapsulated (Pharmazie, 2001 (), p. 783-786).</p>
<p>Lipid nanoparticles (CLN, = Crystalline Lipid anoparticles) as described in lnternat.</p>
<p>J. Pharmaceutics, 2002, 242, P. 373-375 can be used as active carrier for UV filter according to the invention.</p>
<p>The cosmetic formulations or pharmaceutical compositions according to the present inven-tion may additionally contain one or more than one further UV filter as listed in Tables 1-3. *... S...</p>
<p>The cosmetic or pharmaceutical preparations can be prepared by physically mixing the UV absorber(s) with the adjuvant using customary methods, for example by simply stirring to- * gether the individual components, especially by making use of the dissolution properties of * : already known cosmetic UV absorbers, like octyl methoxy cinnamate, salicylic acid isooctyl * 20 ester, etc.. The UV absorber can be used, for example, without further treatment, or in the micronised state, or in the form of a powder.</p>
<p>Cosmetic or pharmaceutical preparations contain from 0.05-40% by weight, based on the total weight of the composition, of one UV absorber or UV absorber mixtures.</p>
<p>Preference is given to the use of mixing ratios of the UV absorber of formula (1) according to the present invention and optionally further light-protective agents (as described in table 1-3) from 1:99 to 99:1, preferably from 1:95 to 95:1 and most preferably from 10:90 to 90:10, based on weight. Of special interest are mixing ratios of from 20:80 to 80:20, preferably from 40.60 to 60:40 and most preferably approximately 50:50. Such mixtures can be used, inter a/ia, to improve the solubility or to increase UV absorption.</p>
<p>The UV absorbers of formula (1) according to the present invention or combinations of UV filters are useful to protect skin, hair and/or natural or artificial hair color.</p>
<p>Table 2: Suitable UV filter substances which can be additionally used with the UV absorbers according to the present invention p-aminobenzoic acid derivatives, for example 4-dimethylam inobenzoic acid 2-ethylhexyl ester; salicylic acid derivatives, for example salicylic acid 2-ethyihexyl ester; benzophenone derivatives, for example 2-hydroxy-4-methoxybenzophenone and its 5-sulfonic acid derivative; dibenzoylmethane derivatives, for example 1 -(4-tert-butylphenyl)-3-(4-methoxyphenyt)-propane-i,3-dione; diphenylacrylates, for example 2-ethyihexyl 2-cyano-3, 3-diphenylacrylate, and 3-(benzo-furanyl) 2-cyanoacrylate; 3-imidazol-4-ylacrylic acid and esters; benzofuran derivatives, especially 2-(p-aminophenyl)benzofuran derivatives, described in EP-A-582 189, US-A-5 338 539, US-A-5 518 713 and EP-A-613 893; : polymeric UV absorbers, for example the benzylidene malonate derivatives described in ... EP-A-709 080; S...</p>
<p>cinnamic acid derivatives, for example the 4-rnethoxycinnamic acid 2-ethylhexyl ester and isoamyl ester or cinnamic acid derivatives described in US-A-5 601 811 and WO 97/00851; :. camphor derivatives, for example 3-(4'-methyl)benzyhdene-bornan-2-one, 3-benzylidene- bornan-2-one, N-[2(and 4)-2-oxybom-3-ylidene-methyl)-benzyl]acrylamide polymer, 3-(4'-trimethylammonium)-benzylidene-bornan-2-one methyl sulfate, 3, 3'-(l,4-phenylenedi-methine)-bis(7, 7-dimethyl-2-oxo-bicyclo[2.2. 1]heptane-1 -methanesulfonic acid) and salts, 3-(4'-sulfo)benzylidene-bornan-2-one and salts; camphorbenzalkonium methosulfate; hydroxyphenyltriazine compounds, for example 2-(4'-methoxyphenyl)-4,6-bis(2'-hydroxy-4'- n-octyloxyphenyl)-1, 3, 5-triazine; 2,4-bis{[4-(3-(2-propyloxy)-2-hydroxy-propyloxy)-2-hy-droxy]-phenyl}-6(4-methoxyphenyl)-1, 3,5-triazine; 2,4-bis{[4-(2-ethyl-hexyloxy)-2-hyciroxy]-phenyl}-6-[4(2-methoxyethyl-carboxyl)-phenyl amino]-1,3,5-triazine; 2,4-bis{[4-(tris(tnmethylsilyloxy-silylpropyloxy)-2-hydroxy]-ph enyl}-6-(4-methoxyphenyl)-1,3, 5-triazine; 2,4-bis{[4-(2"-methylpropenyloxy)-2-hydroxyj-phenyl}-6-(4-methoxyphenyl) -1,3, 5-triazine; 2,4-bis{[4-( 1', 11,1,3',5',5',5'-heptamethyltrisilyl-2"-methyl-propyloxy)-2-hydroxy] -phenyl}-6_ (4-methoxyphenyl)-1,3, 5-triazine; 2, 4-bis{[4-(3-(2-propyloxy)-2-hydroxy-propyloxy)-2-hydroxyj-phenyl}-6[4-ethylcarboxy)-phenylam ino]-1, 3,5-triazi ne; benzotriazole compounds, for example 2,2'-methylene-bis(6-(2H-benzotriazol-2-yI)-4-(1,1,3,3-tetramethylbutyl) -phenol; trianilino-s-triazine derivatives, for example 2,4,6-trianiline-(p-carbo-2'-ethyl-i'-oxy)-l 3,5-triazine and the UV absorbers disclosed in US-A-5 332 568, EP-A-5i7 104, EP-A-507 691, 2-phenylbenzimidazole-5-sulfonic acid and salts thereof; menthyl o-aminobenzoates; physical sunscreens coated or not as titanium dioxide, zinc oxide, iron oxides, mica, MnQ, Fe203, Ce203, A1203, Zr02. (surface coatings: polymethylmethacrylate, methicone -19-Table 2: Suitable UV filter substances which can be additionally used with the UV absorbers according to the present invention (methyihydrogenpolysiloxane as described in CAS 9004-73-3), dimethicone, isopropyl titanium triisostearate (as described in CAS 61417-49-0), metal soaps as magnesium stearate (as described in CAS 4086-70-8), perfluoroalcohol phosphate as C9-15 fluoroalcohol phosphate (as described in CAS 74499-44-8; JP 5-86984, JP 4-330007)).</p>
<p>The primary particle size is an average of l5nm-35nm and the particle size in dispersion is in the range of lOOnm -300nm.</p>
<p>aminohydroxy-benzophenone derivatives disclosed in DE 10011317, EP 1133980 and EP phenyl-benzimidazole derivatives as disclosed in EP 1167358 the UV absorbers described in "Sunscreens", Eds. N.J. Lowe, N.A.Shaath, Marcel Dekker, Inc., New York and Basle or in Cosmetics & Toiletries (107), 50ff (1992) also can be used as additional UV protective substances.</p>
<p>Table 3: Suitable UV filter substances which can be additionally used with the UV :. absorbers according to the present invention (Abbreviations T: table, R: row, Comp: compound, Ex: compound(s) of patent example, p: page); the generic scope of the UV absorbers is described in the left-hand column; specific compounds are indicated in the right-hand column : *, DE 100331804 Tab 1 p 4, tab 2 + 3 p 5 EP 613893 Ex 1-5 + 15, T 1, pp 6-8 EP 1000950 Comp. in table 1, pp 18-21 EP1005855 T3,p13 . : EP1008586 Ex 1-3, pp 13-15 * EP1008593 Exl-8,pp4-5 EP1027883 Compound VII, p3 EP1027883 Comp 1-VI, p 3 EP1028120 Ex 1-5, pp 5-13 EP1059082 Exl;T1,pp9-11 EP 1060734 T 1-3, pp 11-14 EP 1064922 Compounds 1-34, pp 6-14 EP 1081140 Ex 1-9, pp 11-16 EP 1103549 Compounds 1-76, pp 39-51 EP1 108712 4,5-Dimorpholino-3-hydroxypyridazine EP1123934 T3,plO EP1129695 Ex 1-7, pp 13-14 EP1167359 Ex 1 p11 and ex2 p12 EP1258481 Ex 1, pp 7,8 EP 420707 Bi Ex 3, p 13 (GAS Regno 801 42-49-0) EP503338 Ti, pp 9-10 EP 517103 Ex 3,4,9,10 pp 6-7 EP517104 Exl,T1pp4-5;Ex8, T2,pp6-8 EP 626950 all compounds EP669323 Exl-3,p5 EP780382 Exl-11,pp5-7 EP 823418 Ex 1-4, pp 7- 8 Table 3: Suitable UV filter substances which can be additionally used with the UV absorbers according to the present invention (Abbreviations T: table, R: row, Comp: compound, Ex compound(s) of patent example, p: page); the generic scope of the UV absorbers is described in the left-hand column; specific compounds are indicated in the right-hand column EP826361 T1,pp5-6 EP 832641 Ex 5+6 p 7; t 2, p 8 EP 832642 Ex 22, T 3 pp, 10-15; T 4, p 16 EP852137 T2, pp 41-46 EP858318 T1,p6 EP863145 Ex 1-11, pp 12-18 EP 895776 Comp. in rows 48-58, p 3; R 25+33, p 5 EP911020 T2, p11-12 EP 916335 T 2-4, pp 19-41 EP924246 T2,p9 EP 933376 Ex 1-15, pp 10-21 EP944624 Exl+2,ppl3-15 EP 945125 T 3 a+b, pp 14-15 EP 967200 Ex 2; T 3-5, pp 17-20 EP 969004 Ex 5, 1 1, pp 6-8 JP 2000319629 CAS Regno. 80142-49-0, 13721 5-83-9, 307947-82-6 US 5635343 all compounds on pp 5-10 : *. US 5338539 Ex 1-9, pp 3+4 US5346691 Ex40,p7;T5,p8 *: US5801244 Exl-5,pp6-7 : wO 0168047 Tables on pp 85-96 * W00181297 Exl-3pp9-11 WO 0238537 All componds p 3, compounds on rows 1-10 p 4 WO 9220690 Polymeric comp in examples 3-6 Table 4: Suitable UV fUter substances and adiuvants which can be additionally used with the UV absorbers according to the present invention Chemical Name CAS No. I (-i-I-)-1, 7, 7-trimethyl-3-[(4-methylphenyl)methylene]bicyclo[2.2. 1]-36861-47-9 _____ heptan-2-one; p-methyl benzylidene camphor 2 1,7, 7-trimethyl-3-(phenylmethylene)bicyclo[2.2.1]heptan-2-one; 15087-24-8 _____ benzylidene camphor 3 (2-Hydroxy-4-methoxyphenyl)(4-methylphenyl)methanone 1641-17-4 4 2,4-dihydroxybenzophenone 131-56-6 2,2',4,4'-tetrahydroxybenzophenone 131-55-5 6 2-Hydroxy-4-methoxy benzophenone 131-57-7 - -21 -Table 4: Suitable UV filter substances and adiuvants which can be additionally used with the UV absorbers according to the resent invention Chemical Name CAS No. 7 2-Hydroxy-4-methoxy benzophenone-5-sulfonic acid 4065-45-6 8 2,2'-dihydroxy-4,4'-dimethoxybenzophenone 131-54-4 9 2, 2'-Dihydroxy-4-methoxybenzophenone 131-53-3 Alpha-(2-oxoborn-3-ylidene)toluene-4-sulphonic acid and its salts; 56039-58-8 _____ Mexoryl SL 11 1 -[4-( 11 -dimethylethyl)phenyl]-3-(4-methoxyphenyl)propane-1 3-70356-09-1 diane; avobenzone 12 Methyl N, N, N-trimethyl-4-[(4, 7, 7-trimeth yl-3-oxobicyclo[2,2, 1 Jhept-2-52793-97-2 _____ ylidene)methyl]anilinium sulphate; Mexoryl SO 22 3,3,5-Trimethyl cyclohexyl-2-hydroxy benzoate; homosalate 118-56-9 23 Isopentyl p-methoxycinnamate; isoamyl methoxy cinnamate 7161 7-10-2 - 27 Menthyl-o-aminobenzoate 134-09-8</p>
<p>_______ __________________________________________________________________________ _______</p>
<p>28 Menthyl salicylate 89-46-3 29 2-Ethylhexyl 2-cyano, 3,3-diphenylacrylate; Octocrylene 6197-30-4 * 30 2-ethylhexyl 4-(dimethylamino)benzoate 21245-02-3 31 2-ethylhexyl 4-methoxycinnamate; octyl methoxy cinnamate 5466-77-3 *: * 32 2-ethylhexyl salicylate 118-605 33 Benzoic acid, 4, 4', 4"-(1, 3, 5-triazine-2, 4, 6-triyltriimino)tris-, 881 22-99-0 tris(2-ethylhexyl)ester; 2,4, 6-Tria nilino-( p-carbo-2'-ethylhexyl-l -oxi)- 1,3,5-triazine; octyl triazone 34 4-aminobenzoic acid 150-13-0 Benzoic acid, 4-amino-, ethyl ester, polymer with oxirane 113010-52-9 - 38 2-phenyl-1H-benzimidazole-5-sulphonic acid; 27503-81-7 - _____ phenylbenzimidazolsulfonic acid 39 2-Propenamide, N-[4-[(4,7,7-trimethyl-3-oxobicyclo[2.2. 1]hept-2-147897-12-9 _____ ylidene)methyl]phenyl]methyl]-, homopolymer Triethanolamine salicylate 21 74-16-5 - 41 3, 3'-( I,4-phenylenedimethylene)bis[7, 7-dimethyl-2-oxo-90457-82-2 ____ bicyclo[2.2.1]heptane-1 methanesulfonic acid]; Cibafast H 42 Titanium dioxide 13463-67-7 44 Zinc oxide 1314-13-2 2, 2'-Methylene-bis-[6-(2H-benzotriazol-2-yl)-4-( 1,1,3, 3-tetramethyl-103597-45-1 _____ butyl)-phenol]; Tinosorb M 46 2,4-bis{[4-(2-ethylhexyloxy)-2-hyd roxy]-phenyl}-6-(4-187393-00-6_- -22 -Table 4: Suitable UV filter substances and adjuvants which can be additionally used with the UV absorbers according to the present invention No Chemical Name GAS No. _____ methoxyphenyl)-(1,3,5)-triazine; Tinosorb S 47 1 H-Benzimidazole-4,6-disuffonic acid, 2, 2'-( 1,4-phenylene)bis-, 180898-37-7 disodium salt 48 Benzoic acid, 4,4'-[6-[4-[( 1,1 -dimethylethyl)amino]carbonyl]phenyl]-154702-15-5 aminoJ 1,3,5-triazine-2,4-diyl)diimino]bis-, bis(2-ethylhexyl)ester; di- _____ ethylhexyl butamido triazone; Uvasorb HEB 49 Phenol, 2-(2 l-l-benzotriazol-2-yl)-4-methyl-6-[2-methyl-3-[1 3,3,3-155633-54-8 tetramethyl-1 -[(trimethylsilyl)oxyjdisiloxanyl]propyl]-; drometrizole _____ trisiloxane; Mexoryl XL Dimethicodiethylbenzalmalonate; Polysilicone 15; Parsol SLX 207574-74-1 51 Benzenesulfonic acid, 3-(2H-benzotriazol-2-yl)-4-hydroxy-5-( 1-92484-48-5 _____ methyipropyl)-, monosodium salt; Tinogard HS : ... 52 Benzoic acid, 2-[4-(diethylamino)-2-hydroxybenzoyl]-, hexyl ester; 302776-68-7 **., Uvinul a plus 53 1 -Dodecanaminium, N-[3-[4-(dimethylamino)benzoyl]amino]propyl]-156679-41-3 : ** N,N-dimethyl-, salt with 4-methylbenzenesulfonic acid (1:1); Escalol HP61O * 54 1 -Propanaminium, N, N,N-trimethyl-3-[( 1-oxo-3-phenyl-2-propenyl)-177190-98-6 _____ amino]-, chloride 1 H-Benzimidazole-4,6-disulfonic acid, 2,2'-( 1, 4-phenylene)bis-170864-821 56 1,3,5-Triazine, 2,4,6-tris(4-methoxyphenyl)-7753-12-0 57 1,3,5-Triazine, 2,4,6-tris[4-[(2-ethylhexyl)oxy]phenyl]-208114-14-1 58 1 -Propanaminium, 3-[3-[3-(2H-benzotriazol-2-yl)-5-( 1,1 -340964-15-0 dimethylethyl)-4-hydroxyphenyl]-1 -oxo propyl]amino]-N, N-diethyl-N- _____ methyl-, methyl sulfate (salt) 59 2-Propenoic acid, 3-(1 H-imidazol-4-yl)-104-98-3 Benzoic acid, 2-hydroxy-, [4-(1 -methylethyl)phenyl]methyl ester 94134-93-7 61 1,2,3-Propanetriol, 1-(4-aminobenzoate); glyceryl PABA 136-44-7 62 Benzeneacetic acid, 3,4-d imethoxy-a-oxo-4732-70-1 63 2-Propenoic acid, 2-cyano-3,3-diphenyl-, ethyl ester 5232-99-5 64 Anthralinic acid, p-menth-3-yl ester 134-09-8 2,2'- bis( 1,4-phenylene)-1 H-benzimidazole-4,6-disulphonic acid mo-349580-12-7, no sodium salt or Disodium phenyl dibenzimidazole tetrasulfonate or _____ Neoheliopan AP 66 1,3,5-Triazine-2,4,6-triamine, N,N'-bis[4-[5-( 1,1 -dimethylpropyl)-2-288254-16-0 benzoxazolyl]phenyl]-N"-(2-ethylhexyl)-or Uvasorb K2A -23 -Table 4: Suitable UV filter substances and adiuvants which can be additionally used with the UV absorbers according to the present invention flp.. Chemical Name GAS No. 67 Merocyanine derivatives as described in WO 2004006878 and in 1PCOM000022279D H H i-f CN 68 sterols (cholesterol, lanosterol, phytosterols), as described in 69 mycosporines and/or mycosporine-like amino acids as described in W02002039974, e.g. Helioguard 365 from Milbelle AG, isolated :. mycosporine like amino acids from the red alga porphyra umbilicalis ____ (INCI: Porphyra Umbilicalis) that are encapsulated into liposomes,) ____________ alpha-lipoic-acid as described in DE 10229995 : *** 71 synthetic organic polymers as described in EP 1371358, [0033]- ____ [0041] ___________ 72 phyllosilicates as described in EP 1371357 [0034]-[0037] _____________ 73 silica compounds as described in EP1371356, [0033]-[00411 ___________ 74 inorganic particles as described in DEl 0138496 [00431-[0055] _____________ latex particles as described in DE1O1 38496 [0027]-[0040] ____________ 76 1 H-Benzimidazole-4,6-disulfonic acid, 2,2'-( 1,4-phenylene)bis-, 180898-37-7 disodium salt; Bisimidazylate; Neo Heliopan APC Preferred cosmetic and/or dermatological compositions according to the present invention are: Ia. Cosmetic and/or dermatological compositions for the protection from UV radiation comprising a compound of formula (1) and powders having a core of at least one siloxane elastomer coated with trimethylsiloxylate andlor its derivatives as described in DE 101 57 489 from page 2, line 46 to page 4, line 6 and page 4, line 49 -54.</p>
<p>lb. Cosmetic and/or dermatological compositions for the protection from UV radiation comprising a compound of formula (1) and powders having a core of at least one siloxane elastomer coated with trimethylsiloxylate and/or its derivatives and a further UV filter selected from the group of triazines, benzotriazoles, UV filters being liquid at room temperature, sulfonated, water soluble UV filters, oil soluble UV broadband filters and organic and/or anorganic pigments, which are preferably suface-coated as described in DE 101 57 489, ≈[051] -[0079].</p>
<p>2. Self-tanning composition comprising a cosmetic acceptable carrier: (a) at least a self tanning agent; and (b) at least a compound of formula (1) as described in EP-A-1.31 7,920.</p>
<p>3. Cosmetic and/or dermatological composition for topical use comprising in a cosmetic</p>
<p>acceptable medium</p>
<p>:. (a) 0.1 -15% b.w. of 1.4-di(3-methylidene-10-comphosulfonic) benzoic acid; and (b) 0.1 -15% b.w. of a compound of formula (1). S...</p>
<p>As described in EP-A-1,317,919. *</p>
<p>* . 15 * S :. 4. Cosmetic and/or dermatological composition for topical use, preferably for the photoprotection of the skin and/or hair comprising in a cosmetic acceptable medium</p>
<p>S</p>
<p>(a) at least an insoluble organic UV filter having a particle size from 10 nm to 5 pm as first filter as desribed, for example in EP-A-1,317,918 ≈[0025]-[0050]; and (b) as second filter at least one compound of formula (1).</p>
<p>5. Cosmetic and/or dermatological composition for the protection against UV radiation with UV filters selected from a compound of formula (1), anorganic micro pigments and at least one siloxane elastomer selected from the group existing of siloxane elastomers ob- tamable either by the reaction of vinyl-terminal polymethylsiloxane and methylhydrodi-menthylsiloxane or by reaction of hydroxy-terminal dimethylpolysiloxane and trimethyl-siloxy-terminal methylpolysioxane in form of spheric powder or in form of gels as described in DE 101 55 865, ≈[0009] -[001 3], [0020] -[0021] and [0045] -[0050].</p>
<p>6. Cosmetic and/or dermatological compositions for the protection against UV radiation comprising (a) at least one compound of formula (1); (b) at least one triazine-or benzotriazole derivative as described in WO 03/039507, pages 5-16; and optionally further cosmetic actives, adjuvants and additives as described in 7a. Cosmetic and/or dermatological compositions comprising (a) at least one compound of formula (1); (b) at least one dialkylnaphthalate of formula I ? , wherein o,-,-R2 R1 and R2 independently from each other are branched or unbranched C6-C24alkyls As described in WO 03/039506 * ** * . * 7b. Cosmetic and/or dermatological compositions comprising * (a) at least one compound of formula (1); ** * 0 *. .: (b) at least a dialkylnaphthalate of formula i I " , wherein 0,-R2 R1 and R2 independently from each other are branched or unbranched C6-C24alkyls; and (c) a further UV filter selected from the group of triazines, benzotriazoles, liquid UV filters and organic and/or inorganic pigments as described in WO 03/039506, page 17, line 20 and page 18-20.</p>
<p>8a. Cosmetic and/or dermatological composition comprising (a) a compound of formula (1) and (b) 8-hexadecene-1.16-dicarboxylic acid; as described in WO 03/039,502.</p>
<p>8b. Cosmetic and/or dermatological composition comprising (a) a compound of formula (1); -26 (b) 8-hexadecene-1.1 6-dicarboxylic acid; and (c) a further UV-A filter and/or broadband filter selected from the group of dibenzoyl- methane derivatives, preferably 4-(tert. butyl)-4'-methoxydibenzoylmethane, pheny-lene-1,4-bis-(2-benzimidazyl)-3,3'-5,5'-tetrasulfonic-bissodium salt, 1,4-di(2-oxol 0- sulfo-3-bornylidenemethyl)-benzene and the salts thereof and 2,4-bis-{4-(2-ethyl-hexyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-1,3, 5-triazi ne, wherein the fil- ters may be present as single substances or in any combination of each sub-stance.</p>
<p>9. Self-foaming, foaming, after-foaming or foamable cosmetic and/or dermatological compositions comprising I. an emulsifier system as described for example in WO 03/039493, pages 6 -19, consisting of A. at least one emulsifier A selected from the group of totally partially or not *... 15 neutralized, branched and/or unbranched, saturated and/or unsaturated C10-C40fatty acids; B at least one emulsifier B selected from the group of polyethoxylated C10-Cfatty acid esters having an ethoxylation degree of 5 -50; C at least one co-emulsifier C selected from the group of saturated and/or * *: 20 unsaturated branched and/or unbranched Cio-Cofatty alcohols; and II. until 30 % b.w., based on the overall weight of the composition,of a lipid phase comprising (a) one or more lipids selected from silicon oils and silicon waxes; and (b) one or more lipids selected from inpolar lipids having a polarity = 30 mM/rn wherein the ratio (a): (b) is in the range of 1:3 -3:1; and (c) 0.5-10, preferably 0.5-10% b.w. of at least one compound of formula (1).</p>
<p>10. Cosmetic and/or dermatological compositions for the protection against UV radiation comprising (a) at least one compound of formula (1); and (b) potassium-ethylenediaminetetramethlenephosphonate as described in EP-A-1,310,239 ≈[0027] -[0028]. -27</p>
<p>11. Cosmetic and/or dermatological compositions for the protection against UV radiation comprising (a) at least one compound of formula (1); and (b) at least an acrylamide polymer, acrylamide copolymer, and derivatives thereof and/or an acrylamide polymer, acrylamide copolymer and derivatives thereof; as described in EP-A-1,31 0,239.</p>
<p>12. Cosmetic and/or dermatological compositions for the protection from UV radiation comprising (a) at least one compound of formula (1); and :. (b) imidosuccinic acid and/or derivatives thereof as described for example in EP-A-1,310,236 ≈[00281-[0030].</p>
<p>13. Pickering emulsions comprising fine disperse systems of Wl0 or 01W type comprising (1) an oil phase (2) an aqueous phase, (3) at least one type of a micronised particle, which (a) have a mean particle size of < 200 nm and which (b) have hydrophilic and lipophilic properties which have also amphiphilic character and are dispersible in water and in oil and which have (4) at least one compound of formula (1) as described in EP-A-1,310,235.</p>
<p>14. Cosmetic and/or dermatological compositions for the protection against UV radiation producing a permanent and non-covering colaration on the skin natural bronzing comprising in a cosmetical acceptable medium at least a susceptible pigment obtained from the extraction with an organic or hydroorganic solvent in a medium of myromydete culture of the type monascus; and -28 -at least one compound of formula (1): as described in EP-A-1,302,199.</p>
<p>15. Cosmetic and/or dermatological composition in form of an 01W emulsion comprising at least one compound of formula (1).</p>
<p>The basic compontents of the 01W emulsion are disclosed in EP-A-1,291,O1 2, ≈[0049] -[0277].</p>
<p>16. Cosmetic and/or dermatological composition in form of an W/0 emulsion comprising at least one compound of formula (1).</p>
<p>The basic compontents of the W/0 emulsion are disclosed in EP-A-1 291,009, ≈[0047] -[0245]. S. * S * ...</p>
<p>17. Cosmetic and/or dermatological composition representing finedisperse systems of 01W * .*.</p>
<p>type comprising *5 :.: * (a) an oil phase, (b) an aqueous phase, (c) one or more stabilzers as disclosed in EP-A-1,291,007 ≈[0022] -[0080].</p>
<p>(d) at most 2.00% b.w. of oner or more emulsifiers, and (e) at least one compound of formula (1).</p>
<p>Further basic components of this cosmetic or dermatological composition are disclosed in EP-A-1,291,007.</p>
<p>18. Cosmetics sticks comprising a) a lipid phase comprising at least an oil component and/or at least a wax component as described in EPA-1,290,999 ≈[0031]-[0058] and b) at least one compound of formula (1).</p>
<p>19. UV filter combination, comprising (a) a compound which absorbs essentially in he UVA range, and (b) further compounds which absorb in the UV-A-, UV-B-range and in the UV-A-and UV-B-range, wherein the moiety is in the UV-A-range (a) an effective amount of at least one compound of formula -29 -H CQOR2 cooi3 I, wherein R1, R2 and R3 independently from each other are C1-C8alkyl; and (b) an effective amount of one or more compounds selected from ba) at least one compound of formula (1); bb) a compound of formula al-c c00R6 R4J5</p>
<p>LI /</p>
<p>wherein R7 and R8 independently from each other are C1-C12alkyI or C3-C10cycloalkyl; bc) the compound of formula * * * H H * * y N.y ****</p>
<p> NN * S. Iv' ***</p>
<p>S *</p>
<p>S. S Ijx; N}1 L*,_.JJ * ** o *. S * * * bd)the compound of formula %% N</p>
<p>OH</p>
<p>be) the compound of formula (J=N HO HG " -30 -bf) the compound of formula CH3 OSi(CH3)3 CH2CHCH2SiCI-13 (VII) OSI(CH3)3 bg) the compound of formula CH, r cx3 CH-1 CH I Ii _____ I I h1t__1__O_[Si_O Si-1-Si-Vt JtIta, CHj CH3 V CK wherein V11 is the group of formula I..-C(O)OC2H5 CH=C * ** CO)OC =} * * S :. V1 is methyl or V1' is group of formula CH3 r c3 CH 1 CH3</p>
<p>I II __ I II</p>
<p>* Vi-Sj-O-J-Sj-Q si-oj_si_v2 VILIb, CH...CK V uCH) wherein V2' is a group of formula CM,C-CH2-O-H' 2-CHC</p>
<p>C OOCH</p>
<p>V2 is methyl or V'2; or mixtures of the compounds Villa and VII1b, wherein t is a number up to 100 and u is a avalue up to 20 with the proviso that u is = 0, when V1 = V1' and/or V2 = V2', and u has a value from 1 -20, when V1 is CH3 and/or V3 is CH3; bh) a compound of formula 31 -RN rri</p>
<p>I -, NH</p>
<p>QOC</p>
<p>bi) a compound of formula bj) a compound of formula ::Erz>--:ccI:::: S....</p>
<p>* ** wherein X is hydrogen, sodium, potassium, ammonium or triethanolammonium; bk) a compound of formula * OH OH S.. I i; i : XII,</p>
<p>I I II</p>
<p>H OH</p>
<p>as photostable UV filter formulation for the protection of the human skin and hair from Uv radiation, optionally together with further known cosmetic UV filters.</p>
<p>21. Cosmetic and/or dermatological composition for the protection of the human epidermis or hair from UV radiation in the range of 280 -400 nm, comprising in a cosmetic or pharmaceutical suitable carrier an effective amount of UV filter combinations as photostable UV filters, wherein the effective component of the absorbing part in the UV- A range consists of a) an effective amount of a compound of formula and component b) comprises an effective amount of one or more compounds selected from ba) the compound of formula bb) the compound of formula</p>
<p>H H</p>
<p>N N N NiN III, S. NH o * S * S.. S... * . S... 0 0 * S. * S S S.. * *.</p>
<p>S</p>
<p>bc) the compound of formula * . . * S. Me</p>
<p>NN OH )OH</p>
<p>bd) the compound of formula</p>
<p>HO HO</p>
<p>L</p>
<p>-33 -be) CH3 OSi(CH3)3 CH2CHCH2SICH3 OSI(CFI3)3 H3 bf) an orga nosiloxanebenzalmalonate of formula Cu3 1cH3 043] CH</p>
<p>I I _____ I II</p>
<p>Si-Cj--i-V1 VILa.</p>
<p>CR3 CH3 t V] CR3 *. 5 wherein S...</p>
<p>V1' is the group of formula * S. * S S *.... I..-C(O)OC2H5 CMiCCR2O' CH=C =1 C(O)OC21 S. * * . V1 is methyl orV1' is group of formula CH3 CH CR3 CR3 V2-Si-O+Sj_O Si-01 Si-v2 VIIb,</p>
<p>I II I II</p>
<p>Cr13 I CH3 t V2 J CR3 wherein V2' is a group of formula CHCCFIO C(O)OC2H5 CW)oc2H V2 is methyl or V'2; or mixtures of compounds Vhs and Vllb, wherein t is a number upt o 100 and u is a avalue up to 20 with the proviso that u is = 0, when V1 = V1 and/or /2 = V2' and u has a value from 1 -20, when V1 is CH3 and/or V3 is CH3; bg) the compound of formula -34-VIII'</p>
<p>N-N</p>
<p>bh) the compound of formula Ix. Ph Ph</p>
<p>bi) the compound of forniula * . * .** *** * . * * * * S.. * *:. 5 0 * bj) a compound of formula * S * * * s03x * .. XI,</p>
<p>wherein X is hydrogen, sodium, potassium, ammonium or triethanolammonium; bk) the compound of formula 0 0 XII, Ph'LPh bj)the compound of formula (1) bm) the compound of formula -35 -4H xiv OEr bn) the compound of formula</p>
<p>OH OH</p>
<p>-. -xv,</p>
<p>I I</p>
<p>H OH</p>
<p>bo) the compound of formula xvi and bp) tin oxide and/or titanium dioxide, *: . optionally together with further known cosnietic UV filters.</p>
<p>22. Cosmetic and/or dermatological composition for topical use, preferably for the photoprotection of the skin and/or hair comprising in a cosmetic acceptable medium (a) at least one dibenzoyl methane deivative as described in EP-A-1,323,413 ≈[0027 -0030] (b) at least one 1,3,5triazine derivative as described in EP-A-1,323,413 ≈[0019- 00271 being photosensitive in the presence of the dibenzoylmethane derivative; (c) at least one compound of formula (1) 23. Cosmetic and/or dermatological composition for topical use, preferably for the photoprotection of the skin and/or hair comprising in a cosmetic acceptable medium (a) at least one dibenzoyl methane derivative as described in EP-A-1 323,412 ≈[0040 -0042]; (b) at least one compound of formula (1).</p>
<p>-36 - 24. Cosmetic and/or dermatological composition for topical use, preferably for the photoprotection of the skin and/or hair comprising in a cosmetic acceptable medium (a) at least one si/ide derivative benzotriazole (first filter) as described in EP-A- 1,323,411 [0021 -0036] (b) at least one dibenzoyl methane deivative (c) at least one compound of formula (1) (= third filter) 25. Cosmetic and/or dermatological composition comprising one or more lecithins for increasing the light protection factor and/or UVA protection as described in EP-A-l,166,759; and at least one compound of formula (1).</p>
<p>26. Cosmetic and/or dermatological composition comprising (a) triglyceride waxes as decribed in EP-A-1,000,611 to increase the UVA protection factor of cosmetic or dermatological compositions containing conventional UV-A-filters; * and/or (b) at least one compound of formula (1) that also provide protection against UV radiation with a wavelength above 355 nm.</p>
<p>27. Cosmetic and/or dermatological composition comprising (a) ethylhexyl 2-cyano-3,3-diphenylacrylate (octocrylene) as described in EP A-i 034,778; and (b) at least one compound of formula (1) for solubilizing and for increasing the light protection factor and/or the UV-A protection performance of the compound of formula (1).</p>
<p>28. Oil-free cosmetic or dermatological composition comprising (a) at least one compound of formula (1) and (b) at least one UV filter liquid at room teniperature as described in EP-A-1,074,241 29. 01W emulsion, preferably O/W-microemulsion or OIWIO-emulsions or O/VV/0'-emulsions comprising (a) water phase -37 - (b) optionally usual water soluble or dispersible substances, (C) an oil phase, wherein at least one cosmetic or dermatologic UV filter substance selected from at least one compound of formula (1) is present in suspended form, (d) at least one emulsifier (A) selected from emulsifiers with the following properties -the lipophilic property is either dependent on the pH inasmuch rising or lowering the pH the lipophilic property will increase or decrease being insubstantial which of both alternatives of changing the Hpophilic properties by rising or lowering the pH is effected and/or -the lipophilic property is dependent on the temperature, inasmuch the lipophilic properties will increase with rising temperature and the hydrophilic properties will increase with rising temperature, (e) and further substances which are optionally soluble or dispersible in the oil phase, preferably those substances which are outside the definition of emulsifier (A), preferably :... those substances which predominantly act as WIO emulsifiers. * . ****</p>
<p>* * 30. Cosmetic light protection formulation comprising .: (a) one or more amide oils as described in DE-A-1 9942714; and (b) atleastone compound of formula (1) ** . * The cosmetic or pharmaceutical preparations may be, for example, creams, gels, lotions, al-coholic and aqueous/alcoholic solutions, emulsions, wax/fat compositions, stick preparations, powders or ointments. In addition to the above-mentioned UV filters, the cosmetic or pharma-ceutical preparations may contain further adjuvants as described below.</p>
<p>As water-and oil-containing emulsions (e.g. W/0, 01W, OIW/O and W/0/W emulsions or ml-croemulsions) the preparations contain, for example, from 0.1 to 30 % by weight, preferably from 0.1 to 15 % by weight and especially from 0.5 to 10 % by weight, based on the total weight of the composition, of one or more UV absorbers, from 1 to 60 % by weight, espec-ially from 5 to 50 % by weight and preferably from 10 to 35 % by weight, based on the total weight of the composition, of at least one oil component, from 0 to 30 % by weight, especially from 1 to 30 % by weight und preferably from 4 to 20 % by weight, based on the total weight of the composition, of at least one emulsifier, from 10 to 90 % by weight, especially from 30 to 90 % by weight, based on the total weight of the composition, of water, and from 0 to 88.9 -38 - % by weight, especially from 1 to 50 % by weight, of further cosmetically acceptable adju-vants.</p>
<p>The compounds of formula (1) may also be used as as an anti-wrinkle perception modifier (see Example 29). This is a futher object of the present invention.</p>
<p>Preferably, the following combinations comprising UV absorbers are of special interest: A CASNo.ofA B UV absorber selected from the formulas ____ _____________________________ ___________ (101)-(105) Comb (+I-)-1, 7, 7-trimethyl-3-[(4-methylphe-36861-47-9 001 nyl)methylene]bicyclo[2.2. 1]hepta n-2-X _____ one; p-methyl benzylidene camphor ____________ _______________________ Comb 1, 7,7-trimethyl-3-(phenyl methyllene)-15087-24-8 002 bicyclo[2.2.1]heptan-2-one; benzylidene X _____ camphor ___________ _____________________ *... Comb (2-Hydroxy-4-methoxyphenyl)(4-methyl-1641-17-4 003)henyl)methanone ____________ x : *. Comb 2,4-dihydroxybenzophenone 131-56-6 X 004 ______________________________ ___________ ____________________ ** Comb 2,2',4,4'-tetrahydroxybenzophenone 131-55-5 X</p>
<p>___________________________________ _____________ _______________________</p>
<p>Comb 2-Hydroxy-4-methoxy benzophenone; 131-57-7 X * . 006 _______________________________ ___________ ____________________ Comb 2-Hydroxy-4-methoxy benzophenone-5-4065-45-6 X 007 sulfonic acid ____________ _______________________ Comb 2,2'-dihydroxy-4,4'-dimethoxybenzophe-131-54-4 X 008 none ____________ ______________________ Comb 2,2'-Dihydroxy-4-methoxybenzophenone 131-53-3 X 009 ____________________________________ _____________ ________________________ Comb Alpha-(2-oxoborn-3-ylidene)toluene-4-56039-58-8 X sulphonic acid and its salts; Mexoryl SL ____________ _______________________ Comb 1 -[4-(1, 1 -dimethylethyl)phenyl]-3-(4-70356-09-1 X 011 methoxyphenyl)propane-1,3-dione; _____ avobenzone ____________ Comb Methyl N,N,N-trimethyl-4-[(4,7,7-52793-97-2 X 012 trimethyl-3-oxobicyclo[2,2, 1 Jhept-2-ylidene)methyl]anilinium sulphate; ____-Mexoryl SO __________ ___________________ Comb 3,3,5-Trimethyl cyclohexyl-2-hydroxy 118-56-9 X 013 benzoate; homosalate ____________ Comb Isopentyl p-methoxycinnamate; isoamyl 71617-10-2 X 014 methoxy cinnamate ____________ Comb Menthyl-o-aminobenzoate 134-09-8 X</p>
<p>________________________________ ___________ _____________________</p>
<p>-39 -No A CASNo.ofA B UV absorber selected from the formulas ____ _______________________________ ___________ (101)-(105) Comb Menthyl salicylate 89-46-3 X 016 _________________________________ ____________ ______________________ Comb 2-Ethyihexyl 2-cyano,3,3-6197-30-4 X 017 diphenylacrylate; octocrylene ____________ ______________________ Comb 2-ethylhexyl 4-(dimethylamino)benzoate 21245-02-3 X 018 __________________________________ ____________ ______________________ Comb 2-ethylhexyl 4-methoxycinriamate; octyl 5466-77-3 X 019 methoxy cinnamate ___________ ____________________ Comb 2-ethylhexyl salicylate 118-60-5 X</p>
<p>___________________________________ ____________ _______________________</p>
<p>Comb Benzoic acid,4,4',4"-(1, 3, 5-triazine-88122-99-0 X 021 2,4,6-triyltriimino)tris-,tris(2-ethylhexyl)- ester; 2, 4,6-Trianilino-(p-carbo-2'-ethyl-hexyi-1 -oxi)-1,3, 5-triazine; Octyl _____ Triazone ____________ * . __________________________________ ____________ ______________________ * Comb 4-aminobenzoic acid 150-13-0 X * * . 022 __________________________________ ____________ ______________________ *S* ______________________________ Comb Benzoic acid, 4-amino-, ethyl ester, poly-113010-52-9 X * .. 023 mer with oxirane ____________ :.: * Comb 2-phenyl-1H-benzimidazole-5-sulphonic 27503-81-7 X 024 acid; phenylbenzimidazolsulfonic acid ___________ _____________________ Comb 2-Propenamide, N-[4-[(4, 7, 7-tnmethyl-3-147897-12-9 X oxobicyclo[2.2. 1]hept-2-ylidene)methyl]- ____ phenyl]methyl}-, homopolymer ___________ _____________________ Comb Triethanolarnine salicylate 2174-16-5 X 026 ___________________________________ ____________ _______________________ Comb 3, 3'-(l, 4-phenylenedimethylene)bis-90457-82-2 X 027 [7,7-dimethyl-2-oxobicyclo[2.2. 1]hep- _____ tane-1 methanesulfonic acid]; Cibafast H ____________ _______________________ Comb Titanium dioxide 13463-67-7 X 028 __________________________________ ____________ ______________________ Comb Zinc oxide 1314-13-2 x 029 ___________________________________ ____________ _______________________ Comb 2,2'-Methylene-bis-[6-(2H-benzotriazol-2-103597-45-1 X yl)-4-(l, 1,3,3-tetramethylbutyl)-phenolj; _____ Tinosorb M ____________ ______________________ Corn b 2,4-bis{[4-(2-ethylhexyloxy)-2-hydroxy] -187393-00-6 x 031 phenyl}-6-(4-methoxyphenyl)-( 1,3,5)- _____ triazine; Tinosorb S ____________ Comb 1 H-Benzimidazole-4,6-disulfonic acid, 180898-37-7 X 032 2,2'-(1,4-phenylene)bis-, disodium salt Comb Benzoic acid, 4,4'-[6-[4-[(1,1-dimethyl-154702-15-5 X 033 ethyl)am ino]carbonyl]phenyl]amino] 1,3,5- triazine-2,4-diyl]d iimino]bis-, bis(2-ethyl- _____ hexyl)ester; diethyihexyl butamido tria _____________ ________________________ No A CASNo.ofA UV absorber selected from the formulas ______ ____________________________________________ ________________ (101) -(105) _____ zone; Uva sorb HEB ____________ ______________________ Comb Phenol, 2-(2H-benzotriazol-2-yl)-4-me-155633-54-8 X 034 thyl-6-[2-methyt-3-[1,3, 3, 3-tetramethyl-1- [(trimethylsilyl)oxy]disiloxanyI]propyl-; _____ drometrizole trisiloxane; Mexoryl XL ____________ ______________________ Comb Dimethicodiethylbenzalmalonate; 207574-74-1 X Polysilicone 15; Parsol SLX ___________ _____________________ Comb Benzenesulfonic acid, 3-(2H-benzotri-92484-48-5 X 036 azol-2-yl)-4-hydroxy-5-(1 -methyipropyl)-, ____ monosodium salt; Tinogard HS ____________ _____________________ Comb Benzoic acid, 2-[4-(diethylamino)-2-hy-302776-68-7 X 037 droxybenzoyl]-, hexyl ester; Uvinul a plus _____________ _______________________ Comb 1-Dodecanaminium, N-[3-[4-(dimethyl-156679-41-3 X 038 amino)benzoyl]amino]propyl]N, N- dimethyl-, salt with 4-methylbenzene- * . sulfonic acid (1:1); EscalolHP6lO ___________ ___________________ * " Comb 1 -Propanaminium, N, N,N-trimethyl-3-[( 1-177190-98-6 X 039 oxo-3-phenyl-2-propenyl)amino]-, * ** _____ chloride _____________ * Comb 1H-Benzimidazole-4,6-disulfonic acid, 170864-82-1 X 2,2'-(1,4-phenylene)bis-____________ ______________________ Comb 1,3,5-Triazine, 2,4,6-tris(4-methoxy-7753-12-0 X 041 phenyl) ____________ _______________________ Comb 1,3, 5-Triazine, 2,4,6-tris[4-[(2-ethyl-208114-14-1 x 042 hexyl)oxy]phenylj-(Rinosorb S) _____________ _______________________ Comb 1-Propanaminium, 3-[3-[3-(2H-benzo-340964-15-0 X 043 triazol-2-yl)-5-( 1,1 -dimethylethyl)-4- hydroxyphenyl]-1 -oxopropyl]amino]-N, N- _____ diethyl-N-methyl-, methyl sulfate (salt) _____________ ________________________ Comb 2-Propenoic acid, 3-(1 H-imidazol-4-yl)-104-98-3 X 044 _________________________________ ____________ ______________________ Comb Benzoic acid, 2-hydroxy-, [4-(1-methyl-941 34-93-7 X ethyl)phenyl]methyl ester _____________ _______________________ Comb 1,2,3-Propanetriol, 1 -(4-aminobenzoate); 136-44-7 X 046 glyceryl PABA ____________ ______________________ Comb Benzeneacetic acid, 3,4-dimethoxy-a-4732-70-1 X 047 oxo ____________ _______________________ Comb 2-Propenoic acid, 2-cyano-3,3-diphenyl-, 5232-99-5 X 048 ethyl ester ____________ _______________________ Comb Anthralinic acid, p-menth-3-yl ester 134-09-8 X 049 __________________________________ ____________ ______________________ Comb 2,2'-bis( 1,4-phenylene)-1 H-benzimida-349580-1 2-7, X zole-4,6-disulphonic acid mono sodium salt or Disodium phenyl dibenzimidazole _____ tetrasulfonate (Neoheliopan AP) ____________ _______________________ Comb 1,3,5-Triazine-2,4,6-triamine, N,N'-bis[4-288254-16-0 X No A CASNo.ofA B UV absorber se'ected from the formulas ____ ______________________________ ___________ (101)-(105) 051 [5-(1,1-dimethylpropyl)-2-benzoxazolyll- _____ phenyl]-N"-(2-ethylhexyl)-(Uvasorb K2A) ____________ _______________________ Comb Merocyanine derivatives as described in X 052 WO 2004006878 and in _____ 1PC0M000022279D ___________ _____________________ Comb,-X</p>
<p>H H H</p>
<p>Comb sterols (cholesterol, lanosterol, phyto-X 054 sterols), as described in W00341675 ____________ ______________________ Combmycosporines and/or mycosporine-like X : ... 55 amino acids as described in from Milbelle AG, isolated mycosporine like amino acids from the red alga : .". porphyra umbilicalis (INCI: Porphyra Umbilicalis) that are encapsulated into _____ liposomes,) _____________ ________________________ Comb alpha-lipoic-acid as described in DE X : 056 10229995 ___________ * Comb synthetic organic polymers as described X 057 in EP 1371358, [0033]-[0041} ___________ _____________________ Comb phyllosilicates as described in EP X 058 1371357 [0034]-[0037] ___________ _____________________ Comb silica compounds as described in X 059 EP1371356, [0033]-[0041] ___________ ____________________ Comb inorganic particles as described in X DEl 0138496 [0043]-[0055] ____________ ______________________ Comb latex particles as described in X 061 DE10138496 [0027]-[0040] ___________ ____________________ Furthermore, the following specific UV filter combinations are of specific interest: No A CAS No. of A UV absorber selected from the formulas ____ _________________________________ _________ (101)-(105) Comb (+I-)-1,7,7-trimethyl-3-[(4-methylphenyl)-36861-47-9 X 062 methylene]bicyclo[2.2. 1]heptan-2-one; p- _____ methyl benzylidene camphor ___________ -42 -No A CAS No. of A UV absorber selected from the formulas ______ ______________________________________________ _____________ (101)-(105) Comb 1,7, 7-trimethyl-3-(phenylmethylene)bi-15087-24-8 X 063 cyclo[2.2. 1 Jheptan-2-one; benzylidene ____ camphor Comb (2-Hydroxy-4-methoxyphenyl)(4-1641-17-4 X 064 methylphenyl)methanone Comb 2,4-dihydroxybenzophenone 131-56-6 X</p>
<p>________________________________________ ___________</p>
<p>Comb 2,2',4,4'-tetrahydroxybenzophenone 131-55-5 X Comb 2-Hydroxy-4-methoxy benzophenone; 131-57-7 X Comb 2-Hydroxy-4-methoxy benzophenone-5-4065-45-6 X 068 sulfonic acid Comb 2,2'-dihydroxy-44'-dimethoxybenzophenone 131-54-4 X :. 069 ___________________________________ __________ ___________________ Comb 2,2'-Dihydroxy-4-methoxybenzophenone 131-53-3 X * * 070 ______________________________________ ___________</p>
<p>______________________________________________________ _______________ _____________________________</p>
<p>Comb Alpha-(2-oxoborn-3-ylidene)toluene-4-sul-56039-58-8 X : *.** 071 phonic acid and its salts; Mexoryl SL * I _______________ _____________________________ : * Comb 1 -[4-( 1,1 -dimethylethyl)phenyl]-3-(4-methoxy-70356-09-1 X 072 phenyl)propane-1,3-dione; avobenzone * Comb Methyl N,N,N-trimethyl-4-[(4,7,7-trimethyl-3-52793-97-2 X 073 oxobicyclo[2,2, 1]hept-2-ylidene)methyl]-anilinium sulphate; Mexoryl SO Comb 3,3,5-Trimethyl cyclohexyl-2-hydroxy 118-56-9 X 074 benzoate; homosalate Comb Isopentyl p-methoxycinnamate; isoamyl 71617-10-2 X methoxy cinnamate Comb Menthyl-o-aminobenzoate 134-09-8 X 076 _______________________________________ ___________ ____________________ Comb Menthyl salicylate 89-46-3 X 077 ______________________________________ ___________ Comb 2-Ethyihexyl 2-cyano,3,3-diphenylacrylate; 6197-30-4 X 078 octocrylene Comb 2-ethylhexyl 4-(dimethylamino)benzoate 21245-02-3 X Comb 2-ethylhexyl 4-methoxycinnamate; octyl 5466-77-3 X methoxy cinnamate Comb 2-ethylhexyl salicylate 118-60-5 X Comb Benzoic acid,4,4',4"-(1, 3, 5-triazine-2,4,6-88122-99-0 X 082 triyltriimi no)tris-,tris(2-ethylhexyl)ester; 2,4,6-_____________ ________________________ -43 -No. A CAS No. of A UV absorber selected from the formulas ______ ________________________________________________ ______________ (101)-(105) Trianilino-(p-carbo-2'-ethylhexyl-l -oxi)-l,3, 5-triazine; octyl triazone Comb aminobenzoic acid 150-13-0 X 083 ________________________________________ ___________ Comb Benzoic acid, 4-amino-,ethyl ester, polymer 11301 0-52-9 X 084 with oxirane Comb 2-phenyl-1 H-benzimidazole-5-sulphon ic acid; 27503-81-7 X phenylbenzimidazolsulfonic acid Comb 2-Propenamide, N-[4-[(4, 7, 7-trimethyl-3-oxo-147897-12-9 X 086 bicyclo[2.2. 1]hept-2-ylidene)methyl]phenyl]- _____ methyl]-, homopolymer ___________ Comb Triethanolamine salicylate 2174-16-5 X 087 ________________________________________ ___________ Comb 3, 3'-(l, 4-phenylenedimethylene)bis[7,7-90457-82-2 X 088 dimethyl-2-oxo-bicyclo[2.2.1]heptane-1-methanesulfonic acid]; Cibafast H Comb Titanium dioxide 13463-67-7 X * * 089 _____________________________________ __________ ___________________ .: * Comb Zincoxide 1314-13-2 x * 090 ______________________________________ ___________ *** ________________________ * Comb 2,2'-Methylene-bis-[6-(2H-benzotriazol-2-yI)-103597-45-1 X * 091 4-( 1,1,3,3-tetramethylbutyl)-phenol]; Tinosorb Comb 2,4-bis{[4-(2-ethylhexyloxy)-2-hydroxy]-187393-00-6 X 092 phenyl}-6-(4-methoxyphenyl)-( 1,3,5)-triazine; Tinosorb S Comb 1H-Benzimidazole-4,6-disulfonic acid, 2,2'-180898-37-7 X 093 (1,4-phenylene)bis-, disodium salt Comb Benzoic acid, 4,4'-[6-[4-[( 1,1 -dimethylethyl)-154702-15-5 X 094 amino]carbonyl]phenylJamino]1 3,5-triazine- 2,4-diyl]diiminojbis-, bis(2-ethylhexyl)ester; _____ diethylhexyl butamido triazone; Uvasorb HEB Comb Phenol, 2-(2H-benzotriazol-2-yl)-4-methyl-6-155633-54-8 X [2-methyl-3-[1, 3,3,3-tetramethyl-1 -[(trirne-thylsilyl)oxy]disiloxanyl]propyl]-; drometrizole _____ trisiloxane; Mexoryl XL Comb Dimethicodiethylbenzalmalonate; Polysilicone 207574-74-1 X 096 15; Parsol SLX Comb Benzenesulfonic acid, 3-(2H-benzotriazol-2-92484-48-5 X 097 yl)-4-hydroxy-5-(1 -methyipropyl)-, monosodium salt; Tinogard HS -44 -No A GAS No. of A UV absorber selected from the formulas ________________________________________________ _____________ (101)-(105) Comb Benzoic acid, 2-[4-(diethylamino)-2-hydroxy-302776-68-7 X 098 benzoyl]-, hexyl ester; Uvinul a plus ___________ Comb 1-Dodecanaminium, N-[3-[4-(dimethylami-156679-41-3 X 099 no)benzoyljaminojpropyljN, N-dimethyl-, salt with 4-methylbenzenesulfonic acid (1:1) ____ (Escalol HP6IO) Comb 1-Propanaminium, N,N, N-trimethyl-3-[( 1 -oxo-177190-98-6 X 3-phenyl-2-propenyl)aminoj-, chloride Comb 1H-Benzimidazole-4,6disulfonic acid, 2,2'-170864-82-1 X 101 (1,4-phenylene)bis-___________ Comb 1,3,5-Triazine, 2,4,6-tris(4-methoxyphen yl)-7753-12-0 X Comb 1,3,5-Triazine, 2,4,6-tris[4-[(2-ethylhexyl)oxy]-208114-14-1 X 103 phenyl]-(Tinosorb S) ___________ Comb 1-Propanaminium, 3-[3-13-(2H-benzotriazol-340964-15-0 X 104 2-yl)-5-( 1,1 -dimethylethyl)-4-hydroxyphe nyl]- * * 1 -oxopropyl]amino]-N, N-diethyl-N-methyl-, :.: * _____ methyl sulfate (salt) ___________ Comb 2-Propenoic acid, 3-( 1 H-imidazol-4-yl)-104-98-3 X Comb Benzoic acid, 2-hydroxy-, [4-(1-methylethyl)-94134-93-7 X 106 phenyl]methyl ester Comb 1,2,3-Propanetriol, 1 -(4-aminobenzoate); 136-44-7 X 107 glyceryl PABA Comb Benzeneacetic acid, 3,4-dimethoxy-a-oxo-4732-70-1 X 108 _____________________________________ ___________ Comb 2-Propenoic acid, 2-cyano-3,3-diphenyl-, 5232-99-5 X 109 ethyl ester Comb Anthralinic acid, p-menth-3-yl ester 134-09-8 X</p>
<p>___________________________________ __________</p>
<p>Comb 2,2'-bis( 1,4-phenylene)-1 H-benzimidazo le-349580-12-7, X 111 4,6-disulphonic acid mono sodium salt or Disodium phenyl dibenzimidazole tetrasulfonate or Neoheliopan AP Comb 1,3,5-Triazine-2,4,6-triamine, N, N'-bis[4-[5-288254-16-0 X 112 (1,1 -d imethylpropyl)-2-benzoxazolyl]phe nyl)- _____ N"-(2-ethylhexyl)-(Uvasorb K2A) ___________ _____________________ Comb Merocyanine derivatives as described in X 113 wo 2004006878 and 1PC0M000022279D No A CAS No. of A UV absorber selected from the formulas ______ ________________________________________________ _____________ (101)-(105) Comb 114 0 1_ç_J/__ x N-C= C-C_k</p>
<p>H H I-I CN</p>
<p>Comb sterols (cholesterol, lanosterol, phytosterols), X as described in W00341 675 Comb mycosporines and/or mycosporine-like amino X 116 acids as described in W02002039974, e.g. Helioguard 365 from Milbelle AG, isolated mycosporine like amino acids from the red alga porphyra umbilicalis (INCI: Porphyra Umbilicalis) that are encapsulated into *.</p>
<p>* liposomes,) * *.* Comb alpha-lipoic-acid as described in DE X * * 117 10229995 * ** Comb synthetic organic polymers as described in X ** * 118 EP 1371358, [0033]-[0041] __________ ___________________ Comb phyllosilicates as described in EP 1371357 X 119 [00341-[0037J ___________ S. * ______ * S S * *. Comb silica compounds as described in X EP1371356, [0033]-[0041] __________ ___________________ Comb inorganic particles as described in X 121 DE1O1 38496 [0043]-[0055] __________ Comb latex particles as described in DE1O1 38496 X 122 [002 7]-[0040] ___________ Furthermore, the following specific UV filter combinations are of specific interest: No. UV filter (A) UV filter (B) UV filter (C) Comb 2-ethylhexyl 4-methoxy-micronized (JV absorber of UV absorber selected 124 cinnamate; octyl methoxy formula (103) from the formulas cinnamate (101)-(105) Comb 2-ethylhexyl 4-Benzoic acid, 2-[4-(diethyl-UV absorber selected methoxycinnamate; octyl amino)-2-hydroxybenzoyl]-, from the formulas ____ methoxy cinnamate hexyl ester; Uvinul a plus (101)(105) Comb 2-ethylhexyl 4-methoxy-Benzoic acid, 2-[4-(diethyl-UV absorber selected _____ cinnamate; octyl methoxy amino)-2-hydroxybenzoyll-, from the formulas No. UV filter (A) UV filter (B) UV filter (C) 126 cinnamate hexyl ester; Uvinul a plus (101)-(105) Comb 2-ethylhexyl 4-methoxy-Benzoic, 4,4'-[6-[4-[( 1,1 -UV absorber selected 127 cinnamate; octyl methoxy dimethylethyl)amino]carbo-from the formulas cinnamate nyl]phenyl]arnino]1,3,5-triazine-(101) -(105) 2,4-diyI]diiminojbis-, bis(2-ethylhexyl)ester; diethyihexyl butamido triazone (Uvasorb ____ __________________ HEB) Comb 2-ethylhexyl 4-methoxy-2,2'-bis(l,4-phenylene)-1 H-UV absorber selected 128 cinnamate; octyl methoxy benzimidazole-4,6-disulphonic from the formulas cinnamate acid mono sodium salt or Di-(101) -(105) sodium phenyl dibenzimida- zole tetrasulfonate (Neohelio- ____ _____________________ pan AP) Comb 2-ethylhexyl 4-methoxy-2-Ethyihexyl 2-cyano,3,3-UV absorber selected * 129 cinnamate; octyl methoxy diphenylacrylate; octocrylene from the formulas * cinnamate (101)-(105) **** _______ ______________________________ Comb 2-ethylhexyl 4-methoxy-Benzoic acid, 4, 4', 4"-(l, 3, 5.. UV absorber selected * ,. 130 cinnamate; octyl methoxy triazine-2,4,6-triyltriimino)tris-, from the formulas :.: ** cinnamate tris(2-ethylhexyl)ester; 2,4,6-(101)-(105) *:. Trianilino-(p-carbo-2'-ethyl-hexyl-1 -oxi)-1, 3,5-triazine; _____ ______________________ octyl triazone Comb 2-ethylhexyl 4-methoxy-2-phenyl-1H-benzimidazole-5-UV absorber selected 131 cinnamate; octyl methoxy sulphonic acid; phenylbenz-from the formulas cinnamate imidazolsulfonic acid (101)(105) Comb 2-ethylhexyl 4-methoxy-1 -[4-(1, 1 -dirnethylethyl)phenyl)-UV absorber selected 132 cinnamate; octyl methoxy 3-(4-methoxyphenyl)propane-from the formulas cinnamate 1,3-dione; avobenzone (101) -(105) Comb 2-ethylhexyl 4-methoxy-Phenol, 2-(2H-benzotriazol-2-UV absorber selected 133 cinnamate; octyl methoxy yl)-4-methyl-6-[2-methyl-3-from the formulas cinnamate [1,3,3,3-tetramethyl-1-[(tri-(101)-(105) methylsilyl)oxy]disiloxanyl]prop yl]-; drometrizole trisiloxane; _____ _____________________ Mexoryl XL Comb 2-ethylhexyl 4-methox-Dimethicodiethylbenzalmalonat UV absorber selected 134 ycinnamate; octyl methoxy e; Polysilicone 15; Parsol SLX from the formulas cinnamate (101)-(105) Comb 2-ethylhexyl 4-methoxy-2,2'-Methylene-bis-[6-(2H-ben-UV absorber selected cinnamate; octyl methoxy zotriazol-2-yl)-4-(1,1,3,3-tetra-from the formulas cinnamate methylbutyl)-phenol]; Tinosorb (101)(105)</p>
<p>____ M</p>
<p>Comb 2-ethylhexyl 4-methoxy-2,4-bis{[4-(2-ethylhexyloxy)-2-UV absorber selected 136 cinnamate; octyl methoxy hydroxy]-phenyl}-6-(4-me-from the formulas -47 -No. UV fitter (A) UV filter (B) UV filter (C) cinnamate thoxyphenyl)-(1,3,5)-triazine; (101)-(105) _____ Tinosorb S Comb 2,4-bis{[4-(2-ethylhexyl-2,2'-Methylene-bis-[6-(2H-UV absorber selected 137 oxy)2-hydroxyj-phenyl}-6-benzotriazol-2-yI)-4-(1, ,3.. from the formulas (4-methoxyphenyl)..( 1,3,5)-tetramethylbutyl)-phenolj; (101) -(105) _____ triazine; Tinosorb S Tinosorb M Comb Benzoic acid, 2-[4-(diethyt-1-[4-(1 1-dirnethylethyl)phenylj-UV absorber selected 138 amino)-2-hydroxybenzoyl]-3-(4-methoxyphenyl)propane-from the formulas _____ hexyl ester; Uvinul a plus 1,3-dione; avobenzone (101)(b05) Comb 2,4-bis{[4-(2-ethylhexyl-1 -[4-( 1,1 -dirnethylethyl)phenyl]-UV absorber selected 139 oxy)-2-hydroxy]-phenyl}-6-3-(4-methoxyphenyl)propane-from the formulas (4-methoxyphenyl)-( 1,3,5)-1,3-dione; avobenzone (101) -(105) triazine; Tinosorb S Comb 1 -[4-( 1,1 -dimethylethyl)-2,2'-bis( 1,4-phenytene)-1 H-UV absorber selected phenyl]-3-(4-methoxy-benzimidazole-4,6-disulphonic from the formulas : .. phenyl)propane-1,3-dione; acid mono sodium salt or Di-(101) -(105) avobenzone sodium phenyl dibenzimidazole tetrasulfonate or Neoheliopan</p>
<p>____ AP</p>
<p>* S. _____________________________ ___________________________________ * I * *5. * a:. The cosmetic or pharmaceutical preparations may be, for example, creams, gels, lotions, alcoholic and aqueous/alcoholic solutions, emulsions, wax/fat compositions, stick prepa-rations, powders or ointments. In addition to the above mentioned UV filters, the cosmetic or pharmaceutical preparations may contain further adjuvants as described below.</p>
<p>As water-and oil-containing emulsions (e.g. WI0, 01W, OIWIO and WIOIW emulsions or microemulsions) the preparations contain, for example, from 0.1 to 30 % by weight, pre-ferably from 0.1 to 15 % by weight and especially from 0.5 to 10 % by weight, based on the total weight of the composition, of one or more UV absorbers, from 1 to 60 % by weight, especially from 5 to 50 % by weight and preferably from 10 to 35 % by weight, based on the total weight of the composition, of at least one oil component, from 0 to 30 % by weight, especially from 1 to 30 % by weight und preferably from 4 to 20 % by weight, based on the total weight of the composition, of at least one emulsifier, from 10 to 90 % by weight, especially from 30 to 90 % by weight, based on the total weight of the composition, of water, and from 0 to 88.9 % by weight, especially from 1 to 50 % by weight, of further cosmetically acceptable adjuvarits.</p>
<p>The cosmetic or pharmaceutical compositions/preparations according to the invention may also contain one or one more additional compounds as described below.</p>
<p>Fatty alcohols Guerbet alcohols based on fatty alcohols having from 6 to 18, preferably from 8 to 10 carbon atoms including cetyl alcohol, stearyl alcohol, cetearyl alcohol, oleyl alcohol, octyldodecanol, benzoate of C12-C15 alcohols, acetylated lanolin alcohol, etc..</p>
<p>Esters of fatty acids Esters of linear C6-C24 fatty acids with linear C3-C24 alcohols, esters of branched C6-C13car-boxylic acids with linear C6-C24 fatty alcohols, esters of linear C6-C24 fatty acids with branched alcohols, especially 2-ethyihexanol, esters of hydroxycarboxylic acids with linear or branched C6-C22 fatty alcohols, especially dioctyl malates, esters of linear and/or branched fatty acids : with polyhydric alcohols (for example propylene glycol, dimer diol or trimer triol) and/or</p>
<p>U</p>
<p> 15 Guerbet alcohols, for example caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, * *, launc acid, isotridecanoic acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeo-*** stearic acid, arachidic acid, gadoleic acid, behenic acid and erucic acid and technical-grade mixtures thereof (obtained, for example, in the pressure removal of natural fats and oils, in the reduction of aldehydes from Roelen's oxosynthesis or in the dimerisation of unsaturated fatty acids) with alcohols, for example, isopropyl alcohol, caproic alcohol, capryl alcohol, 2-ethyihexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linoyl alcohol, linolenyl alcohol, elaeostearyl alcohol, arachidyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and technical-grade mixtures thereof (obtained, for example, in the high-pressure hydrogenation of technical-grade methyl esters based on fats and oils or aldehydes from Roelen's oxosynthesis and as monomer fractions in the dimerisation of unsaturated fatty alcohols).</p>
<p>Examples of such ester oils are isopropylmyristate, isopropylpalmitate, isopropylstearate, iso- propyl isostearate, isopropyloleate, n-butylstea rate, n-hexyllaurate, n-decyloleate, isooctyl- stearate, iso-nonyistearate, isononyl isonona noate, 2-ethylhexylpalmitate, 2-hexyllaurate, 2- hexyldecylstearate, 2-octyldodecylpal mitate, ol eyloleate, oleylerucate, erucyloleate, erucyl-erucate, cetearyl octanoate, cetyl palmitate, cetyl stearate, cetyl oleate, cetyl behenate, cetyl -49 -acetate, myristyl myristate, myristyl behenate, myristyl oleate, myristyl stearate, myristyl pal-mitate, myristyl lactate, propylene glycol dicaprylate/caprate, stearyl heptanoate, diisostearyl malate, octyl hydroxystearate, etc..</p>
<p>Other adiuvants alpha glucosylrutin (CAS No. 130603-71-3), 2-butyloctyl o-hydroxybenzoate (CAS No. 190085-41-7), vitamin E (CAS No. 1406-18-4),, vitamin E acetate (CAS No. 58-95-7), diethylhexyl 2,6-naphthalate, di-n-butyl adipate, di(2-ethylhexyl)-adipate, di(2-ethylhexyl)-succinate and diisotridecyl acelaat, and also dial esters, such as ethylene glycol dioleate, ethylene glycol diisotridecanoate, propylene glycol di(2-ethylhexanoate), propylene glycol diisostearate, propylene glycol dipelargonate, butanediol dilsostearate and neopentyl glycol dicaprylate. Esters of C6-C24 fatty alcohols and/or Guerbet alcohols with aromatic carboxylic acids, saturated and/or unsaturated, especially benzoic acid, esters of C2-C12dicarboxylic acids with linear or branched alcohols having from 1 to 22 carbon atoms or polyols having *** 15 from 2 to 10 carbon atoms and from 2 to 6 hydroxy groups, or iminodisuccinic acid and : imiondisuccinic acid salts [GAS 7408-20-0] or latex particles, aloe vera, chamomile, ginko biloba, ginseng, coenzyme Q10, laminaria ochroleuca extract, magnolia oborata extract, melalenca alternifolia leaf oil, rubus idaeus seed oil, vaccinium macrocarpon seed oil, pumpkin seed extract, pumpkin seed oil, grape seed extract, carnosine, alpha-arbutin, S:20 madecassoside, termino-laside, tetrahydrocurcu minoids (THC), mycosporines, mycosporine like amino acids from the red alga porphyra umbilicalis, mycosporine-like amino acids (as described in W02002039974), cis-9-octadecenedjoic acid, lipoic acid,laurimino dipropiomic acid tocopheryl phosphates (LDTP), microcrystalline cellulose (MGC), polycarbonates as described in WO 0341676, sterols (cholesterol, lanosterol, phytosterols), as described in W00341675 and linear poly-alpha-glucans as described in US6616935 Natural or synthetic triglycerides including glyceryl esters and derivatives Di- or tri-glycerides, based on G6-C18 fatty acids, modified by reaction with other alcohols (caprylic/capric triglyceride, wheat germ glycerides, etc.). Fatty acid esters of polyglycerin (polyglyceryl-n such as polyglyceryl-4 caprate, polyglyceryl-2 isostearate, etc. or castor oil, hydrogenated vegetable oil, sweet almond oil, wheat germ oil, sesame oil, hydrogenated cottonseed oil, coconut oil, avocado oil, corn oil, hydrogenated castor oil, shea butter, cocoa butter, soybean oil, mink oil, sunflower oil, safflower oil, macadamia nut oil, olive oil, hydro-genated tallow, apricot kernel oil, hazelnut oil, borago oil, etc. -50 - Waxes including esters of long-chain acids and alcohols as well as compounds having wax-like properties, e.g., carnauba wax, beeswax (white or yellow), lanolin wax, candellila wax, ozokerite, japan wax, paraffin wax, microcrystalline wax, ceresin, cetearyl esters wax, syn-thetic beeswax,etc. Also, hydrophilic waxes as Cetearyl Alcohol or partial glycerides.</p>
<p>Pearlescent waxes: Ikylene glycol esters, especially ethylene glycol distearate; fatty acid alkanolamides, especially coco fatty acid diethanolamide; partial glycerides, especially stearic acid monoglyceride; esters of polyvalent, unsubstituted or hydroxy-substituted carboxylic acids with fatty alcohols having from 6 to 22 carbon atoms, especially long-chained esters of tartaric acid; fatty substances, for example fatty alcohols, fatty ketones, fatty aldehydes, fatty ethers and fatty carbonates, which in total have at least 24 carbon atoms, especially laurone : ..* and distearyl ether; fatty acids, such as stearic acid, hydroxystearic acid or behenic acid, * .. . 15 ring-opening products of olefin epoxides having from 12 to 22 carbon atoms with fatty * ** alcohols having from 12 to 22 carbon atoms and/or polyols having from 2 to 15 carbon atoms and from 2 to 10 hydroxy groups, and mixtures thereof. ***</p>
<p>: Hydrocarbon oils: * *20 Mineral oil (light or heavy), petrolatum (yellow or white), microcrystalline wax, paraffinic and isoparaffin ic compounds, hydrogenated isoparaffinic molecules as polydecenes and polybu-tene, hydrogenated polyisobutene, squalane, isohexadecane, isododecane and others from plant and animal kingdom.</p>
<p>Silicones or siloxanes (organosubstituted polysiloxanes) Dimethylpolysiloxanes, methyiphenylpolysiloxanes, cyclic silicones, and also amino-, fatty acid-, alcohol-, polyether-, epoxy-, fluorine-, glycoside-and/or alkyl-modified silicone com- pounds, which at room temperature may be in either liquid or resinous form. Linear poly-siloxanes, dimethicone (Dow Corning 200 fluid, Rhodia Mirasil DM), dimethiconol, cyclic silicone fluids, cyclopentasiloxanes volatiles (Dow Corning 345 fluid), phenyltrimethicone (Dow Corning 556 fluid). Also suitable are simethicones, which are mixtures of dimethicones having an average chain length of from 200 to 300 dimethylsiloxane units with hydrogenated silicates. A detailed survey by Todd et a!. of suitable volatile silicones may in addition be found in Cosm. Toil. 91,27(1976).</p>
<p>-51 -Fluorinated or perfluorinated oils Peruluorhexane, dimethylcyclohexane, ethylcyclopentane, polyperfluoromethylisopropyl ether.</p>
<p>Emulsifiers Any conventionally usable emulsifier can be used for the compositions. Emulsifier systems may comprise for example: carboxylic acids and their salts: alkaline soap of sodium, potassium and ammonium, metallic soap of calcium or magnesium, organic basis soap such as Lauric, palmitic, stearic and oleic acid etc... Alkyl phosphates or phosphoric acid esters, acid phosphate, diethanolamine phosphate, potassium cetyl phosphate. Ethoxylated carboxylic acids or polyethyleneglycol esters, PEG-n acylates. Linear fatty alcohols having from 810 22 carbon atoms, branched from 2 to 30 mol of ethylene oxide and/or from 0 to 5 mol propylene oxide with with fatty acids having from 12 to 22 carbon atoms and with alkylphenols having from 8 to 15 carbon atoms in the alkyl group. Fatty alcohol polyglycol-ether such as laureth-n, ceteareth-n, steareth-n, oleth-n. Fatty acid polyglycolether such as PEG-n stearate, PEG-n oleate, PEG-n cocoate. Monoglycerides and polyol esters. C12-C22 * * fatty acid mono-and di-esters of addition products of from 1 to 30 mol of ethylene oxide with polyols. Fatty acid and polyglycerol ester such as monostearate glycerol, diisostearoyl *20 polyglyceryl-3-diisostearates, polyglyceryl-3-diisostearates, triglyceryl dilsostearates, polyglyceryl-2-sesquiisostearates or polyglyceryl dimerates. Mixtures of compounds from a plurality of those substance classes are also suitable. Fatty acid polyglycolesters such as monostearate diethylene glycol, fatty acid and polyethylene glycol esters, fatty acid and saccharose esters such as sucro esters, glycerol and saccharose esters such as sucro glycerides. Sorbitol and sorbitan, sorbitan mono-and di-esters of saturated and unsaturated fatty acids having from 6 to 22 carbon atoms and ethylene oxide addition products.</p>
<p>Polysorbate-n series, sorbitan esters such as sesquiisostearate, sorbitan, PEG-(6)-isostearate sorbitan, PEG-( 1 0)-sorbitan laurate, PEGi 7-dioleate sorbitan. Glucose derivatives, C8-C22 alkyl-mono and oligo-glycosides and ethoxylated analogues with glucose being preferred as the sugar component. O/W emulsifiers such as methyl gluceth-20 sesquistearate, sorbitan stearate/sucrose cocoate, methyl glucose sesquistearate, cetearyl alcohol/cetearyl glucoside. W/O emulsifiers such as methyl glucose dioleate/ methyl glucose isostearate. Sulfates and sulfonated derivatives, dialkylsulfosuccinates, dioctyl succinate, alkyl lauryl sulfonate, linear sulfonated parafins, sulfonated tetraproplyne sulfonate, sodium -52 -lauryl sulfates, amonium and ethanolamine lauryl sulfates, lauyl ether sulfates, sodium laureth sulfates, sulfosuccinates, aceyl isothionates, alkanolamide sulfates, taurines, methyl taurines, imidazole sulfates. Amine derivatives, amine salts, ethoxylated amines, oxide amine with chains containing an heterocycle such as alkyl imidazolines, pyridine derivatives, isoquinoteines, cetyl pyridinium chlorure, cetyl pyridinium bromide, quaternary ammonium such as cetyltrimethylbroide amonium broide (CTBA), stearylalkoniurn. Amide derivatives, alkanolamides such as acylamide DEA, ethoxylated amides such as PEG-n acylamide, oxy- deamide. Polysiloxane/polyalkyl/polyether copolymers and derivatives, dimethicone, copo-lyols, silicone polyethylene oxide copolymer, silicone glycol copolymer. Propoxylated or POE-n ethers (Meroxapols), Polaxamers or poly(oxyethylene)m-block-poly(oxypropylene)n-block(oxyethylene). Zwitterionic surfactants that carry at least one quaternary ammonium group and at least one carboxylate and/or sulfonate group in the molecule. Zwitterionic sur-factants that are especially suitable are betaines, such as N-alkyl-N,N-dimethylammon,um glycinates, cocoalkyldimethylammonium glycinate, N-acylaminopropyl-N,N-dimethyl- 15 ammonium glycinates, cocoacylaminopropyldimethylammonium glycinate and 2-alkyl-3-carboxymethyl-3-hydroxyethylimidazolines each having from 8 to 18 carbon atoms in the alkyl or acyl group and also cocoacylaminoethylhydroxyethylcarboxymethylglycinate, N-alkylbetaine, N-alkylaminobetaines. Alkylimidazolines, alkylopeptides, lipoaminoacides, self . : emulsifying bases and the compounds as described in K.F.DePolo, A short textbook of cosmetology, Chapter 8, Table 8-7, p250-251.</p>
<p>Non ionic emulsifiers such as PEG-6 beeswax (and) PEG-6 stearate (and) polyglyceryl - 2-isostearate [Apifacj, glyceryl stearate ( and) PEG-100 stearate. [Arlacel 165], PEG-5 glyceryl stearate [arlatone 983 SI, sorbitan oleate (and) polyglyceryl-3 ricinoleate.[Arlacel 1689], sorbitan stearate and sucrose cocoate [arlatone 2121], glyceryl stearate and laureth- 23 [Cerasynth 945], cetearyl alcohol and ceteth-20 [Cetomacrogol Wax], cetearyl alcohol and colysorbate 60 and PEG-i 50 and stearate-20[Folawax GP 200, Polawax NE], cetearyl alcohol and cetearyl polyglucoside [Emulgade PL 1618], cetearyl alcohol and ceteareth-20 [Emulgade 1000NI, Cosmowax], cetearyl alcohol and PEG-40 castor oil [Emulgade F Special], cetearyl alcohol and PEG-40 castor oil and sodium cetearyl sulfate [Emulgade F], stearyl alcohol and steareth-7 and steareth-lO (Emulgator E 2155], cetearyl alcohol and szeareth-7 and steareth-lO [Emulsifying wax U.S.N.F], glyceryl stearate and PEG-75 stearate [Gelot 64], propylene glycol ceteth-3 acetate.[Hetester PCS], propylene glycol isoce(h-3 acetate [Hetester PHA], cetearyl alcohol and ceteth-12 and oleth-12 (Lanbritol Wax -53 -N 21), PEG -6 stearate and PEG-32 stearate [Tefose 1500], PEG-6 stearate and ceteth-20 and steareth-20 ITefose 2000], PEG-6 stearate and ceteth-20 and glyceryl stearate and steareth-20 [Tefose 2561], glyceryl stearate and ceteareth20 [Teginacid H, C, X].</p>
<p>Anionic emulsifiers such as PEG-2 stearate SE, glyceryl stearate SE [Monelgine, Cutina KD]I propylene glycol stearate [Tegin P], cetearyl Alcohol and Sodium cetearyl sulfate [Lanette N, Cutina LE, Crodacol GP], cetearyl alcohol and sodium lauryl sulfate [Lanette W], trilaneth-4 phopshate and glycol stearate and PEG-2 stearate [Sedefos 75], glyceryl stearate and sodium lauryl Sulfate [Teginacid Special]. Cationic acidbases such as cetearyl alcohol and cetrimonium bromide.</p>
<p>The emulsifiers may be used in an amount of, for example, from 1 to 30 % by weight, especially from 4 to 20 % by weight and preferably from 5 to 10 % by weight, based on the total weight of the composition. * .15 ***.</p>
<p>When formulated in 01W emulsions, the preferably amount of such emulsifier system could represent 5% to 20% of the oil phase.</p>
<p>Adiuvants and additives ** * The cosmetic I pharmaceutical preparations, for example creams, gels, lotions, alcoholic and aqueous/alcoholic solutions, emulsions, wax/fat compositions, stick preparations, powders or ointments, may in addition contain, as further adjuvants and additives, mild surfactants, su-per-fatting agents, consistency regulators, thickeners, polymers, stabilisers, biogenic active ingredients, deodorising active ingredients, anti -dandruff agents, film formers, swelling agents, further UV light-protective factors, antioxidants, hydrotropic agents, preservatives, insect repellents, self-tanning agents, solubilisers, perfume oils, colourants, bacteria-inhibiting agents and the like.</p>
<p>SuDer-fattinq agents Substances suitable for use as super-fatting agents are, for example, lanolin and lecithin and also polyethoxylated or acrylated lanolin and lecithin derivatives, polyol fatty acid esters, monoglycerides and fatty acid alkanolamides, the latter simultaneously acting as foam stabilisers.</p>
<p>Surfactants Examples of suitable mild surfactants, that is to say surfactants especiafly well tolerated by the skin, include fatty alcohol polyglycol ether sulfates, monoglyceride sulfates, mono-and/or di-alkyl sulfosuccinates, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, fatty acid glutamates, a-olefin sulfonates, ethercarboxytic acids, alkyl oligoglucosides, fatty acid glucamides, alkylamidobetaines and/or protein fatty acid condensation products, the latter preferably being based on wheat proteins.</p>
<p>Consistency regulators/thickeners and rheology modifiers Silicium dioxide, magnesium silicates, aluminium silicates, polysaccharides or derivatives thereof for example hyaluronic acid, xanthan gum, guar-guar, agar-agar, alginates, carra- ghenan, gellan, pectines, or modified cellulose such as hydroxycellulose, hydroxypropyl-methylcellulose. In addition polyacrylates or homopolymer of reticulated acrylic acids and :... potyacrylamides, carbomer (carbopol types 980, 981, 1382, ETD 2001, ET02020, Ultrez 10) *::::* 15 or Salcare range such as Salcare SC8O(steareth-10 allyl ether/acrylates copolymer), Salcare SC81 (acrylates copolymer), Salcare SC91 and Salcare AST(sodium acrylates copoly-mer/PPG-1 tndeceth-6), sepigel 305(polyacrylamide/laureth-7), Simulgel NS and Simulgel * EG (hydroxyethyl acrylate / sodium acryloyldimethyl taurate copolymer), Stabilen 30 (acrylates / vinyl isodecanoate crosspolymer), Pemulen TR-1 (acrylates / Cl 0-30 alkyl acrylate crosspolymer), Luvigel EM (sodium acrylates copolymer), Aculyn 28 (acrylates/beheneth-25 methacrylate copolyme r), etc. Polymers Suitable cationic polymers are, for example, cationic cellulose derivatives, for example a qua-ternised hydroxymethyl cellulose obtainable under the name Polymer JR 400 from Amerchol, cationic starches, copolymers of diallylammonium salts and acrylamides, quarternised vinyl-pyrrolidone/vinyl imidazole polymers, for example Luviquat (BASF), condensation products of polyglycols and amines, quaternised collagen polypeptides, for example lauryldimonium hydroxypropyl hydrolyzed collagen (LamequatUGrunau), quaternised wheat polypeptides, polyethyleneimine, cationic silicone polymers, for example amidomethicones, copolymers of adipic acid and dimethylaminohydroxypropyldiethylenetriamine (Cartaretin/Sandoz), copoly-mers of acrylic acid with dimethyldiallylammonium chloride (Merquat 550 / Chemviron), poly- aminopolyamides, as described, for example, in FR-A-2 252 840, and the crosslinked water-soluble polymers thereof, cationic chitin derivatives, for example of quaternised chitosan, optionally distributed as microcrystals; condensation products of dihaloalkyls, for example -55-dibromobutane, with bisdialkylamines, for example bisdimethylamino-1,3-propane, cationic guar gum, for example Jaguar C-i 7, Jaguar C-i 6 from Celanese, quaternised ammonium salt polymers, for example Mirapol A-15, Mirapol AD-i, Mirapol AZ-i from Miranol. As an-ionic, zwitterionic, amphoteric and non-ionic polymers there come into consideration, for example, vinyl acetate I crotonic acid copolymers, vinylpyrrolidone I vinyl acrylate copoly-mers, vinyl acetate I butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic anhydride copolymers and esters thereof, uncrosslinked polyacrylic acids and polyacrylic acids crosslinked with polyots, acrylamidopropyl-trimethylammonium chloride /acrylate copolymers, octyl acrylamide/methyl methacrylatetert-butylaminoethyl methacrylate/2-hydroxypropyl methacrylate copolymers, polyvinylpyrrolidone, vinylpyrrolidone/vinyl acetate copolymers, vinylpyrrolidone/dimethylaminoethyl methacrylate/vinyl caprolactam terpolymers and also optionally derivatised cellulose ethers and silicones. Furthermore the polymers as described in EP 1093796 (pages 3-8, paragraphs i7-68) may be used.</p>
<p> 15 Biogenic active ingredients Biogenic active ingredients are to be understood as meaning, for example, tocopherol, toco-pherol acetate, tocopherol palmitate, ascorbic acid, deoxyribonucleic acid, retinol, bisabolol, allantoin, phytantnol, panthenol, AHA acids, amino acids, ceramides, pseudoceramides, essential oils, plant extracts and vitamin complexes. * 20</p>
<p>Deodorising active ingredients As deodorising active ingredients there come into consideration, for example, antiperspi-rants, for example aluminium chiorohydrates (see J. Soc. Cosm. Chem. 24, 281 (1973)).</p>
<p>Under the trade mark Locron of Hoechst AG, Frankfurt (FRG), there is available corner-cially, for example, an aluminium chlorohydrate corresponding to formula Al2(OH)5Cl x 2.5 H20, the use of which is especially preferred (see J. Pharm. Pharmacol. 26, 531 (1975)).</p>
<p>Besides the chiorohydrates, it is also possible to use aluminium hydroxyacetates and acidic aluminium/zirconium salts. Esterase inhibitors may be added as further deodorising active ingredients. Such inhibitors are preferably trial kyl citrates, such as trimethyl citrate, tripropyl citrate, triisopropyl citrate, tributyl citrate and especially triethyl citrate (Hydagen CAT, Hen-kel), which inhibit enzyme activity and hence reduce odour formation. Further substances that come into consideration as esterase inhibitors are sterol sulfates or phosphates, for example lanosterol, cholesterol, campesterol, stigmasterol and sitosterol sulfate or phos- phate, dicarboxylic acids and esters thereof, for example glutaric acid, glutaric acid mono- -56 -ethyl ester, glutaric acid diethyl ester, adipic acid, adipic acid monoethyl ester, adipic acid diethyl ester, malonic acid and malonic acid diethyl ester and hydroxycarboxylic acids and esters thereof, for example citric acid, malic acid, tartaric acid or tartaric acid diethyl ester.</p>
<p>Antibacterial active ingredients that influence the germ flora and kill or inhibit the growth of sweat-decomposing bacteria can likewise be present in the preparations (especially in stick preparations). Examples include chitosan, phenoxyethanol and chlorhexidine gluconate. 5-chloro-2-(2,4-dichlorophenoxy)-ptienol (Triclosan, lrgasan, Ciba Specialty Chemicals Inc.) has also proved especially effective.</p>
<p>Anti-dandruff agents As anti-dandruff agents there may be used, for example, climbazole, octopirox and zinc pyri- thione. Customary film formers include, for example, chitosan, microcrystalline chitosan, qua-ternised chitosan, polyvinylpyrrolidone, vinylpyrrolidone/vinyl acetate copolymers, polymers :.. of quaternary cellulose derivatives containing a high proportion of acrylic acid, collagen, *:* 15 hyaluronic acid and salts thereof and similar compounds. * **</p>
<p>:.: . Antioxidants In addition to the primary light-protective substances it is also possible to use secondary light-protective substances of the antioxidant kind that interrupt the photochemical reaction chain triggered when UV radiation penetrates the skin or hair. Typical examples of such anti- oxidants are amino acids (e.g. glycine, histidine, tyrosine, tryptophan) and derivatives there-of, imidazoles (e.g. urocanic acid) and derivatives thereof, peptides, such as D,L-carnosine, D-carnosine, L-carnosine and derivatives thereof (e.g. anserine), carotinoids, carotenes, lycopene and derivatives thereof, chlorogenic acid and derivatives thereof, lipoic acid and derivatives thereof (e.g. dihydrolipoic acid), aurothioglycose, propylthiouracil and other thiols (e.g. thioredoxin, glutathione, cysteine, cystine, cystamine and the glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl, lauryl, palmitoyl, oleyl, linoleyl, cholesteryl and glyceryl esters thereof) and also salts thereof, dilauryl thiodipropionate, distearyl thiodipropionate, thiodi- propionic acid and derivatives thereof (esters, ethers, peptides, lipids, nucleotides, nucleo- sides and salts) and also sulfoximine compounds (e.g. buthionine sulfoximines, homo-cysteine sulfoximine, buthionine sulfones, penta-, hexa-, hepta-thionir,e sulfoximine), also (metal) chelating agents (e.g. hydroxy fatty acids, palmitic acid phytic acid, lactoferrin), hydroxy acids (e.g. citric acid, lactic acid, malic acid), humic acid, bile acid, bile extracts, bilirubin, biliverdin, EDTA, EDDS, EGTA and derivatives thereof, unsaturated fatty acids and -57 -derivatives thereof (e.g. linolenic acid, linoleic acid, oleic acid), folic acid and derivatives thereof, ubiquinone and ubiquinol and derivatives thereof, vitamin C and derivatives (e.g. ascorbyl patmitate, magnesium ascorbyl phosphate, ascorbyl acetate), tocopherols and derivatives (e.g. vitamin E acetate), vitamin A and derivatives (e.g. vitamin A palmitate) and also coniferyl benzoate of benzoin resin, rutinic acid and derivatives thereof, glycosyirutin, ferulic acid, furfurylidene glucitol, carnosine, butyl hydroxytoluene, butyl hydroxyanisole, nordihydroguaiaretic acid, trihydroxybutyrophenone, uric acid and derivatives thereof, mannose and derivatives thereof, superoxide dismutase, N-[3-(3, 5-di-tert-butyl-4-hydroxy-phenyl)propionyljsulfanilic acid (and salts thereof, for example the disodium salts), zinc and derivatives thereof (e.g. ZnO, ZnSO4), selenium and derivatives thereof (e.g. selenium me-thionine), stilbene and derivatives thereof (e.g. stilbene oxide, trans-stilbene oxide) and the derivatives suitable according to the invention (salts, esters, ethers, sugars, nucleotides, nucleosides, peptides and lipids) of those mentioned active ingredients. HALS (="Hindered Amine Light Stabilizers") compounds may also be mentioned.</p>
<p>*:* 15 Further synthetic and natural antioxidants are listed e.g. in patent WO 0025731: Structures 1-3 (page 2), structure 4 (page 6), structures 5-6 (page 7) and compounds 7-33 (page 8-14). S..</p>
<p>S</p>
<p>* * The amount of antioxidants present is usually from 0.001 to 30 % by weight, preferably from * **o 0.01 to 3% by weight, based on the weight of the UVabsorber of formula (1).</p>
<p>Hydrotropic agents To improve the flow behaviour it is also possible to employ hydrotropic agents, for example ethoxylated or non ethoxylated mono-alcohols, diols or polyols with a low number of carbon atoms or their ethers (e.g. ethanol, isopropanol, 1,2-dipropanediol, propyleneglycol, glyerin, ethylene glycol, ethylene glycol monoethylether, ethylene glycol monobutylether, propylene glycol monomethylether, propylene glycol monoethylether, propylene glycol monobutylether, diethylene glycol monomethylether; diethylene glycol monoethylether, diethylene glycol monobutylether and similar products). The polyols that come into consideration for that purpose have preferably from 2 to 15 carbon atoms and at least two hydroxy groups. The polyols may also contain further functional groups, especially amino groups, and/or may be modified with nitrogen. Typical examples are as follows: glycerol, alkylene glycols, for example ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, hexylene glycol and also polyethylene glycols having an average molecular weight of from 100 to 1000 -58 -Dalton: technical oligoglycerol mixtures having an intrinsic degree of condensation of from 1.5 to 10, for example technical diglycerol mixtures having a diglycerol content of from 40 to % by weight; methylol compounds, such as, especially, trimethylolethane, trimethylol-propane, trimethylolbutane, pentaerythritol and diperitaerythritol; lower alkyl-glucosides, especially those having from 1 to 8 carbon atoms in the alkyl radical, for example methyl and butyl glucoside; sugar alcohols having from 5 to 12 carbon atoms, for example sorbitol or mannitol; sugars having from 5 to 12 carbon atoms, for example glucose or saccharose; amino sugars, for example glucamine; dialcohol amines, such as diethanolamine or 2-amino- 1,3-propanediol.</p>
<p>Preservatives and Bacteria-inhibiting agents Suitable preservatives include, for example,Methyl-,Ethyl-, Propyl-, Butyl-parabens, Benzal-konium chloride, 2-Bromo-2-nitro-propane-I,3-diol, Dehydroacetic acid, Diazolidinyl Urea, 2- :.. Dichloro-benzyl alcohol, DMDM hydantoin, Formaldehyde solution, Methyldibromoglu- * * 15 tanitrile, Phenoxyethariol, Sodium Hydroxymethylglycinate, Imidazolidinyl Urea, Triclosan and further substance classes listed in the following reference: K.F.DePolo -A short textbook of cosmetology, Chapter 7, Table 7-2, 7-3, 7-4 and 7-5, p210-219. *..</p>
<p>I</p>
<p>Typical examples of bacteria-inhibiting agents are preservatives that have a specific action against gram-positive bacteria, such as 2,4,4'-trichloro-2'-hydroxydiphenyl ether, chlorhexi-dine (1,6-di(4-chlorophenyl-biguanido)hexane) or TCC (3,4,4'-trichlorocarbanilide). A large number of aromatic substances and ethereal oils also have antimicrobial properties. Typical examples are the active ingredients eugenol, menthol and thymol in clove oil, mint oil and thyme oil. A natural deodorising agent of interest is the terpene alcohol farnesol (3,7,1 1-tn-methyt-2,6,1a-dodecatrien-1-ol), which is present in lime blossom oil. Glycerol monolaurate has also proved to be a bacteniostatic agent. The amount of the additional bacteria-inhibiting agents present is usually from 0.1 to 2 % by weight, based on the solids content of the preparations.</p>
<p>Perfume oils There may be mentioned as perfume oils mixtures of natural and/or synthetic aromatic sub-stances. Natural aromatic substances are, for example, extracts from blossom (lilies, lavender, roses, jasmine, neroli, ylang-ylang), from stems and leaves (geranium, patchouli, petitgrain), from fruit (aniseed, coriander, carraway, juniper), from fruit peel (bergamot, -59 -lemons, oranges), from roots (mace, angelica, celery, cardamom, costus, iris, calmus), from wood (pinewood, sandalwood, guaiacum wood, cedarwood, rosewood), from herbs and grasses (tarragon, lemon grass, sage, thyme), from needles and twigs (spruce, pine, Scots pine, mountain pine), from resins and balsams (galbanum, elemi, benzoin, myrrh, olibanum, opoponax). Animal raw materials also come into consideration, for example civet and castoreum. Typical synthetic aromatic substances are, for example, products of the ester, ether, aldehyde, ketone, alcohol or hydrocarbon type. Aromatic substance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethylmethyiphenyl glycinate, allylcyclohexyl propionate, styrallyl propionate and benzyl salicylate. The ethers include, for example, benzyl ethyl ether; the aldehydes include, for example, the linear alkanals having from 8 to 18 hydrocarbon atoms, citral, citronellal, citronellyl oxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal; the ketones include, for example, the ionones, isomethylionone and methyl * **.</p>
<p>cedryl ketone; the alcohols include, for example, anethol, citronellol, eugenol, isoeugenol, * ** geraniol, linalool, phenyl ethyl alcohol and terpinol; and the hydrocarbons include mainly the :.: terpenes and balsams, it is preferable, however, to use mixtures of various aromatic * substances that together produce an attractive scent. Ethereal oils of relatively low volatility, ** * which are chiefly used as aroma components, are also suitable as perfume oils, e.g. sage oil, * *J camomile oil, clove oil, melissa oil, oil of cinnamon leaves, lime blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil, labolanum oil and lavandin oil. Preference is given to the use of bergamot oil, dihydromyrcenol, lilial, lyral, citronellol, phenyl ethyl alcohol, 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, damascone, bourbon geranium oil, cyclohexyl salicylate, vertofix coeur, iso-E-Super, Fixolide NP, evernyl, iraldein gamma, phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide, romillat, irotyl and floramat alone or in admixture with one another.</p>
<p>Colourants There may be used as colourants the substances that are suitable and permitted for cos-metic purposes, as compiled, for example, in the publication "Kosmetische Färbemittel" of the Farbstoffkommission der Deutschen Forsc hungsgemeinschaft, Verlag Chemie, Wein- -60 -heim, 1984, pages 81 to 106. The colourants are usually used in concentrations of from 0.001 to 0.1 % by weight, based on the total mixture.</p>
<p>Other adiuvants It is furthermore possible for the cosmetic preparations to contain, as adjuvants, anti-foams, such as silicones, structurants, such as maleic acid, solubilisers, such as ethylene glycol, propylene glycol, glycerol or diethylene glycol, opacifiers, such as latex, styrene/PVP or sty-rene/acrylamide copolymers, complexing agents, such as EDTA, NTA, alaninediacetic acid or phosphonic acids, propellants, such as propane/butane mixtures, N20, dimethyl ether, C02, N2 or air, so-called coupler and developer components as oxidation dye precursors, reducing agents, such as thioglycolic acid and derivatives thereof, thiolactic acid, cysteamine, thiomalic acid or mercaptoethanesulfonic acid, or oxidising agents, such as hydrogen peroxide, potassium bromate or sodium bromate.</p>
<p>*** 15 Suitable insect repellents are, for example, N,N-diethyl-m-toluamide, 1,2-pentanediol or in- : * sect repellent 3535; suitable self-tanning agents are, for example, dihydroxyacetone and/or * S erythrulose or dihydroxy acetone and/or dihydroxy acetone precursors as described in WO 01/85124 and/or erythrulose. ** .</p>
<p>S Polymeric beads or hollow spheres as SPF enhancers The combination of the UV-absorbers and UV-absorber combinations, listed above, with SPF enhancers, such as non-active ingredients like Styrene/acrylates copolymer, silica beads, spheroidal magnesium silicate, crosslinked Pol ymethylmethacrylates (PMMA; Micopearl M305 Seppic), can maximize better the UV protection of the sun products. Holosphere additives (Sunspheres ISP, Silica Shells Kobo.) deflect radiation and the effective path length of the photon is therefore increased.( EP08931 19). Some beads, as mentioned pre-viously, provide a soft feel during spreading. Moreover, the optical activity of such beads, e.g.Micropearl M305, cans modulate skin shine by eliminating reflection phenomena and indirectly may scatter the UV light.</p>
<p>Cosmetic or pharmaceutical preparations Cosmetic or pharmaceutical formulations are contained in a wide variety of cosmetic preparations. There come into consideration, for example, especially the following preparations: -61 - -skin-care preparations, e.g. skin-washing and cleansing preparations in the form of tablet-form or liquid soaps, soapless detergents or washing pastes, -bath preparations, e.g. liquid (foam baths, milks, shower preparations) or solid bath preparations, e.g. bath cubes and bath salts; -skin-care preparations, e.g. skin emulsions, multi-emulsions or skin oils; -cosmetic personal care preparations, e.g. facial make-up in the form of day creams or powder creams, face powder (loose or pressed), rouge or cream make-up, eye-care preparations, e.g. eyeshadow preparations, mascara, eyeliner, eye creams or eye-fix creams; lip-care preparations, e.g. lipsticks, lip gloss, lip contour pencils, nail-care preparations, such as nail varnish, nail varnish removers, nail hardeners or cuticle removers; -foot-care preparations, e.g. foot baths, foot powders, foot creams or foot balsams, special deodorants and antiperspirants or callus-removing preparations; .. 15 -light-protective preparations, such as sun milks, lotions, creams or oils, sunblocks or tropicals, pre-tanning preparations or after-sun preparations; -skin-tanning preparations, e.g. self-tanning creams; -depigmenting preparations, e.g. preparations for bleaching the skin or skin-lightening * preparations; * 20 -insect-repellents, e.g. insect-repellent oils, lotions, sprays or sticks; * .: -deodorants, such as deodorant sprays, pump-action sprays, deodorant gels, sticks or roll-ons; -antiperspirants, e.g. antiperspirant sticks, creams or roll-ons; -preparations for cleansing and caring for blemished skin, e.g. synthetic detergents (solid or liquid), peeling or scrub preparations or peeling masks; -hair-removal preparations in chemical forni (depilation), e.g. hair-removing powders, liquid hair-removing preparations, cream-or paste-form hair-removing preparations, hair-removing preparations in gel form or aerosol foams; -shaving preparations, e.g. shaving soap, foaming shaving creams, non-foaming shaving creams, foams and gels, preshave preparations for dry shaving, aftershaves or aftershave lotions; -fragrance preparations, e.g. fragrances (eau de Cologne, eau de toilette, eau de parfum, parfum de toilette, perfume), perfume oils or perfume creams; -62 - -cosmetic hair-treatment preparations, e.g. hair-washing preparations in the form of shampoos and conditioners, hair-care preparations, e.g. pretreatment preparations, hair tonics, styling creams, styling gels, pomades, hair rinses, treatment packs, intensive hair treatments, hair-structuring preparations, eg. hair-waving preparations for permanent waves (hot wave, mild wave, cold wave), hair-straightening preparations, liquid hair-setting preparations, hair foams, hairsprays, bleaching preparations, e.g. hydrogen per-oxide solutions, lightening shampoos, bleaching creams, bleaching powders, bleaching pastes or oils, temporary, semi-permanent or permanent hair colourants, preparations containing self-oxidising dyes, or natural hair colourants, such as henna or camomile.</p>
<p>Presentation forms The final formulations listed may exist in a wide variety of presentation forms, for example: -in the form of liquid preparations as a W/O, 01W, O/WIO, WIOIW or PIT emulsion and all n... 15 kinds of microemulsions, -intheformofagel, -in the form of an oil, a cream, milk or lotion, * *.</p>
<p>-in the form of a powder, a lacquer, a tablet or make-up, -intheformofastick, * 20 -in the form of a spray (spray with propellent gas or pump-action spray) or an aerosol, * -intheformofafoam,or -in the form of a paste.</p>
<p>Of special importance as cosmetic preparations for the skin are light-protective preparations, such as sun milks, lotions, creams, oils, sunbiocks or tropicals, pretanning preparations or after-sun preparations, also skin-tanning preparations, for example self-tanning creams. Of particular interest are sun protection creams, sun protection lotions, sun protection milk and sun protection preparations in the form of a spray.</p>
<p>Of special importance as cosmetic preparations for the hair are the above-mentioned prepa-rations for hair treatment, especially hair-washing preparations in the form of shampoos, hair conditioners, hair-care preparations, e.g. pretreatment preparations, hair tonics, styling creams, styling gels, pomades, hair rinses, treatment packs, intensive hair treatments, hair- -63 -straightening preparations, liquid hair-setting preparations, hair foams and hairsprays. Of special interest are hair-washing preparations in the form of shampoos.</p>
<p>A shampoo has, for example, the following composition: from 0.01 to 5 % by weight of a UV absorber according to the invention, 12.0 % by weight of sodium laureth-2-sulfate, 4.0 % by weight of cocamidopropyl betaine, 3.0 % by weight of sodium chloride, and water ad 100%.</p>
<p>For example, especially the following hair-cosmetic formulations may be used: a1) spontaneously emulsifying stock formulation, consisting of the UV absorber according to the invention, PEG-6-C10oxoalcohol and sorbitan sesquioleate, to which water and any desired quaternary ammonium compound, for example 4 % minkamidopropyl dimethyl- 2- hydroxyethylammonium chloride or Quaternium 80 is added; a2) spontaneously emulsifying stock formulation consisting of the UV absorber according to : *.* 15 the invention, tributyl citrate and PEG-20-sorbitan monooleate, to which water and any desired quaternary ammonium compound, for example 4 % minkamidopropyl dimethyl- * *. 2-hydroxyethylammonium chloride or Quaternium 80 is added; b) quat-doped solutions of the UV absorber according to the invention in butyl triglycol and * tributyl citrate; * 20 C) mixtures or solutions of the UV absorber according to the invention with * * n-alkylpyrrolidone.</p>
<p>Other typical ingredients in such formulations are preservatives, bactericides and bacterio-static agents, perfumes, dyes, pigments, thickening agents, moisturizing agents, humectants, fats, oils, waxes or other typical ingredients of cosmetic and personal care formulations such as alcohols, poly-alcohols, polymers, electrolytes, organic solvents, silicon derivatives, emollients, emulsifiers or emulsifying surfactants, surfactants, dispersing agents, antioxi-dants, anti-irritants and anti-inflammatory agents etc. Examples of cosmetic and pharmaceutical preparations (X = preferred combinations) 01W systems: -Ingredients 1 4 Emulsifiers Potassium Cetyl Phosphate 2%-5% X -64- 01W systems: Ingredients 1 4 L Q Cetearyl Alcohol/ Dicetyl Phosphate/Ceteth- lO Phos-X phate 2%-6% Sodium Stearyl Phtalamate I %-2% -X -Cetearyl Alcohol/Behentrimonium Methosulfate 1 %-5% Quaternium-32 1 %-5% -X -Dimethicone copolyol/ Caprylic/Capric Triglyceride (1%---X - 4%) ---Steareth-2 /Steareth-21 2%-5% --X Polyglyceryl Methyl Glucose Distearate 1 %-4% ---( Lipophilic emollientJdispersant oil 15%-20% X X X X X X X_ Fatty Alcohols and/or Waxes 1 %-5% X X X K X X K L Thickeners (water swellable thickeners) 0.5% -1.5% X X X X K X X ( Preservatives 0. 5% -1% X X X X X X X Chelating agents (such as EDTA) 0%-0.2% X X X X X X K Antioxidants 0.05% -0.2% X X X K X X K Water deionized Qs 100% X X X X K X K Perfume oils 0.1% -0.4% X X X X X X X : ** UV-absorber according to the invention 0,1% -20% X X X K X X K L UV-absorber as described in table 2-4 0% -30% X X X X X X K S... ------ W/Osystems -Ingredients L 1. .4.... . Emulsifiers K K X X X * ** Polyglyceryl-2 Dipolyhydroxystearate 2%-4% K K X X X PEG-30 Dipolyhydroxystearate 2%-4% -K -- Rapeseed Oil Sorbitol Esters 1%-5% -X -- PEG-45/Dodecyl Glycol Copolymer 1%-5% --X -Sorbitan Oleate I Polycerol-3 ricinoleate 1%-5% ----X Lipophilic emollient/dispersant oil 10% -20% K K X X X Fatty Alcohols and/or Waxes 10% -15% K K X X X Electrolytes (NaCI, MgSO4) 0.5% -1% K K X X X Polyol phase (Propylene glycol, glycerin) 1% -8% K K X X X Preservatives 0.3% -0.8% K K X X X Perfume oils 0.1% -0.4% K K X X X Chelating agents (such as EDTA) 0% -0.2% K X)( X Antioxidants 0.05% -0.2% K K X X X Water deionized Qs 100% ( K X X X UV-absorber according to the invention 0,1% -20%. K K X X X UV-absorber as described in table 2-4 0% -30%. K K X X X WlSilicone systems Ingredients i.</p> <p>Dimethicone Copolyol / Cyctomethicone 5%-i 0% X X -65 -W/Silicone
systems Ingredients i 2 3 4 Laurylmethicone Copolyol 5%-10% X X Cyclopentasiloxane 1 5%-25% X --X Dimethicone 15%-25% X X DimethiconeNinyldimethicone Crosspolymer 1%-10% X X X X Humectani/polyols (Propylene glycol, glycerin...) 2%-8% X X X X Chelating agents (such as EDTA) 0%-0.2% X X X X Antioxidants 0.05%-0.2% X X X X Preservatives 0.3%-0.8% X X X X Perfume oils 0.1%-0.4% X X X X Water deionized Qs 100% & .2L.& .& UV-absorber according to the invention 0,1% -20% X X X X UV-absorber as described in table 2-4 0%-30% X X X X Multiple emulsions Ingredients PEG-30 Dipolyhydroxystearate X --X - (2%-6%) -----Cetyl Dimethicone Copolyol X X :.. 1%-3% PEG-30 Dipolyhydroxystearate/ X X Steareth-2/ Steareth-21 4%-6% ---Polyglyceryl- 2 Dipolyhydroxy-X X stearate 1 %-3% *.: Polyglyceryl-6 Ricinoleate 1%-3% -X X -- Oil phase 15%-30% --Fatty acid esters X X X X X X _ Natural and synthetic Triglycerides X X X X X X X Hydrocarbon oils X X X X X X X Silicone oils X X X X X X X Preservatives 0.3% -0.8% X X X X X X X X X X X X Water Deioniz. gs 100% X X X X X X X X X X X X Sorbitan Stearate/Sucrose Cocoate X X X 3%-7% Sucrose Laurate 3%-7% X --X X Potoxamer 407 3%-7% X X X Polyoxyethylene(20)Sorbate X X -Monoleate 3%-5% Primary emulsion WhO 50% X X X X X X X X X X X X Thickeners (water swellable X X X X X X X X X X X X polymers) 0.3%-1% ------Water deionized Qs 100% X X X X X X X X X X X X Perfume oils 0.1%-0.4% )( X X X X X X X X X X X Multiple emulsions Ingredients 1 2 3 4 5 6 7 8 9 10 11 12 UV-absorber according to the X X X X X X X X X X X X invention 0,1%-20% UV-absorber as described in table X X X X X X X X X X X X 2-4 0% -30% 011W102 emulsions Ingredients 1. 4 Z Primary emulsion 011W --PEG-60 Hydrogenated Castor Oil 25% X X X X Steareth-25 25% X X X X Oil phase 75% --Fatty acid esters X Natural and synthetic Triglycerides X X Hydrocarbon oils --X Silicone oils -X X : * Preservatives 0.3% -0.8% X X X X X X X X Water deionized Qs 100% X X X X X X X X Non ionic multifunctional W/0 emulsifier 2%-X X X X X X X X Waxesl/o-5/o X X X X X X X X Oil phase 20%-30% X X X X X Silicone oils Primaryemulsion0llW 15% X X X X X X X X Electrolytes (NaCI, MgSO4) 0.1%-0.5% X X X X X X X X Water deionized Qs 100% X X X X X X X X Perfume oils 0.1%-0.4% X X X X X X X X UV-absorber according to the invention X X X X X X X X 0,1%-20% UV-absorber as described in table 2-4 X X X X X X X X 0%-30% Microemulsions Ingredients 1 2 3 4 5 6 z PEG-8 Caprylic/Capric Glycerides 10%-25% X X X --X X -PPG-5-ceteth-20 10%-25% X X -X X -X Polyglyceryl-6 Isostearate 5%-I 5% X -X ----- Polyglyceryl-3 Diisostearate 5%-15% --X --- Polyglyceryl-6 Dioleate 5%-15% ----X -X --- PPG-10 Cetyl Ether 5%-15% X X -Ethoxydiglycol 5%-15% ---X X Oil phase 1 0%-80% X X X X X X X X X X Isostearyl Benzoate 2. 2L Isostearyl Isostearate X X X X X X X X X X -67 -Microemulsions Ingredients.1 4 Z 1Q PEG-7 Glyceryl Cocoate X X X X X X X X X X Qyclomethicone X X X X X X X X X X Polyalcohols/Humectants 1%-10% X X X X X X X X X X Preservatives 0.3 -0.8% X X X X X X X X X X Perfume oils 0.1%-0.4% X X X X X X X X X X Water Deioniz. gs 100% X X X X X X X X X X UV-absorber according to the invention 0,1%-X X X X X X X X X X 20% UV-absorber as described in table 2-4 X X X X X X X X X X 0%-30% 01W Spray emulsions Ingredients.1. 4 Alkyl Phosphates 0.1 %-5% X X X Glucosidic derivatives 0.1 %-5% X X x Solubilisants : ... Ethoxylated Glyceryl ethers 0.1%-1% -X -Polysorbates 0.1%-1% X X Ethoxylated Oleyl ethers 0.1%-1% ---X X * ** PVPNA Coplymer 1%-10% X X -X : . PVM/MA Copolymer 1%-10% X X :. Oil phase 5%-20% X X X X X X * Natural oils (Meadowfoam, Jojoba, Macadamia...) X X X X X X Fatty acids esters X X X X X X Mineral oils X X X X X X Silicone oils X X X X X X Alcohol 0%-50% X X X X X X Thickeners 0.1%-0.5% X X X X X X Polyacrylates.2S_.L.. .&.... X X X Aluminium/Magnesium Silicates X X X X X X Gums X X X X X X Neutralizing agents 0%-1% X X X X X X Polyalcohols/Humectants 1 %-5% X X X X X X Chelating agents (such as EDTA) 0%-0.2% X X X X X X Antioxidants 0.05%-0.2% X X X X X X Water Deioniz. gs 100% X X X X X X Perfume oils 0.1%-0.5% X X X X X X preservatives 0.4%-1% X X X X X X UV-absorber according to the invention 0,1% -20% X X X UV-absorber as described in table 2-4 0% -30% X X X X X X -68-G -Aciueous Inciredients 1 2 3 4 5 6 7 8 9 10 11 12 Thickeners Natural Thickener 1%-5% X --X X ____ X Semi-synthetic Thickener 1%-5% x -x -Synthetic Thickener 0.3% -1.3% X X X X ____ Neutralizing Agents 0.5% -1.5% X X X X X X X X X X X X Polyols -Humectants 5%-50% X X X X X X X X X X X X Polyguaternium series 1%-5% X X X X X X ____ PVM/MA Copolymer 1%-5% X X X X X X Preservatives 0.5%-1% X X X X X X X X X X X X Chelating Agents (as EDTA) < X X X X X X X X X X X X 0.1% ____ Water Deioniz. gs 100% X X X X X X X X X X X X Perfume oils 0.05%-0.4% X X X X X X X X X X X X Ethoxylated Glyceryl ethers X X X 0.1%-5% Polysorbates 0.1%-5% X X X = * Ethoxylated Oleyl ethers X X X X X X 0.1%-5% * UV-absorber according to the X X X X X X X X X X X X :.: ** invention 0,1%-20% -------- * UV-absorber as described in table X X X X X X X X X X X X * 2-4 0%-30% *:*. Oleogels Ingredients 1. 4 Z Hydrogenated Lecithin 1%-10% X X Silica Dimethyl Silylate 1%-10% X X -Silica 1%-5% --X --X C24.28 Alkyl Dimethicone 1 %-5% ---X -X Aluminium or Magnesium Stearate 1%-5% X X -Polyols -Humectants 5%-70% X X X X X X X X X X Oil phase 20% -90% - DicaprylylEther -- Phenyl Trimethicone -- Hydrogenated Polyisobutene - Isopropyl Isostearate -Oleogel basis (Mineral oil and hydrogenated X X Butylene/Ethylene or Ethylene/Propylene Styrene Copolymer) -Silicone wax 1%-10% X X X X X X X X X X Dimethiconol Behenate X X X X X X X X X X Dimethiconol Stearate X X)( X X X X X X X Perfume oils 0.1%-0.5% X X X X X X X X X X -69 -Oleogels Ingredients 1 4 1 1Q Antioxidants 0.05%-0.2% X X X X X X X X X X UV-absorber according to the invention 0,1%-X X X X X X X X X X 20% UV-absorber as described in table 2-4 X X X X X X X X X X 0%-30%) Light/dry cosmetic oils Ingredients 4 Hydrocarbon oils 30%-70% X X Fatty acid esters branched or not 1 0%-50% X X Silicones/Sitoxanes 0% -10% X X Perfluorinated oils and Periluoroethers 0%-10% -X -X Viscosifying agents 0%-i 0% X X X X Esters of long chain acids and alcohols 0% -2% X X X X Antioxidants 0.1%-1% X X X X Solubilisants/dispersing agents 0%-5% X X X X : ... Perfume oils 0.1%-0. 5% X X X X ****** UV-absorber according to the invention 0,1%-20%. X X X X UV-absorber as described in table 2-4 0%-30% X X X X Foaming/mousse Droducts Ingredients.1 SD Alcohol 40 0%-8% X</p>
<p>S</p>
<p>Propellant 8%-15% X Nonionic Emulsifier/Surfactant 0.5% -3% Corrosion Inhibitor 0% -1% Perfume oils 0.1% -0.5% X Preservatives 0.1%- 1% X Miscellaneous 0%-1% X UV-absorber according_to_the_invention_0,1%-20%. _____ UV-absorber as described in table 2-4 0%-30% X Stick products Ingredients 1 Waxes 1 5%-30% x Natural and silicone oils 20%-75% X Lanoline derivatives 5%->50% -_____ Esters of lanolin x Acetylated lanolin x Lanolin oil x Colorants and pigments 10% -15% X Antioxidants 0.1% -0.8% X -70-Stick products Ingredients 1.</p>
<p>Perfumeoils 0.1%-2% X Preservatives O.1%-0.7% X UV-absorber according to the invention 0,1 %-20% X UV-absorber as described in table 2-4 O%-30% X Liquid and compact Ingredients 1 _____ Liquid foundation _____ ______ Powder phase 10%-15% X ____ Oil phase 30% -40%; 75% (only for anhydrous form) X _____ Thickener/suspending agents 1 %-5% X _____ Film forming polymers 1%-2% X _____ Antioxidants 0.1% -1% X _____ Perfume oils 0.1% -0.5% X _____ Preservatives 0.1%-0.8% X _____ Water deionized Qs 100% X _____ : *** Compact powder ____ _____ Powder phase 15%-50% _____ X Oilphase 15%-50% ____ X * .* Polyol phase 5% -15% ____ X :.: * Antioxidants 0.1%-1% _____ X *:. Perfume oils 0.1% -0.5% _____ X Preservatives 0.1%-0.8% _____ X * For the two product forms _____ _____ UV-absorber according to the invention 0,1%-20% X X UV-absorber as described in table 2-4 0%-30% X X The cosmetic preparation according to the invention is distinguished by excellent protection of human skin against the damaging effect of sunlight.</p>
<p>-71 -A. Preparation Examples Example Al: Preparation of the compound of formula (101) N -)-NN---(\ 1N</p>
<p>N NO</p>
<p>1.8g (0.O2lmol) piperazine are added to a solution of 4.4g (0.01 mol) of the monochiorotriazine of formula (lOla) N'")-CI in 50m1 dimethylformamide and stirred at 75 C for 2h.</p>
<p> 10 The reaction solution is decanted on lOOmI water and stirred.</p>
<p>*, * The raw product is filtered off, washed with water, stirred in aceton, filtered off and dried in * vacuo at 80 C.</p>
<p>A white product is obtained.</p>
<p>Yield: 2.Og (44.6%) colorless cristals; Fp= 287-290 C NMR: 13C NMR (90 MHz): ö 14.61 (CH3), 60.63. (CH2), 119.35 (CH), 122.99 (Cq), 130.35 (CH), 145.02 (Cq), 164.38 (Cq), 164.98 (Cq), 165.88 (Cq). -72 -</p>
<p>Example A2: Preparation of the compound of formula</p>
<p>N</p>
<p>(102 y>N N-=N / /_ N-IO O-\ 0.3g ethylendiamine (0.OO5mol) and 1.1.g triethylamine (0.Ollmol) are added to a solution of 4.4g (0.01 mol) of the monochiorotriazine of formula (lOla) in 50ml dimethylformamide and stirred for 2h at 75 C.</p>
<p>The reaction solution concentrated with a rotary evapoarator until drying, gathered in water and weakly acidified with hydrochloric acid (IN).</p>
<p>: . The raw product is filtered off and washed neutral. S...</p>
<p>*..s. After decocting in acetone a white product is obtained.</p>
<p>*.. 10 Yield: 2.7g (62.0%); Fp = 21 3-215 C.</p>
<p>* 3C NMR (90 MHz1): 5= 14.55 (CH3), 14.58 (CH3), 60.52 (CH2), 60.55 (CH2), 119.20 (CH), 122.73 (CH), 122.82 (CH), 130.15 (CH), 145.13 (Cq), 145.29 (Cq), 164.22 (Cq), 164.41 (Cq), 165.87 (Cq), 166.16 (Cq).</p>
<p>Example A3: Preparation of the compound of formula (103) N__(O A solution of 34.7g (0.255mol) 4-aminobenzamide in lOOmI methyl-2-pyrrolidone is added to a solution of 46.lg cyanuric chloride (0.25mo1) in a 800ml dioxan/water mixture (9:1) at 5 C and a pH of 3.5.</p>
<p>Then a solution of 34.7g 4-aminobenzamide (0.255mol) in lOOmI methylpyrrolidone is added at 60-90 C and pH of 8.5.</p>
<p>-73 -The suspension is diluted at 60 C, filterd off warm and washed with dioxan and water.</p>
<p>After decocting with in dimethylfomamide and acetone a white product of formula H2N \/ (103a) N\ ,)_CI HN0 >-N is obtained.</p>
<p>0.432g (0.OO5mol) piperazine and 1.lg triethylamine (0.Olniol) are added to a solution of 3.84g (0.Olmol) of the monochlorotriazine of formula (103a) in dimethylfomamide.</p>
<p>The reaction mixture is stirred at 75 C for 6h and then at 90 C for 1 h. After concentrating with the rotary evaporator until drying the residue is gathered in water, :. 10 weakly acidified with hydrochloric acid, filtered off and washed neutral with water.</p>
<p>After recrystallization from 1-methyl-2-pyrrolidone and decocting in methanol a white product S.,.</p>
<p>is obtained.</p>
<p>Yield: 1.95g (49.9%) * Melting point: decomposition starting at 260 C Elemental anylysis of the compound of formula (103:</p>
<p>C N</p>
<p>Calculated 58.45 4.65 28.70 LFound 58.07 4.93 28.13 Example A4: Preparation of the compound of formula H2N"L) H N''r N' N (104) 2 N...N 0 NH2 L*cro NH2 0.30g (0.OO5mol) ethylenediamine and 1.lg triethylamine (0.Olmol) are added to a solution of 3.84g (O.Olmol) of the monochiorotriazine of formula (103a) in 5Oml dimethylformamide and stirred for 5.5h at 75 C.</p>
<p>The clear solution is concentrated with a rotary evapoarator until drying, gathered in water, weakly acidified with hydrochloric acid, filtered off and washed neutral with water.</p>
<p>After recrystallization from a dimethylformamide/water mixture (4:6) and decocting in acetone a white product is obtained.</p>
<p>Yield: 0.8g (21.2%) NMR: 13C NMR (90 MHz): o= 31.14, 36.14, 119.26 (CH), 127.72 (Cq), 128.51 (CH), 128.69, 143.09 (Cq), 162.70 (Cq), 163.35 (CH), 163.90 (Cq), 165.13 (Cq), 168.03 (Cq).</p>
<p>Example A5: Preparation of the compound of formula S... * . **.* -0 -* I. * NN (105)</p>
<p>* * N N</p>
<p>O</p>
<p>0.37g (0.OO5mol) propylenediamine and 1.lg (0.01 mol) triethylamine are added to a solution of 4.4g (0.01 mol) of the monochlorotriazine of formula (lOla) in 5Oml dimethylformamide and stirred for 4h at 75 C.</p>
<p>After concentrating with the rotary evaporator until drying the residue is gathered in water and filtered off.</p>
<p>After dissolving in tert. butylmethylether the organic phase is shaken out with brine solution (5%), dried over sodium sulfate and concentrated until drying.</p>
<p>A white product is obtained by column chromatographic purification.</p>
<p>Yield: 2.3g (52%) -75-NMR: 13C NMR (90 MHz): E 14.53 (CH3), 14.58 (CH3), 19.04 (CH3), 46.03. (CH2), 46.68.(CH), 60.54 (CH2), 119.22(CH), 122.73(Cq), 122.85 (Cq), 130.13(CH), 145.11 (Cq), 145.25(Cq), 145.32 (Cq), 164.25 (Cq), 164.38 (Cq), 165.75 (Cq), 165.84 (Cq), 165.87 (Cq), 166.26 (Cq).</p>
<p>Example A6:</p>
<p>The compound of formula (5) (Table 1) is prepared according to the method as described in Example 1. Piperazine is replaced by p-phenylene-diamine.</p>
<p>Example A7:</p>
<p>The compound of formula (18) (Table 1) is prepared according to the method as described in Example 1. Piperazine is replaced by isophoron-diamine (CAS No. 2855-13-2). The compound of formula (lOla) is replaced by -N)-CI *:*.</p>
<p>Example A8:</p>
<p>The compound of formula (19) (Table 1) is prepared according to the method as described in Example 1. Piperazine is replaced by 4,4-diarnino-3,3'-dimethyldicyclohexylmethane. The compound of formula (lOla) is replaced by o'-i-'--</p>
<p>NCI</p>
<p>JL:-o-)N</p>
<p>Example A9:</p>
<p>The compound of formula (20) (Table 1) is prepared according to the method as described in Example 1. Piperazine is replaced by dodecane-1,12-diamine. The compound of formula (lOla) is replaced by -76-</p>
<p>Example AlO:</p>
<p>The compound of formula (30) (Table 1) is prepared according to the method as described in Example 1. Piperazine is replaced by isophoron-diamine. The compound of formula (lOla) is replaced by s0,--' N' )-ci / OQ)N</p>
<p>-H * * /l</p>
<p>Example All:</p>
<p>The compound of formula (32) (Table 1) is prepared according to the method as described in Example 1. Piperazine is replaced by dodecane-l, 1 2-diamine. The compound of formula (lOla) is replaced by - 77 -\/ Si0.-' N</p>
<p> N /\</p>
<p>Example A12:</p>
<p>The compound of formula (43) (Table 1) is prepared according to the method as described in 5 Example 1. Piperazine is replaced by 4,4'-diarnino-3,3'-dimethyldicyclohexylmethane The compound of formula (lOla) is replaced by * ** * S S 5*55 -Si \/ H N' \)-ci / /ONH -H /I</p>
<p>Example A13:</p>
<p>The compound of formula (31) (Table 1) is prepared according to the method as described in Example 1. Piperazine is replaced by 4,4'-Diarnino-3,3'-dimethyldicyclohexylmethane. The compound of formula (lOla) is replaced by -78 -S0,V N /\</p>
<p>Example A14:</p>
<p>The compound of formula (51) (Table 1) is prepared according to the method as described in Example 1. Piperazine is replaced by 1,6-hexandiol. The compound of formula (lOla) is .. 5 replaced by *..S %1 :.: * \==/ __J N' )-ci</p>
<p>Example Al 5:</p>
<p>The compound of formula (53) (Table 1) is prepared according to the method as described in Examp'e 1. Piperazine is replaced by neopentylglycol (CAS No. 126-30-7). The compound of formula (lOla) is replaced by o,-o--</p>
<p>-</p>
<p>Example A16:</p>
<p>The compound of formula (57) (Table 1) is prepared according to the method as described in Example 1. Piperazine is replaced by neopentylglycol. The compound of formula (lOla) is replaced by Si," N -/ O%jN o' \1 H . / : ..* *.I. / * I S. * **</p>
<p>:.: * Example A17:</p>
<p>The compound of formula (50) (Table 1) is prepared according to the method as described in *. Example 1. Piperazine is replaced by 1,6-hexandiol. The compound of formula (lOla) is * .10 replaced by Si.0,' N' \)i-cl / O-%)N o-J \=! H /\ L -80-</p>
<p>Example A18:</p>
<p>The compound of formula (49) (Table 1) is prepared according to the method as described in Example 1. Piperazine is replaced by 1,6-hexandiol. The compound of formula (lOla) is replaced by Si-0.-" N / O-)N 0---.... NH \=J H . / : ...</p>
<p>S... /</p>
<p>S I *SIS</p>
<p>B. Application examples 5.5 ExampleBi: A Q E F G *1 5 * . S _____________________________________ ____ ____ ____ ____ * INCI-Name i wlw w/w w/w w/w w/w w/w wlw Ethyihexyl Methoxycinnnamate 9.8 9.8 98 8 9.8 9.8 9.8 Cyclomethicone 7.0 7.0 7.0 70 7.0 7.0 7.0 Octadecene/MA Copolymer (and) Methyl Acethyl 3.0 Ricinoleate (and) Di-methylhepthyl Adipate _____ _____ _____ _____ C30-38 olefin/isopropyl maleate/MA copolymer ____ 2.0 Hydrogenated Dimer Dilinoleyl/Dimethylcarbonate 3.0 Copolymer _____ _____ _____ _____ _____ Cyclopentasiloxane (and) 7.0 Acrylates/Polytrimethylsiloxymethacrylate Copolymer Isododecane (and) 8.0 Acrylates/Polytrimethylsiloxymethacrylate Copolymer PoIy(Glycol Adipate)/Bis-Hydroxyethyoxypropyl 5.0 Dimethicone Copolymer ____ ____ ____ ____ _____ Ethylhexyl Palmitate 5.0 50 O 5.0 5.0 5.0 5.0 Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine 2.0 2.0 2.0 2.0 2.0 2.0 2. 0 Pentaerythrityl Distearate _____ 1.5 _____ _____ _____ 3.0 -81 -</p>
<p>Example BI: P E</p>
<p>INCI-Name % % % % % % % wlw w/w w/w w/w w/w wiw w/w Glyceryl Dibehenate (and) Tribehenin (and) -2.0 4.0 Glyceryl Behenate _____ _____ _____ _____ _____ Glyceryl Stearate 1.5 1.5 _____ 1.5 _____ C20-22 Alkyl Phosphate (and) C20-22 Alcohols _____ 3.0 _____ _____ 2.5 _____ Candelilla/Jojoba/Rice Bran Polyglyceryl-3 esters 6.0 4.0 (and) glyceryl stearate (and) Cetearyl alcohol (and) Sodium stearoyl lactylate _____ _____ _____ _____ _____ Glyceryl oleate citrate (and) Caprylic/Capric 5.0 Triglycerides ______ _____ ______ _____ ______ Potassium Cetyl Phosphate 1.8 -_____ 1.8 _____ _____ VP/Eicosene Copolymer 0.6 -____ 0.6 ____ _____ Aqua Qsto Qsto Qsto Qsto Qsto Qsto Qsto 100 100 100 100 100 100 Methylene Bis-Benzotriazolyl 2.0 2.0 20 2.0 2.0 2.0 2.0 Tetramethylbutytphenol _____ _____ _____ _____ _____ : * PVP/dirnethylconylacrylate/polycarbamyl/polyglycol * ester *.** Polyester-5 _____ _____ _____ _____ _____ Acrylates/Palmeth-25 Acrylate Copolymer 0.3 -____ _____ ____ _____ a ** Disteareth-75 IPDI _____ 0.3 3. 0 _____ ____ _____ * a * __________________________________ ____ ____ ____ ____ Disteareth-100 IPDI _____ 0.3 3.0 _____ _____ ** AcrylatesNinyl Neodecanoate Crosspolymer 1.5 5.0 Compound of formula (56) or (3) or (12) or (17) or 2.0 4.0 6.0 8.0 10.0 12.0 14.0 * : (18) or (19) or (20) or (24) or (30) or (31) or (32) or * *. (35) or (41) or (42) or(43) or (44) or (50) or (51) or (53) Micronized 2,4,6-Tris(p-biphenylyl)-s-triazine [CAS No. 31274-51 -8] 5.0 9.0 3.0 1.0 7.0 2.0 15.0 Glycerin 6.0 6.0 6.0 60 6.0 6.0 6.0 Disodium EDTA 0.2 02 0.2 0.2 0.2 0.2 0.2 Phenoxyethanol (and) Methylparaben (and) 0.7 0.7 0.7 0.7 0.7 0.7 0.7 Ethylparaben (and) Butylparaben (and) Propylparaben (and) Isobutylparaben _____ _____ _____ _____ _____ Tocopheryl Acetate 0.3 0.3 03 0.3 0.3 0.3 0.3 Example B2 A B C P E F G lNCl-Name j % % w/w wlw w/w w/w w/w wiw wiw C12-l5Alkyl Benzoate 4.0 4.0 4.0 4.0 4.0 4.0 4.0 Butyl Methoxydibenzoylmethane 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Octocrylene 7.5 7.5 7.5 7.5 7.5 7.5 7.5 Isohexadecane 3.0 3.0 3.0 3.0 3.0 3.0 3.0 Cyclopentasiloxane 4.0 4.0 4.0 4.0 4.0 4.0 4.0 Terephthalylidene Dicamphor Sulfonic Acid 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Titanium Dioxide particles size 10 to 100 nm 1.7 1.7 1.7 1.7 1.7 1.7 1.7 1102 (and) isodeceth-6(and)Qleth-_____ 1.5 _____ _____ _____ _____ 1.0 Example B2 A B C D E E INCI-Name % % % % % % % w/w wlw wiw w/w w/w w/w wlw 10(and)Alumina(and) Simethicone ____ ____ ____ _____ _____ _____ Alumina coated Ti02 ____ 2.0 ____ 4.0 _____ ____ Ti02(and)isolaureth-4 Phosphate(and)Vinylbuteth-0.5 0.5 0.5 0.5 0.5 0.5 0.5 25/Sodium maleate copolymer _____ _____ _____ _____ _____ _____ _____ Ti02(and)Diethylhexylcarbonate(and)polyglyceryl-0.8 0.8 0.8 0.8 0.8 0.8 0.8 6 polyhydroxystearate _____ _____ _____ _____ _____ _____ _____ Ti02(and)Aluminurn hydroxide(and)Dimethiconol 3.0 methicone copolymer _____ _____ _____ _____ _____ _____ _____ T102(and)Aluminum hydroxide(and)Dimethiconol 2.0 methicone copolymer _____ _____ _____ _____ _____ _____ _____ Silica coated Ti02 _____ _____ _____ 3.0 _____ _____ _____ Ti02(and)Aluminium hydroxide(and) lsostearic 7.0 acid _____ _____ _____ _____ _____ _____ _____ Maganese modified Ti02 ____ ____ ____ ____ _____ 8.0 _____ ZnO particles size 10 to 100 nm 3.0 3.0 3.0 3.0 3.0 3.0 3.0 Pentaerythrityl Distearate _____ 1.5 _____ _____ _____ _____ 1.0 Glyceryl Dibehenate (and) Tribehenin (and) 2.0 4.0 * * Glyceryl Behenate ____ ____ ____ ____ _____ _____ _____ *..:: Stearic Acid 0.5 0.5 0.5 0.5 0.5 0.5 0.5 PEG-looStearate(and)Glyceryl Stearate 0.8 0.8 0.8 0.8 0.8 0.8 0.8 Octadecene/MA Copolymer (and) Methyl Acethyl 3.0 Ricinoleate (and) Di-methylhepthyl Adipate _____ _____ _____ _____ _____ _____ _____ * C30-38 olefin/isopropyl maleate/MA copolymer ____ ____ 2.0 ____ _____ _____ _____ : * Hydrogenated Dimer Dilinoleyl/Dimethylcarbonate 3.0 Copolymer ____ ____ ____ ____ _____ _____ _____ Cyclopentasiloxane (and) 7.0 * : Acrylates/Polytrimethylsiloxymethacrylate * . Copolynier ____ ____ ____ ____ _____ _____ _____ Isododecane (and) 8.0 Acrylates/Polytrimethylsiloxymethacrylate Copolyrner ____ ____ ____ _____ _____ _____ Poly(Glycol Adipate)/Bis-Hydroxyethyoxypropyl 5.0 Dimethicone Copolymer _____ _____ _____ _____ _____ _____ C20-22 Alkyl Phosphate (and) C20-22 Alcohols ____ 2.5 ____ ____ _____ 3.0 _____ Candelilla/Jojoba/Rice Bran Polyglyceryl-3 esters 5.0 6.0 (and) glyceryl stearate (and) Cetearyl alcohol (and) Sodium stearoyl lactylate _____ _____ _____ _____ _____ _____ Glyceryl oleate citrate (and) Caprylic/Capric 4.0 Triglycerides _____ _____ _____ _____ _____ _____ Potassium Cetyl Phosphate 1.3 _____ _____ 1.3 _____ _____ PVP/Eicosene Copolymer 1.0 ____ ____ _____ _____ _____ Aqua Qsto Qsto Qsto Qsto Qsto Qsto Osto _____________________________________ 100 100 100 100 100 100 Glycerin 4. 0 Q. 4.0 4.0 4.0 4.0 4.0 Compound of formula (56) or (3) or (12) or (17) or 2.0 4.0 6.0 8.0 10.0 12.0 14.0 (18) or (19) or (20) or (24) or(30) or(31) or (32) or (35) or (41) or (42) or (43) or (44) or (50) or (51) or (53) _____ _____ _____ _____ _____ _____ Micronized 2 4,6-Tris(p-biphenylyl)-s-triazine [CAS No. 31274-51-8] 5.0 90 3.0 1.0 7.0 2.0 15.0 Propylene Glycol 5.0 SM 5.0 5.0 5.0 5.0 5.0 -83 -Example B2 A B C D E E INCI-Name ?l t2 w/w w/w wiw wiw wiw wiw w/w Xanthan Gum 0.2 02 02 02 0.2 0.2 0.2 PVP/dimethylconylacrylate/polycarbamyl/polyglycol ester _____ _____ _____ _____ Polyester-5 _____ _____ _____ _____ Disteareth-75 IPDI _____ 03 3.0 ____ ____ _____ Disteareth-100 IPDI _____ 0.3 3.0 ____ _____ AcrylatesNinyl Neodecanoate Crosspolymer _____ _____ 1.5 5.0 Acrylates/C10-30 Alkyl Acrylate Crosspolymer 0.2 ____ ____ _____ Disodium EDTA 0.2 02 0.2 02 0.2 0.2 0.2 Triethanolamine Qs Qs Qs Qs Qs Qs Qs Dimethicone 0.4 04 0.4 OA 0.4 0.4 0.4 Phenoxyethanol (and) Methylparaben (and) 0.7 0.7 0.7 0.7 0.7 0.7 0.7 Ethylparaben (and) Butyl paraben (and) Propylparaben (and) Isobutylparaben _____ _____ _____ _____ Tocopheryl Acetate 0.9 09 0.9 0.9 0.9 0.9 0.9 ExampleB3 A B C D E E INCI-Name % % % % % % % _______________ _ wi wi _ Synthetic Beeswax 0.5 05 0.5 0.5 0.5 0.5 0.5 Ethylhexyl Methoxycinnamate (stabilized by 9.8 9.8 9.8 9.8 9.8 9.8 9. 8 incorporating into a polymer) _____ _____ _____ _____ -_____ _____ Isoamyl p-Methoxycinnamate 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Ethyihexyl Salicylate 5.0 5.0 5.0 5.0 5.0 5.0 5.0 Butyl Methoxydibenzoylmethane (stabilized by 4.0 4.0 5.0 4.0 4.0 4.0 3.0 incorporating into a polymer) _____ _____ _____ _____ _____ _____ 4-Methylbenzylidene Camphor 4.0 40 4.0 4.0 4.0 4.0 4.0 Bis-Ethyihexyloxyphenol Methoxyphenyl Triazine 2.0 3.0 2.0 1.0 1.0 1.0 1. 0 Octadecene/MA Copolymer (and) Methyl Acethyl 3.0 Ricinoleate (and) Di-methylhepthyl Adipate _____ _____ _____ _____ _____ _____ C30-38 olefin/isopropyl maleate/MA copolymer _____ 2.0 ____ ____ _____ ____ Hydrogenated Dimer Dilinoleyl/Dimethylcarbonate 3.0 Copolymer _____ _____ _____ _____ _____ _____ Cyclopentasiloxane (and) Acrylates/Polytrimethyl-7.0 siloxymethacrylate Copolymer _____ _____ _____ _____ _____ _____ lsododecane (and) Acrylates/Polytrimethylsiloxy-8.0 methacrylate Copolymer _____ ____ ____ _____ _____ ____ Poly(Glycol Adipate)/Bis-Hydroxyethyoxypropyl 5.0 Dimethicone Copolymer _____ ____ ____ _____ _____ ____ Dimethicone 4.5 45 4.5 4.5 4.5 4.5 4.5 C20-22 Alkyl Phosphate (and) C20-22 Alcohols _____ 3.0 _____ _____ _____ 3.0 _____ Candelilla/Jojoba/Rice Bran Polyglyceryl-3 esters 4.0 4.0 (and) glyceryl stearate (and) Cetearyl alcohol (and) Sodium stearoyl lactylate _____ _____ _____ _____ _____ _____ Glyceryl oleate citrate (and) Caprylic/Capric 6.0 Triglycerides ______ _____ _____ ______ ______ _____ Cetearyl Alcohol (and) Dicetyl Phosphate (and) 4.5 4.5 Ceteth-lO Phosphate _____ _____ _____ _____ _____ _____ -84 -ExampleB3 A B C D E E INCI-Name % % % % % % % wiw w/w w/w w/w wiw wiw w/w Cetyl Ricinoleate 3.0 3.0 3.0 3.0 3.0 3.0 3.0 Pentaerythrityl Distearate 1.5 _____ _____ _____ _____ 3.0 Glyceryl Dibehenate (and) Tribehenin (and) 2.0 4.0 Glyceryl Behenate _____ _____ _____ _____ _____ _____ _____ Hydroxypropyl Dimethicone Behenate 2. 2 1.0 _____ 2.2 _____ 2.2 0.5 Decyl Cocoate 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Aqua Qs to Qs to Qs to Qs to Qs to Qs to Qs to 100 100 100 100 100 100 Propylene Glycol 3.0 3.0 3.0 3.0 3.0 3.0 3.0 Compound of formula (56) or (3) or (12) or (17) or 3.0 3.0 3.0 3.0 3.0 3.0 3.0 (18) or (19) or (20) or (24) or (30) or (31) or (32) or (35) or (41) or (42) or (43) or (44) or (50) or (51) or (53) 1,1'-(1,4-piperazinediyl)bis[1-[2-[4-(diethylamino)-2.0 3.0 1.0 8.0 4.0 3.0 1.0 2-hydroxybenzoyl]phenyll-metharione (CAS No. 919803-06-8) ____ _____ ____ ____ ____ ____ Decyl Glucoside 0.5 05 0.5 0.5 0.5 0.5 0.5 AcrylatesNinyl Neodecanoate Crosspolymer _____ _____ _____ _____ _____ _____ Ammonium AcryloyldimethyltaurateNP Copolymer 0.3 03 0.3 0.3 0.3 0.3 0.3 PVP/dimethylconylacrylatelpolycarbamyl/polyglycol ester Polyester-5 _____ _____ _____ _____ _____ _____ PhenylbenzimidazoleSulfonicAcid 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Disteareth-75 IPDI ____ 0.3 3.0 ____ ____ * Disteareth-100 IPDI ____ _____ 0.3 3.0 ____ * . AcrylatesNinyl Neodecanoate Crosspolymer _____ _____ _____ _____ 1.5 5.0 Acrylates/C1030 Alkyl Acrylate Crosspolymer 02 Disodium EDTA 0.2 0.2 0.2 0.2 0.2 0.2 02 Methylene Bis-Benzotriazolyl 5.0 5.0 5.0 5.0 5.0 5.0 50 Tetramethylbutyiphenol _____ _____ _____ _____ Tromethamine 0.8 0.8 0.8 0.8 0.8 0.8 0.8 Cyclohexasiloxane (and) Cyclopentasiloxane 0.8 0.8 0.8 0. 8 0.8 0.8 0.8 Phenoxyethanol (and) Methylparaben (and) Ethyl-0.8 0.8 0.8 0. 8 0.8 0.8 0.8 paraben (and) Butylparaben (and) Propylparaben (and) Isobutylparaben _____ _____ _____ Tocopheryl Acetate OA 04 0.4 04 0.4 0.4 0.4 CAS-Regno. 88122-99-0, Ethylhexyl tnazone (Octyl triazone; Uvinul T 150) 2.0 1.5 2.0 1.0 ____ CAS-Regno.6197-30-4, Octocrylene 3.0 4.0 5.0 ____ 1.0 5.0 CAS-Regno. 180898-37-7, Disodium phenyldibenzimidazoletetrasulfonate Neo Heliopan AP or Neo-Heliopan APC 30 4.0 5.0 3.0 ____ ____ CAS-Regno. 302776-68-7, Uvinul A Plus 4.0 5.0 ____ ____ CAS-Regno. 44481 1-29-4, Propanedioic acid, [(4-hydroxy-3,5-dimethoxyphenyl)methylene]-, bis(2-ethyihexyl) ester (Oxynex ST) 3.0 -1.0 -_____ _____ CAS-Regno. 477844-93-2, Octofluorene ____ 3.0 1.0 ____ ____ ____ 2-phenylethylbenzoate _____ 1.0 1.0 _____ _____ _____ Example B3 A B C D E F G INCI-Name % % % % % % % w/w wiw w/w w/w wlw w/w w/w CAS-Regno. 68890-66-4, Octopirox 2.0 ____ ____ 30 1.0 _____ ____ Tinogard U (INCI Tetradibutyl Pentaerithrityl Hydroxy-hydrocinnamate) 1.0 _____ 1.0 1.0 3.0 _____ _____ Tinogard HS (INC I Sodium Benzotriazolyl Butylphenol Sulfonate) ____ 2.0 3.0 _____ 3.0 ____ Tinogard TL (INCI Benzotriazolyl Dodecyl p-Cresol) 2.0 ____ 1.0 1.0 ____ 1.0 3.0 Phenol, 2-(2H-benzotriazol-2-yl)-6-dodecyl-4-methyl-, branched andlinear _____ 2.0 _____ 3.0 _____ _____ Cibafast H Liquid (INCI Sodium Benzotriazolyl Butyiphenol Sulfonate, Buteth-3, Tributyl Citrate) 1.0 _____ _____ _____ _____ Tinogard AS (INCI Bumetrizole) 2.0 -1.0 _____ _____ ____ Tris(tetramethylhydroxypiperidinol) citrate (Tinogard Q) 1.0 -1.0 _____ _____ _____ 220410-74-2 4-Piperidinol, I -hydroxy-2,2,6,6tetramethyl-, 2-hydroxy-1,2,3-propanetricarboxylate (3:1)(salt) ____ 1.0 _____ _____ 1.0 : CAS-Regno. 1750-49-8, N-(2-Hydroxypropyl)urea ____ 5A ____ ____ 10.0 ____ CAS-Regno. 2078-71-9, N-(2-Hydroxyethyl)urea ____ 10. 0 10.0 _____ ____ mixture of n-butylphthalimide and : *, isopropylphthalimide 0.5 ____ 5.0 _____ _____ ____ CAS-Regno. 872424-70-9 2.0 ____ 1.0 _____ ____ ** CAS-Regno. 872424-71-0 ____ 2.0 ____ ____ 1.0 ____ CAS-Regno. 872424-72-1 ____ 2.0 _____ ____ 1.0 *. : CAS-Regno. 872424-73-2 ____ ____ 20 ____ ____ ____ mixture of glycosyiglycerides or 2-0-beta-glucopyranosyi-sn-glycerin 3.0 _____ 2.0 _____ _____ diaminobenzimidazole 0.1 -____ _____ ____ ____ dihydroxyacetone ____ 2.0 4.0 2.0 _____ _____ 2.0 carnitine 3.0 1.0 -____ 1.0 ____ Tropolone 0.3 ____ 0.2 _____ ____ CAS-Regno. 130603-71-3, aipha-Glucosylrutin 0.5 0.1 ____ 1.0 _____ _____ ____ CAS-Regno. 425371-14-8 ____ ____ ____ ____ ____ CAS-Regno. 425371 -1 5-9 ____ ____ _____ _____ ____ CAS-Regno. 261 356-1 3-2 ____ ____ ____ ____ 2.0 CAS-Regno. 425371-03-5 ____ ____ ____ 2.0 ____ CAS-Regno. 425371-04-6 ____ ____ 2.0 _____ ____ CAS-Regno. 25371-05-7 ____ ____ 2.0 ____ ____ ____ CAS-Regno. 425371-06-8 ____ ____ ____ 2.0 _____ ____ CAS-Regno. 425371 -07-9 ____ ____ ____ _____ _____ 2.0 CAS-Regno. 425371-08-0 ____ ____ ____ _____ _____ ____ CAS-Regno. 425371-09-1 ____ ____ _____ _____ ____ CAS-Regno. 425371 -1 0-4 ____ ____ _____ _____ ____ CAS-Regno. 425371-11-5 ____ ____ ____ 2.0 ____ CAS-Regno. 494198-67-3 ____ ____ _____ _____ ____ CAS-Regno. 803699-05-0 ____ ____ _____ _____ ____ CAS-Regno. 803699-07-2 ____ ____ ____ _____ _____ 2.0 Example B3 A B C 0 E -F G INCI-Name 4 wiw wiw wiw w/w w/w w/w w/w CAS-Regno. 803699-09-4 ____ ____ _____ ____ _____ 2.0 ____ CAS-Regno. 803699-11-8 ____ ____ ____ ____ 2.0 -____ ____ CAS-Regno. 803699-14-1 ____ ____ _____ 2.0 _____ _____ ____ CAS-Regno. 803699-15-2 ____ ____ _____ ____ 2.0 _____ ____ CAS-Regno. 803699-17-4 ____ ____ _____ ____ _____ _____ 2.0 CAS-Regno. 803699-18-5 ____ ____ _____ ____ _____ _____ ____ CAS-Regno. 88137-31-9 ____ ____ _____ 3.0 _____ _____ ____ CAS-Regno. 101220-33-1 ____ ____ ____ ____ ____ 2.0 ____ CAS-Regno.
875878-17-4 ____ ____ _____ ____ _____ _____ ____ CAS-Regno. 875878-18-5 ____ ____ _____ ____ _____ _____ ____ CAS-Regno. 916463-32-6 ____ ____ _____ ____ _____ _____ 2.0 CAS-Regno. 880761-99-9 ____ ____ _____ ____ 2.0 _____ ____ CAS-Regno. 880761 -95-5 ____ ____ _____ 2.0 _____ _____ ____ ExampleB4 A B C D E F G</p>
<p>--</p>
<p>INCI-Name % wiw % w/w % wlw % w/w % w/w % wlw % w/w</p>
<p>________________________________________ ________ ________ ________ ________ ________ ________ ________</p>
<p>C12-15 Alkyl Benzoate 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Butyl Methoxydibenzoylmethane 1.0 1.0 1.0 1.0 1.0 1.0 1.0 : * Octocrylene 7.5 7.5 7.5 7.5 7.5 7.5 7.5 Neopentyl Glycol Diheptanoate 6.0 ______ 5.0 ______ ______ ______ ______ Propylene Glycol Dibenzoate 4.0 _______ ______ ______ ______ ______ _______ Polyester-i and Neopenthyl Glycol 8.0 Diheptanoate ______ _______ ______ ______ ______ ______ _______ * . . ____________________________ _____ ______ _____ _____ _____ _____ ______ * . Diethylhexyl Syringylidenemalonate ______ 6.0 ______ ______ ______ ______ _______ Polyester 8 ______ _______ 4.0 ______ Diethylhexyl Malate ______ _______ ______ 7.0 ______ ______ PPG-3 Myristyl Ether Neoheptanoate ______ ______ ______ ______ ______ 6.0 ______ Phenethyl Benzoate ______ ______ ______ ______ ______ ______ 8.0 Isopropyl PPG-2 Isodeceth-7 Carboxylate ______ _______ ______ ______ ______ ______ _______ Isopropyl Cl 2-1 5-Pareth-9 Carboxylate ______ _______ ______ ______ ______ ______ _______ Cetyl PPG-2 Isodeceth-7 Carboxylate ______ _______ ______ ______ ______ ______ _______ Isohexadecane 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Cyclopentasiloxane 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Terephthalylidene Dicamphor Sulfonic 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Acid ______ _______ ______ ______ ______ ______ _______ Titanium Dioxide particles size 10 to 1.7 1.7 1.7 1.7 1.7 1.7 1.7 nm Stearic Acid 0.5 0.5 0.5 0.5 0.5 0.5 0.5 PEG-i 00 Stearate (and) Glyceryl 0.8 0.8 0.8 0.8 0.8 0 8 0.8 Stearate Potassium Cetyl Phosphate 1.3 1.3 1.3 1.3 1.3 1.3 1.3 PVP/Eicosene Copolymer 1.0 1. 0 1.0 1.0 1.0 1.0 1.0 Aqua Qsto Osto Qsto Qsto Qsto Qsto Qsto 100 100 100 100 100 100 ExampleB4 A B C D E E ____ INCI-Name % wiw % w/w % wiw % wiw % w/w % wlw % w/w Glycerin 4.0 4.0 4.0 4.0 4.0 4.0 4.0 Compound of formula (56) or (3) or (12) 4.0 4.0 4.0 4.0 4.0 4.0 4.0 or (17) or (18) or(19) or (20) or (24) or (30) or (31) or (32) or (35) or (41) or (42) or (43) or (44) or (50) or (51) or (53) ______ ______ ______ ______ ______ ______ _______ 1,1'-(1,4-piperazinediyl)bis[1-[2-[4-2.0 4.0 3.0 4.0 2.0 1.0 4.0 (diethylam ino)-2-hydroxybenzoyl]phenyl]-methanone (CAS No. 919803-06-8) Micronized 2,4,6-Tris(p-biphenylyl)-s-triazine [CAS No. 31274-51-8] 5.0 9.0 3.0 1.0 7.0 2.0 15.0 Propylene Glycol 5.0 5.0 5.0 5.0 5.0 5.0 5.0 Xanthan Gum 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Acrylates/C10-3oAlkylAcrylate 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Crosspolymer ______ ______ ______ ______ ______ ______ _______ Disodium EDTA 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Triethanolamine Qs Qs Qs Qs Qs Qs Qs Dimethicone 0.4 0.4 0.4 0.4 0.4 0.4 0.4 Phenoxyethanol (and) Methylparaben 0.7 0.7 0.7 0.7 0.7 0.7 0.7 (and) Ethylparaben (and) Butylparaben : *. (and) Propylparaben (and) Isobutylparaben ______ ______ ______ ______ ______ ______ _______ Tocopheryl Acetate 0.9 0.9 0.9 0.9 0.9 0.9 0.9 Example 65 A B C D E E _____ INCI-Name % w/w % w/w % w/w % w/w % w/w % wlw % w/w Synthetic Beeswax 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Ethylhexyl Methoxycinnamate 9.8 9.8 9.8 9.8 9.8 9.8 9.8 Isoamyl p-Methoxycinnamate 2.0 2.0 2.0 2.0 2.0 2.0 2. 0 Ethyihexyl Salicylate 5.0 5.0 5.0 5.0 5.0 5.0 5.0 Butyl Methoxydibenzoylmethane 2.8 2.8 2.8 2.8 2.8 2.8 2.8 4-Methylbenzylidene Camphor 4.0 4.0 4.0 4.0 4.0 4.0 4.0 Bis-Ethylhexyloxyphenol 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Methoxyphenyl Triazine ______ ______ ______ Dimethicone 4.5 4.5 4.5 4.5 4.5 4.5 4.5 Cetearyl Alcohol (and) Dicetyl Phos-4.5 4.5 4.5 4.5 4.5 4.5 4.5 phate (and) Ceteth-lO Phosphate ______ ______ ______ ______ ______ ______ ______ Cetyl Ricinoleate 3.0 3.0 3.0 3.0 3.0 3.0 3.0 Butylene Glycol Cocoate 4.0 6.0 4.0 3.0 2.0 1.0 2.5 Hydroxypropyl Dimethicone 2.2 2.2 2.2 2.2 2.2 2.2 2.2 Behenate Decyl Cocoate 1.0 1.0 10 1.0 1.0 1.0 1.0 Aqua Qsto Qsto Qsto Qsto Qsto Qsto Qsto 100 100 100 100 100 100 Propylene Glycol 3.0 3.0 3.0 3.0 3.0 3.0 3.0 -88 -Example B5 A B C D E F G INCI-Name %w/w %w/w %w/w %wlw %w/w %w/w %w/w Micronized 2,4,6-Tris(p-biphenylyl)-s-1.0 3.0 2.0 2.0 1.0 0.5 1.0 triazine [CAS No. 31274-51-8] Micronized 1,1-(1,4-piperazinediyl)-3.0 1.0 1.0 4.0 2.0 1 0 3.0 bis[1 -[2-[4-(diethylamino)-2-hydroxy-benzoyl]phenyl]-methanone (CAS No. 919803-06-8) Compound of formula (56) or(3) or 4.0 3.0 2.0 1.0 3.0 5. 0 3.0 (12) or (1 7) or (18) or (19) or (20)or (24) or (30) or (31) or (32) or (35) or (41) or (42) or (43) or (44) or (50) or (51) or (53) ______ ______ ______ ______ ______ ______ ______ Octocrylene 2.0 4.0 6.0 8.0 10. 0 10.0 8.0 Decyl Glucoside 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Ammonium Acryloyldimethyltauratel-0.3 0.3 0.3 0.3 0.3 0.3 0.3 VP Copolymer ______ ______ ______ ______ ______ ______ ______ Phenylbenzimidazole Sulfonic Acid 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Acrylates/C1O-30 Alkyl Acrylate 0.2 0.2 0.2 0.2 0.2 0.2 0.2 * ** Crosspolymer ______ _____ ______ ______ Disodium EDTA 0.2 0.2 0.2 0.2 0.2 0.2 0.2 **** Methylene Bis-Benzotriazolyl Tetra-5.0 5.0 5.0 5.0 5.0 5.0 5.0 * ** meth.lbutylphenol _______ _____ ______ _______ _______ _______ _______ :.: * Tromethamine 0.8 0.8 0.8 0.8 0.8 0.8 0.8 *:. Styrene/Acrylates Copolymer 5.0 ______ ______ ______ ______ 3.0 ______ PEG-6 Isostearate (and) Hesperetin 3.0 1.0 4.0 Laurate Polyacrylate-1 5 (and) Polyacrylate-1 7 _______ _______ 4.0 _______ _______ _______ _______ Carthamus Tinctorius (Safflower) 5.0 Oleosomes PTFE ______ ______ _____ ______ 4.0 ______ ______ Cyclohexasiloxane (and) Cyclopenta-0.8 0.8 0.8 0.8 0.8 0.8 0.8 siloxane Phenoxyethanol (and) Methylparaben 0.8 0.8 0.8 0.8 0.8 0.8 0.8 (and) Ethylparaben (and) Butylpa-raben (and) Propylparaben (and) Isobutylparaben _______ _______ ______ _______ _______ _______ _______ Tocopheryl Acetate 0.4 0.4 0.4 0.4 0.4 0.4 0.4 -89 -</p>

Claims (2)

  1. <p>Claims 1. Compounds of formula</p>
    <p>R R R4_,f</p>
    <p>R3' )j-N -( =7R3 (1) R2 N N R2,wherein N1 X1 is a bivalent radical of formula (la) -NR9-A-NR9-; (ib) * N/A\N; or A' : *** (ic) *_O..A...O* A and A' independently from each other are unsubstituted or substituted, straight-chain or branched C1-C12alkylene, which is optionally interrupted by C5-C12cycloalkylene, N, 0 or S; C5-C12cycloalkylene; biphenylene; C6-C10arylene; or C5-C1oarylene-(C1-C12alkylene); o a *:*. 10 R1 is a radical of formula (id) *_/< ; (le) (if) O-R5 R5 (ig) **; or (lh) JL1 R2 and R3 independently from each other are hydrogen; C1-C12alkyl; OR7; NR7R8; C6-C10aryl; X2 isO,orNH; W1 is C1-C20alkyl; or a group Sp-Sil; Sp is a straight-chain or branched saturated or single or multiple unsaturated C3-C12 hydrocarbon; Sil is a silane; an oligosiloxane; or a polysiloxane moiety; and R4, R5, R6, R7, R8 and R9 independently from each other are hydrogen; C1-C12alkyl; or C3-C,2cycloalkyl.</p>
    <p>2. Compounds according to claim 1 wherein R1 is a radical of formula (id) ; or (ig) ; wherein O-R5 R' R5 and R6 independently from each other are hydrogen; or C1-C5alkyl.</p>
    <p>3. Compounds according to claim 2, wherein R5 is C1-C5alkyl; or hydrogen; and R6 is hydrogen.</p>
    <p>4. Compounds according to any of claims 1 to 3, wherein X1 is a radical of formula (ib), wherein A1 and A2 are C1-C4alkylene. * S</p>
    <p>5. Compounds according to any of claims 1 to 3, wherein X1 is a radical of formula (la), wherein A1 is C1-C5alkylene; or phenylene; and R9 is hydrogen; 6. Compounds according to any of claims ito 5, wherein X1 is selected from -NH-(CH2)2-NH-; ; -NN---; and 7. Compounds according to any of claims 1 to 6, wherein R2, R3 and R4 are hydrogen.</p>
    <p>8. Compounds according to any of claims 1 to 7, wherein Sil is the group SiR10R11R12, wherein R10, R11 and R12 each independently are C1-C6alkyl; C1-C6alkoxy; or phenyl; or an oligosiloxane of formula -SiMem(OSiMe3)n; or an oligosiloxane of the formulae -91 -Me [Me 1 Me [Me Me Me (ii) Me__O_I_?i_Oi_* ; (1k) Me.j_Si-O Si-O--i-Me. or Me LMe]Me [Me * Me [Me 1 Me (ii) 0-l-?i-O_j--Si-O-SiMe; [Me Ju * Me wherein Me is methyl; m is0;i;or2; :. " isl;2;or3; * ... m+nare3;and ** u is0to6. * I.</p>
    <p>** 10 9. Compounds according to any of claims ito 8, which conform to formula *.S *:*.
  2. (2) R1N' , wherein \).-(/ "N Rl_<)-N> N N< _f-R R1 is a radical of formula (id) _-(ig) or (lh) X1 is radical of formula (la) -NR9-A-NR9-; (ic) *-O-A-O-* ; and.._NcN_ A, W1, X2 and R9 are defined as in formula (1); and R5 and R6 independently from each other are hydrogen; or C1-C4aIkyl.</p>
    <p>10. Compounds according to claim 9, wherein -92 -R1 isaradicalofformula(id) or(lg) 0-R5 R/N R5 X1 is selected from -NH-(CH2)2-NH-; ; _\_N_; and and R5 and R6 independently from each other are hydrogen; or C1-C4alkyl.</p>
    <p>11. Process for the preparation of the compounds of formula (1) which comprises reacting 2 moles of the chiorotriazine of formula (1 m) with 1 mole of the compound of formula (in) :... according to the follwing reaction scheme: S...</p>
    <p>\_N,R4 \_N,R4 R4_,+\ R391)-N _____ R' -N N_( \jR3 :. R2 N >-CI +11-X-K R2 N N R2 R_.>_ N R:_.N N <N( R, **. : R3 R4 == R4 R4)=Th3 * . R2 R2 R2 (im) (in) (i) wherein R1, R2, R3, R4 and X1 are defined as in claim 1.</p>
    <p>12. Process for the preparation of the micronized compound of formula (1) comprising wet-milling,wet-kneading, spray-drying from a suitable solvent, by the expansion according to the RESS process or by reprecipitation from suitable solvents of the compounds of formula (1) to obtain microparticles having a mean particle size from 0,02 to 2 tm.</p>
    <p>13. Cosmetic composition comprising at least one compound of formula (1) according to claim i together with cosmetically tolerable carriers or adjuvants.</p>
    <p>14. Cosmetic composition according to claim 13 wherein the compound of formula (1) is present in the composition in the micronized state.</p>
    <p>15. UV absorber dispersion, comprising (a) at least one micronised UV absorber of formula (1), having a particle size from 0.02 to 2.tm, and (b) a suitable dispersing agent. *.. S... S.</p>
    <p>S S.. *</p>
    <p>S</p>
    <p>S S. * S * S S *S</p>
GB0708326A 2006-05-08 2007-04-30 Triazine derivatives as UV filters for cosmetic compositions Withdrawn GB2438047A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010043588A1 (en) * 2008-10-17 2010-04-22 Basf Se Sunscreen and personal care compositions comprising a random terpolymer
DE102010055763A1 (en) * 2010-12-23 2012-06-28 Beiersdorf Ag Drug combinations of glucosylglycerides and one or more anti-dandruff substances
WO2022260691A1 (en) * 2021-06-09 2022-12-15 Edgewell Personal Care Brands, Llc Sunscreen composition with enhanced photoprotection

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Publication number Priority date Publication date Assignee Title
EP0252508A2 (en) * 1986-07-09 1988-01-13 Mitsubishi Kasei Corporation Water soluble disazo colorant and dyeing method using the same
EP0333653A2 (en) * 1988-03-16 1989-09-20 Ciba-Geigy Ag Reactive dyes, process for their preparation and their use
JPH02202966A (en) * 1989-02-02 1990-08-13 Agency Of Ind Science & Technol Ink composition
EP1426819A2 (en) * 2002-12-06 2004-06-09 Konica Minolta Holdings, Inc. Concentrated bleach-fixer composition for silver halide color photographic material
JP2006208887A (en) * 2005-01-31 2006-08-10 Konica Minolta Photo Imaging Inc Processing composition for silver halide photographic sensitive materials

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0252508A2 (en) * 1986-07-09 1988-01-13 Mitsubishi Kasei Corporation Water soluble disazo colorant and dyeing method using the same
EP0333653A2 (en) * 1988-03-16 1989-09-20 Ciba-Geigy Ag Reactive dyes, process for their preparation and their use
JPH02202966A (en) * 1989-02-02 1990-08-13 Agency Of Ind Science & Technol Ink composition
EP1426819A2 (en) * 2002-12-06 2004-06-09 Konica Minolta Holdings, Inc. Concentrated bleach-fixer composition for silver halide color photographic material
JP2006208887A (en) * 2005-01-31 2006-08-10 Konica Minolta Photo Imaging Inc Processing composition for silver halide photographic sensitive materials

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010043588A1 (en) * 2008-10-17 2010-04-22 Basf Se Sunscreen and personal care compositions comprising a random terpolymer
DE102010055763A1 (en) * 2010-12-23 2012-06-28 Beiersdorf Ag Drug combinations of glucosylglycerides and one or more anti-dandruff substances
WO2022260691A1 (en) * 2021-06-09 2022-12-15 Edgewell Personal Care Brands, Llc Sunscreen composition with enhanced photoprotection

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