New! View global litigation for patent families

US20020004034A1 - Use of sunscreen combinations comprising, as essential constituent, 4,4'-diarylbutadienes as photostable UV filters in cosmetic and pharmaceutical preparations - Google Patents

Use of sunscreen combinations comprising, as essential constituent, 4,4'-diarylbutadienes as photostable UV filters in cosmetic and pharmaceutical preparations Download PDF

Info

Publication number
US20020004034A1
US20020004034A1 US09805238 US80523801A US20020004034A1 US 20020004034 A1 US20020004034 A1 US 20020004034A1 US 09805238 US09805238 US 09805238 US 80523801 A US80523801 A US 80523801A US 20020004034 A1 US20020004034 A1 US 20020004034A1
Authority
US
Grant status
Application
Patent type
Prior art keywords
formula
uv
compounds
sunscreen
cosmetic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
US09805238
Other versions
US6391289B2 (en )
Inventor
Thomas Heidenfelder
Thorsten Habeck
Thomas Wunsch
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date

Links

Images

Classifications

    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K8/00Cosmetics or similar toilet preparations
    • A61K8/18Cosmetics or similar toilet preparations characterised by the composition
    • A61K8/72Cosmetics or similar toilet preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84Cosmetics or similar toilet preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/89Polysiloxanes
    • A61K8/891Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
    • A61K8/893Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone modified by an alkoxy or aryloxy group, e.g. behenoxy dimethicone or stearoxy dimethicone
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K8/00Cosmetics or similar toilet preparations
    • A61K8/18Cosmetics or similar toilet preparations characterised by the composition
    • A61K8/30Cosmetics or similar toilet preparations characterised by the composition containing organic compounds
    • A61K8/33Cosmetics or similar toilet preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/35Ketones, e.g. benzophenone
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K8/00Cosmetics or similar toilet preparations
    • A61K8/18Cosmetics or similar toilet preparations characterised by the composition
    • A61K8/30Cosmetics or similar toilet preparations characterised by the composition containing organic compounds
    • A61K8/49Cosmetics or similar toilet preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/494Cosmetics or similar toilet preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K8/00Cosmetics or similar toilet preparations
    • A61K8/18Cosmetics or similar toilet preparations characterised by the composition
    • A61K8/30Cosmetics or similar toilet preparations characterised by the composition containing organic compounds
    • A61K8/49Cosmetics or similar toilet preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/494Cosmetics or similar toilet 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 TOILET PURPOSES
    • A61K8/00Cosmetics or similar toilet preparations
    • A61K8/18Cosmetics or similar toilet preparations characterised by the composition
    • A61K8/72Cosmetics or similar toilet preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84Cosmetics or similar toilet preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/89Polysiloxanes
    • A61K8/896Polysiloxanes containing atoms other than silicon, carbon, oxygen and hydrogen, e.g. dimethicone copolyol phosphate
    • A61K8/898Polysiloxanes containing atoms other than silicon, carbon, oxygen and hydrogen, e.g. dimethicone copolyol phosphate containing nitrogen, e.g. amodimethicone, trimethyl silyl amodimethicone or dimethicone propyl PG-betaine
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILET 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
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/52Stabilizers
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/57Compounds covalently linked to a(n inert) carrier molecule, e.g. conjugates, pro-fragrances
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/59Mixtures
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILET PREPARATIONS
    • A61Q19/00Preparations for care of the skin
    • A61Q19/001Preparations for care of the lips

Abstract

Sunscreen combinations which comprise, as constituent which absorbs in the UV-A region, 4,4′-diarylbutadienes, and at least one further sunscreen which absorbs in the UV-A region, UV-B region or in both regions, chosen from a group defined in detail in the Description of the Invention below as photostable UV filter combination in cosmetic and pharmaceutical preparations for protecting the human epidermis or human hair against UV radiation, specifically in the range from 320 to 400 nm.

Description

  • [0001]
    Use of sunscreen combinations comprising, as essential constituent, 4,4′-diarylbutadienes as photostable UV filters in cosmetic and pharmaceutical preparations
  • [0002]
    The invention relates to the use of sunscreen combinations which comprise, as constituent which absorbs in the UV-A region, 4,4′-diarylbutadienes, and at least one further sunscreen which absorbs in the UV-A region, UV-B region or in both regions, chosen from a group defined in detail below as photostable UV filter combination in cosmetic and pharmaceutical preparations for protecting the human epidermis or human hair against UV radiation, specifically in the range from 320 to 400 nm.
  • [0003]
    The sunscreens employed in cosmetic and pharmaceutical preparations have the task of preventing, or at least diminishing the consequences of, harmful effects of sunlight on the human skin. However, these sunscreens also serve to protect other ingredients from decomposition or degradation by UV radiation. In hair cosmetic formulations the aim is to reduce damage to the keratin fibers by UV rays.
  • [0004]
    The sunlight reaching the surface of the earth contains proportions of UV-B radiation (280 to 320 nm) and UV-A radiation (>320 nm), which are directly adjacent to the visible light region. The effect on the human skin is manifested, particularly in the case of UV-B radiation, by sunburn. Accordingly, the industry offers a relatively large number of substances which absorb UV-B radiation and thus prevent sunburn.
  • [0005]
    Dermatological investigations have now shown that UV-A radiation is also perfectly capable of causing skin damage and allergies by, for example, damaging the keratin or elastin. This reduces the elasticity and water storage capacity of the skin, i.e. the skin becomes less supple and tends to form wrinkles. The noticeably high incidence of skin cancer in regions where the sun's radiation is strong shows that damage to the genetic information in the cells is evidently also caused by sunlight, specifically by UV-A radiation. All these findings would therefore suggest the need to develop efficient filter substances for the UV-A region.
  • [0006]
    There is a growing demand for sunscreens for cosmetic and pharmaceutical preparations which can be used in particular as UV-A filters and whose absorption maxima ought therefore to be in the range from about 320 to 380 nm. In order to achieve the required effect using the minimum amount, sunscreens of this type ought additionally to have a high specific absorbance. Sunscreens for cosmetic products must also meet a large number of other requirements, for example good solubility in cosmetic oils, high stability of the emulsions produced with them, toxicological acceptability, and low intrinsic odor and low intrinsic color.
  • [0007]
    Another requirement which sunscreens must meet is adequate photostability. However, this is only inadequately ensured, if at all, with the UV-A-absorbing sunscreens hitherto available.
  • [0008]
    French Patent No. 2 440 933 describes 4-(1,1-dimethylethyl)-4′-methoxydibenzoylmethane as a UV-A filter. It is proposed to combine this specific UV-A filter, which is sold by GIVAUDAN under the name “PARSOL 1789”, with various UV-B filters in order to absorb all UV rays having a wavelength from 280 to 380 nm.
  • [0009]
    However, this UV-A filter does not have sufficient photochemical stability, when used alone or in combination with UV-B filters, to ensure sustained protection of the skin during sunbathing for prolonged periods, which means that repeated applications at regular and short intervals are required if effective protection of the skin from all UV rays is desired.
  • [0010]
    For this reason, EP-A-0 514 491 discloses the stabilization of the insufficiently photostable UV-A filters by adding 2-cyano-3,3-diphenylacrylic esters which themselves act as filters in the UV-B region.
  • [0011]
    It has furthermore already been proposed in EP-A-0 251 398 and EP-A-0 416 837 to combine chromophores absorbing UV-A radiation and UV-B radiation into one molecule using a linker This has the disadvantage that firstly a free combination of UV-A and UV-B filters in the cosmetic preparation is no longer possible, and that difficulties in the chemical linkage of the chromophores allow only certain combinations.
  • [0012]
    It is an object of the present invention to propose sunscreens for cosmetic and pharmaceutical purposes which absorb in the UV-A region with high absorbance, which are photostable, have low intrinsic color, i.e. a sharp band structure, and are soluble in oil or water depending on the substituent.
  • [0013]
    We have found that this object can be achieved advantageously by certain sunscreen combinations.
  • [0014]
    Accordingly, this object is achieved according to the invention by the use of sunscreen combinations comprising
  • [0015]
    A) compounds absorbing essentially in the UV-A region and
  • [0016]
    B) further compounds absorbing in the UV-A region, in the UV-B region and over both regions,
  • [0017]
    where the constituents absorbing in the UV-A region comprise effective amounts of at least
  • [0018]
    A) one 4,4′-diarylbutadiene of the formula I
    Figure US20020004034A1-20020110-C00001
  • [0019]
    in which
  • [0020]
    R1 and R2 independently of one another are hydrogen,
  • [0021]
    C1-C20-alkyl, C3-C10-cycloalkyl or C3-C10-cycloalkenyl,
  • [0022]
    and the constituents
  • [0023]
    B) comprise an effective amount of at least one compound chosen from the group consisting of
  • [0024]
    Ba) dibenzoylmethane compounds of the formula III
    Figure US20020004034A1-20020110-C00002
  • [0025]
    in which
  • [0026]
    R3 is C1-C12-alkyl and
  • [0027]
    R4 is hydrogen, C1-C12-alkyl or C1-C12-alkoxy,
  • [0028]
    Bb) triazine derivatives of the formula IV
    Figure US20020004034A1-20020110-C00003
  • [0029]
    in which
  • [0030]
    R5 to R7 independently of one another are optionally substituted C1-C20-alkyl, C5-C10-aryl, C5-C10-heteroaryl or SpSil, where Sp is a spacer and Sil is a silane, oligosiloxane or polysiloxane radical,
  • [0031]
    X is the divalent radical —O— or
    Figure US20020004034A1-20020110-C00004
  • [0032]
    where
  • [0033]
    R8 is hydrogen or optionally substituted C1-C20-alkyl, C5-C10-aryl or C5-C10-heteroaryl,
  • [0034]
    Bc) the triazine derivative of the formula V
    Figure US20020004034A1-20020110-C00005
  • [0035]
    in which at least one o-hydroxyl group and at least one p-alkoxy group having 1 to 20 carbon atoms are bonded to the phenyl rings,
  • [0036]
    Bd) the benzotriazole derivative of the formula VI
    Figure US20020004034A1-20020110-C00006
  • [0037]
    Be) the benzimidazole derivative of the formula VII
    Figure US20020004034A1-20020110-C00007
  • [0038]
    Bf) the benzotriazole derivative of the formula VIII
    Figure US20020004034A1-20020110-C00008
  • [0039]
    Bg) o, o′, p, p′-tetrahydroxybenzophenone of the formula IX
    Figure US20020004034A1-20020110-C00009
  • [0040]
    Bh) an organosiloxane benzalmalonate of the formula Xa
    Figure US20020004034A1-20020110-C00010
  • [0041]
    in which
  • [0042]
    V1′ is the group
    Figure US20020004034A1-20020110-C00011
  • [0043]
    V1 is a methyl group or V1′, or of the formula Xb
    Figure US20020004034A1-20020110-C00012
  • [0044]
    in which V2′ is the group of the structure
    Figure US20020004034A1-20020110-C00013
  • [0045]
    V2 is a methyl group or V2
  • [0046]
    or mixtures of compounds of the formulae Xa and Xb,
  • [0047]
    where t is a value up to 100 and u is a value up to 20, with the proviso that u=0 when V1=V1′ and/or V2=V2′, and u is a value from 1 to 20 when V1=CH3 and/or V2=CH3,
  • [0048]
    as photostable UV filters in cosmetic and pharmaceutical preparations for protecting human skin or human hair against solar rays, optionally together with further compounds which absorb in the UV region and which are known per se for cosmetic and pharmaceutical preparations.
  • [0049]
    The sunscreen combination of the compounds (A) and (B) can be used alone or in combination with other compounds which absorb in the UV range, although at least effective amounts of the compounds (A) and (B) should be present in the sunscreen preparations. “Effective amounts of the compounds (A) and (B)” means generally in each case at least 0.2% by weight, in each case based on the cosmetic preparation.
  • [0050]
    In the sunscreen combinations according to the invention, the amount of compounds which absorb in the UV-B region usually predominates. Accordingly, the content of the compound (A) which absorbs in the UV-A range is generally 5 to 50% by weight, preferably 10 to 25% by weight, in each case based on sunscreen combination of (A) and (3).
  • [0051]
    The combinations of sunscreens (A) and (B) according to the invention have synergistic effects in sun protection action inasmuch as the protective action of the combinations exceeds the sum of the action of the constituents.
  • [0052]
    The compounds (A), i.e. 4,4′-diarylbutadienes of the formula I
    Figure US20020004034A1-20020110-C00014
  • [0053]
    are known from EPA 916 335. The substituents R1 and/or R2 are preferably C1-C8-alkyl and C5-C8-cycloalkyl and very particularly neopentyl.
  • [0054]
    The compounds (B) are all known and are characterized below in more detail:
  • [0055]
    (Ba)
  • [0056]
    The compounds of the formula III are known from FR 2440933. A suitable and preferred compound of the formula III is p-methoxy-p′-t-butyl-dibenzoylmethane (R3=methoxy, R4=t-butyl).
  • [0057]
    (Bb)
  • [0058]
    Compounds of the formula IV where R5 to R7 are alkyl, aryl or heteroaryl are known from EP-A 0796851, EP-A 0087098 and EP-A 0850935. Suitable alkyl radicals are, in particular, straight-chain or branched C1 to C12 radicals, in particular C1 to C8 radicals. Aryl radicals are, for example, phenyl or naphthyl radicals, in particular phenyl radicals. Suitable heteroaryl radicals are single or fused ring systems having one or more heteroaromatic 3- to 6-membered rings. As heteroatoms, one or more nitrogen, sulfur and/or oxygen atoms may be present in the ring or ring system.
  • [0059]
    Compounds of the formula IV with the meaning SpSil are known from EPA 0 933 376.
  • [0060]
    The term spacer for Sp means in this connection a bivalent branched or unbranched C3-C12-alkylene chain or alkenylene chain which links the silane, oligosiloxane or polysiloxane moiety to the triazine radical.
  • [0061]
    Examples of a C3-C12-alkylene chain are propylene, 2-methylpropylene, butylene, pentylene and hexylene.
  • [0062]
    Examples of a C3-C12-alkenylene chain are 2-propen-2-ylene, 2-methyl-3-propenylene, 3-buten-3-ylene and 4-penten-4-ylene.
  • [0063]
    Preferred spacers are —(CH2)3—, —(CH2)4—, —(CH2)5—, —[CH(CH3)]—(CH2)—, —(CH2)2—CH═CH—, —C(═CH2)—CH2—, —C(═CH2)—(CH2)2—O—(CH2)4—, —(CH2)4—O—(CH2)2—.
  • [0064]
    The term silanes in this connection stands for a radical SiR9R10R11, in which R9, R10 and R11, independently of one another, are C1-C6-alkyl, C1-C6-alkoxy or phenyl.
  • [0065]
    Examples which may be mentioned are: Si(CH2—CH3)3, Si(CH2—CH2—CH3)3, Si(isopropyl)3, Si(tert-butyl)3, Si(tert-butyl)(CH3)2, Si(CH3)2 (hexyl), Si(OCH3)3, Si(OEt)3, SiPh3.
  • [0066]
    The term oligosiloxanes means a radical from the group of the general formula, consisting of SiR12 m(OSiR12 3)n where m=0, 1 or 2; n=3, 2 or 1 and m+n=3, R12—[Si(R12)2—O—]r—Si(R12)2—A and R12—[Si(R12)2—O—]r—Si(A)(R12)—O—Si(R12)3, in which A is a chemical bond or a spacer and R12 is a C1-C6-alkyl radical or phenyl radical, and r is a value from 1 to 9.
  • [0067]
    The term polysiloxane includes, for example, a radical from the group of the general formula, consisting of A—[Si(R13)2—O]s—Si(R13]2—A or (R13)3—Si—[O—Si(R13)2]]t—[O—Si(R13)(A)]q—O—Si(R13)3, in which A is a chemical bond or a spacer and R16 is a C1-C6-alkyl radical or phenyl radical, s and t are values from 4 to 250 and q is a value from 1 to 30.
  • [0068]
    Suitable compounds of the formula IV are preferably the triazine compounds of the formula IVa
    Figure US20020004034A1-20020110-C00015
  • [0069]
    or of the formula IVb
    Figure US20020004034A1-20020110-C00016
  • [0070]
    (Bc)
  • [0071]
    Triphenyltriazines of the formula V substituted by at least one o-hydroxyl group and at least one p-alkoxy group are known from WO 99/66896.
  • [0072]
    In particular, triphenyltriazines of the formula Va are suitable
    Figure US20020004034A1-20020110-C00017
  • [0073]
    in which X is hydrogen or a hydroxyl group and Y is a hydroxyl group,
  • [0074]
    R14 is hydrogen or alkoxy having 1 to 12 carbon atoms and R15 and R16 are alkoxy having 1 to 12 carbon atoms.
  • [0075]
    Particular preference is given to the compound of the formula Vb
    Figure US20020004034A1-20020110-C00018
  • [0076]
    (Bd)
  • [0077]
    The compound of the formula VI has the CAS No. 103597-45-1.
  • [0078]
    (Be)
  • [0079]
    The compound of the formula VII has the CAS No. 180898-37-7.
  • [0080]
    (Bf)
  • [0081]
    The compound of the formula VIII has the CAS No. 155633-54-8.
  • [0082]
    (Bg)
  • [0083]
    The compound of the formula IX has the CAS No. 131-55-5.
  • [0084]
    (Bh)
  • [0085]
    The compounds of the formulae Xa and Xb are known from EP-A 0920859.
  • [0086]
    Of the compounds of the formulae Xa and/or Xb those with the CAS numbers 208391-15-5, 208391-15-5D, 177955-90-7, 177955-90-7D and 177995-90-7DP are particularly suitable.
  • [0087]
    In the sunscreen combinations to be used according to the invention, it is possible for not only individual compounds (Ba) to (Bh) to be present, but also mixtures of two or more of these compounds.
  • [0088]
    The present invention further relates to cosmetic and pharmaceutical preparations which have 0.1 to 10% by weight, preferably 1 to 7% by weight, based on the total amount of cosmetic and pharmaceutical preparation, of a sunscreen combination comprising
  • [0089]
    A) compounds absorbing essentially in the UV-A region and
  • [0090]
    B) further compounds absorbing in the UV-A region, in the UV-B region and over both regions,
  • [0091]
    where the constituents absorbing in the UV-A region comprise effective amounts of at least
  • [0092]
    A) one 4,4′-diarylbutadiene of the formula I
    Figure US20020004034A1-20020110-C00019
  • [0093]
    in which
  • [0094]
    R1 and R2 independently of one another are hydrogen, C1-C20-alkyl, C3-C10-cycloalkyl or C3-C10-cycloalkenyl,
  • [0095]
    and as constituents
  • [0096]
    B) an effective amount of at least one compound chosen from the group consisting of
  • [0097]
    Ba) dibenzoylmethane compounds of the formula III
    Figure US20020004034A1-20020110-C00020
  • [0098]
    in which
  • [0099]
    R3 is C1-C12-alkyl and
  • [0100]
    R4 is hydrogen, C1-C12-alkyl or C1-C12-alkoxy,
  • [0101]
    Bb) triazine derivatives of the formula TV
    Figure US20020004034A1-20020110-C00021
  • [0102]
    in which
  • [0103]
    R5 to R7 independently of one another are optionally substituted C1-C20-alkyl, C5-C10-aryl, C5-C10-heteroaryl or SpSil, where Sp is a spacer and Sil is a silane, oligosilane or polysiloxane radical,
  • [0104]
    X is the divalent radical —O— or
    Figure US20020004034A1-20020110-C00022
  • [0105]
    where
  • [0106]
    R8 is hydrogen or optionally substituted C1-C20-alkyl, C5-C10-aryl or C5-C10-heteroaryl,
  • [0107]
    Bc) triazine derivatives of the formula V
    Figure US20020004034A1-20020110-C00023
  • [0108]
    in which at least one o-hydroxyl group and at least one p-alkoxy group having 1 to 20 carbon atoms are bonded to the phenyl rings,
  • [0109]
    Bd) the benzotriazole derivative of the formula VI
    Figure US20020004034A1-20020110-C00024
  • [0110]
    Be) the benzimidazole derivative of the formula VII
    Figure US20020004034A1-20020110-C00025
  • [0111]
    Bf) the benzotriazole derivative of the formula VIII
    Figure US20020004034A1-20020110-C00026
  • [0112]
    Bg) o, o′, p, p′-tetrahydroxybenzophenone of the formula IX
    Figure US20020004034A1-20020110-C00027
  • [0113]
    Bh) an organosiloxane benzalmalonate of the formula Xa
    Figure US20020004034A1-20020110-C00028
  • [0114]
    in which
  • [0115]
    V1′ is the group
    Figure US20020004034A1-20020110-C00029
  • [0116]
    V1 is a methyl group or V1′, or of the formula Xb
    Figure US20020004034A1-20020110-C00030
  • [0117]
    in which V2′ is the group of the structure
    Figure US20020004034A1-20020110-C00031
  • [0118]
    V2 is a methyl group or V2
  • [0119]
    or mixtures of compounds of the formulae Xa and Xb,
  • [0120]
    where t is a value up to 100 and u is a value up to 20, with the proviso that u=0 when V1=V1′ and/or V2=V2′, and u is a value from 1 to 20 when V1=CH3 and/or V2=CH3,
  • [0121]
    optionally together with further compounds which absorb in the UV-A and UV-B region and which are known per se for cosmetic and pharmaceutical preparations, as sunscreens, where the UV-A-absorbing compounds are generally used in a lesser amount than the V-B-absorbing compounds.
  • [0122]
    The sunscreen-containing cosmetic and pharmaceutical preparations are, as a rule, based on a carrier which comprises at least one oil phase. However, preparations based solely on water are also possible if compounds having hydrophilic substituents are used
  • [0123]
    Accordingly, oils, oil-in-water and water-in-oil emulsions, creams and pastes, protective lipstick compositions or fat-free gels are suitable.
  • [0124]
    Suitable emulsions are inter alia also O/W macroemulsions, O/W microemulsions or O/W/O emulsions containing 4,4′-diarylbutadienes of the formula I in dispersed form, the emulsions being obtainable by phase inversion technology, as in DE-A-197 26 121.
  • [0125]
    Conventional cosmetic auxiliaries which may be suitable as additives are, for example, coemulsifiers, fats and waxes, stabilizers, thickeners, biogenic active substances, film formers, fragrances, dyes, pearlizing agents, preservatives, pigments, electrolytes (e.g. magnesium sulfate) and pH regulators. Suitable and preferred coemulsifiers are known W/O and also O/W emulsifiers such as polyglycerol esters, sorbitan esters or partially esterified glycerides. Typical examples of fats are glycerides; waxes which may be mentioned are, inter alia, beeswax, paraffin wax or microwaxes, possibly combined with hydrophilic waxes. Stabilizers which can be employed are metal salts of fatty acids such as, for example, magnesium, aluminum and/or zinc stearate. Examples of suitable thickeners are crosslinked polyacrylic acids and derivatives thereof: polysaccharides, in particular xanthan gum, guar guar, agar agar, alginates and tyloses, carboxymethylcellulose and hydroxyethylcellulose, also fatty alcohols, monoglycerides and fatty acids, polyacrylates, polyvinyl alcohol and polyvinylpyrrolidone. Examples of biogenic active substances are plant extracts, protein hydrolysates and vitamin complexes. Examples of customary film formers are hydrocolloids such as chitosan, microcrystalline chitosan or quaternized chitosan, polyvinylpyrrolidone, vinylpyrrolidone/vinyl acetate copolymers, polymers of the acrylic acid series, quaternary cellulose derivatives and similar compounds. Examples of suitable preservatives are formaldehyde solution, p-hydroxybenzoate or sorbic acid. Examples of suitable pearlizing agents are glycol distearic esters such as ethylene glycol distearate, but also fatty acids and fatty acid monoglycol esters. Dyes which can be used are the substances suitable and approved for cosmetic purposes, as listed, for example, in the publication “Kosmetische Färbemittel” [Cosmetic Colorants] from the Farbstoffkommission der Deutschen Forschungsgemeinschaft [Dyes Commission of the German Research Society], published by Verlag Chemie, Weinheim, 1984. These dyes are normally employed in a concentration of from 0.001 to 0.1%, based on the total weight of the mixture.
  • [0126]
    An additional content of antioxidants is generally preferred. Thus, it is possible to use as favorable antioxidants all antioxidants which are customary or suitable for cosmetic and/or dermatological applications.
  • [0127]
    The antioxidants are advantageously chosen from the group consisting of amino acids (e.g. glycine, histidine, tyrosine, tryptophan) and derivatives thereof, imidazoles (e.g. urocanic acid) and derivatives thereof, peptides such as D,L-carnosine, D-carnosine, L-carnosine and derivatives thereof (e.g. anserine), carotenoids, carotenes (e.g. β-carotene, lycopene) and derivatives thereof, chlorogenic acid and derivatives thereof, lipoic acid and derivatives thereof (e.g. dihydrolipoic acid), aurothioglucose, propylthiouracil and other thiols (e.g thiorodoxin, glutathione, cysteine, cystine, cystamine and the glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl, and lauryl, palmitoyl, oleyl, γ-linoleyl, cholesteryl and glyceryl esters thereof) and salts thereof, dilauryl thiodipropionate, distearyl thiodipropionate, thiodipropionic acid and derivatives thereof (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts), and sulfoximine compounds (e.g. buthionine sulfoximines, homocysteine sulfoximines, buthionine sulfones, penta-, hexa-, heptathionine sulfoximine) in very low tolerated doses (e.g. pmol to μmol/kg), and also (metal) chelating agents (e.g. α-hydroxy fatty acids, palmitic acid, phytic acid, lactoferrin), α-hydroxy acids (e.g. citric acid, lactic acid, malic acid), humic acid, bile acid, bile extracts, bilirubin, biliverdin, EDTA and derivatives thereof, unsaturated fatty acids and derivatives thereof (eg. γ-linolenic acid, linoleic acid, oleic acid), folic acid and derivatives thereof, ubiquinone and ubiquinol and derivatives thereof, vitamin C and derivatives thereof (e.g. ascorbyl palmitate, Mg ascorbylphosphate, ascorbylacetate), tocopherol and derivatives (e.g. vitamin E acetate, tocotrienol), vitamin A and derivatives (vitamin A palmitate), and coniferyl benzoate of benzoin resin, rutinic acid and derivatives thereof, α-glycosylrutin, ferulic acid, furfurylideneglucitol, carnosine, butylhydroxytoluene, butylhydroxyanisole, nordihydroguaiacic acid, nordihydroguaiaretic acid, trihydroxybutyrophenone, uric acid and derivatives thereof, mannose and derivatives thereof, zinc and derivatives thereof (e.g. ZnO, ZnSO4), selenium and derivatives thereof (e.g. selenomethionine), stilbenes and derivatives thereof (e.g. stilbene oxide, trans-stilbene oxide).
  • [0128]
    The amount of the abovementioned antioxidants (one or more compounds) in the preparations is preferably from 0.001 to 30% by weight, particularly preferably from 0.05 to 20% by weight, in particular from 1 to 10% by weight, based on the total weight of the preparation.
  • [0129]
    If vitamin E and/or derivatives thereof are used as the antioxidant(s), it is advantageous to choose their particular concentration from the range 0.001 to 10% by weight, based on the total weight of the formulation.
  • [0130]
    If vitamin A and/or derivatives thereof, or carotenoids are the antioxidant(s), it is advantageous to choose their particular concentration from the range 0.001 to 10% by weight, based on the total weight of the formulation.
  • [0131]
    Customary oil components in cosmetics are, for example, paraffin oil, glyceryl stearate, isopropyl myristate, diisopropyl adipate, cetylstearyl 2-ethylhexanoate, hydrogenated polyisobutene, vaseline, caprylic/capric triglycerides, microcrystalline wax, lanolin and stearic acid.
  • [0132]
    The total amount of auxiliaries and additives can be from 1 to 80% by weight, preferably from 6 to 40% by weight, and the nonaqueous content (“active substance”) can be from 20 to 80% by weight, preferably from 30 to 70% by weight, based on the compositions. The compositions can be prepared in a manner known per se, i.e. for example by hot, cold, hot-hot/cold or PIT emulsification. This is a purely mechanical process; no chemical reaction takes place.
  • [0133]
    Such sunscreen preparations can accordingly be in liquid, paste or solid form, for example as water-in-oil creams, oil-in-water creams and lotions, aerosol foam creams, gels, oils, marking pencils, powders, sprays or alcoholic-aqueous lotions.
  • [0134]
    Finally, it is also possible to co-use other substances which absorb in the UV region and are known per se provided they are stable in the overall system of the combination of UV filters to be used according to the invention.
  • [0135]
    Suitable UV filter substances which can be additionally used with the sunscreen combinations to be used according to the invention are any UV-A and UV-B filter substances. Examples which may be mentioned are:
    CAS No.
    No. Substance (=acid)
     1 4-Aminobenzoic acid 150-13-0
     2 3-(4-Trimethylammonium)benzylidenebornan-2-one 52793-97-2
    methylsulfate
     3 3,3,5-Trimethylcyclohexyl salicylate 118-56-9
    (homosalate)
     4 2-Hydroxy-4-methoxybenzophenone (oxybenzone) 131-57-7
     5 2-Phenylbenzimidazole-5-sulfonic acid and its 27503-81-7
    potassium, sodium and triethanolamine salts
     6 3,3′-(1,4-Phenylenedimethine)-bis(7,7-dimethyl- 90457-82-2
    2-oxobicyclo[2.2.1]heptane-1-methanesulfonic
    acid) and its salts
     7 Polyethoxyethyl 4-bis(polyethoxy)aminobenzoate 113010-52-9
     8 2-Ethylhexyl 4-dimethylaminobenzoate 21245-02-3
     9 2-Ethylhexyl salicylate 118-60-5
    10 Isoamyl 4-methoxycinnamate 71617-10-2
    11 2-Ethylhexyl 4-methoxycinnamate 5466-77-3
    12 2-Hydroxy-4-methoxybenzophenone-5-sulfonic acid 4065-45-6
    (sulisobenzone) and the sodium salt
    13 3-(4′-Sulfo)benzylidenebornan-2-one and salts 58030-58-6
    14 3-Benzylidenebornan-2-one 16087-24-8
    15 1-(4′-Isopropylphenyl)-3-phenylpropane-1,3- 63260-25-9
    dione
    16 4-Isopropylbenzyl salicylate 94134-93-7
    17 2,4,6-Trianiline(o-carbo-2′-ethylhexyl-1′-oxy)- 88122-99-0
    1,3,5-triazine
    18 3-Imidazol-4-yl-acrylic acid and its ethyl 104-98-3
    ester
    19 Ethyl 2-cyano-3,3-diphenylacrylate 5232-99-5
    20 2′-Ethylhexyl 2-cyano-3,3-diphenylacrylate 6197-30-4
    21 Menthyl o-aminobenzoate or: 134-09-8
    5-methyl-2-(1-methylethyl) 2-aminobenzoate
    22 Glyceryl p-aminobenzoate or: 136-44-7
    1-glyceryl 4-aminobenzoate
    23 2,2′-Dihydroxy-4-methoxybenzophenone 131-53-3
    (dioxybenzone)
    24 2-Hydroxy-4-methoxy-4-methylbenzophenone 1641-17-4
    (mexenone)
    25 Triethanolamine salicylate 2174-16-5
    26 Dimethoxyphenylglyoxalic acid or: 4732-70-1
    sodium 3,4-dimethoxyphenylglyoxalate
    27 3-(4-Sulfo)benzylidenebornan-2-one and its 56039-58-8
    salts
    28 4-tert-Butyl-4′-methoxydibenzoylmethane 70356-09-1
    29 2,2′,4,4′-Tetrahydroxybenzophenone 131-55-5
    30 2,2′-Methylenebis-[6(2H-benzotriazol-2-yl)- 103597-45-1
    4-(1,1,3,3,-tetramethylbutyl)phenol]
    31 2,2′-(1,4-Phenylene)-bis-1H-benzimidazole-4,6- 180898-37-7
    disulfonic acid, Na salt
    32 2,4-bis-[4-(2-Ethylhexyloxy)-2-hydroxy]phenyl- 187393-00-6
    6-(4-methoxyphenyl)-(1,3,5)-triazine
  • [0136]
    The cosmetic and dermatological preparations according to the invention can advantageously further comprise inorganic pigments based on metal oxides and/or other metal compounds which are insoluble or virtually insoluble in water, in particular the oxides of titanium (TiO2), zinc (ZnO), iron (eg. Fe2O3), zirconium (ZrO2), silicon (SiO2), manganese (e.g. MnO), aluminum (Al2O3), cerium (e.g. Ce2O3), mixed oxides of the corresponding metals, and admixtures of such oxides. Particular preference is given to pigments based on TiO2 and ZnO.
  • [0137]
    For the purposes of the present invention, it is particularly advantageous, but not obligatory, for the inorganic pigments to be present in hydrophobic form, i.e. to have been surface-treated to repel water. This surface treatment can involve providing the pigments with a thin hydrophobic layer in a manner known per se, as described in DE-A-33 14 742.
  • [0138]
    To protect human hair against UV rays, the suncreen combinations to be used according to the invention can be incorporated into shampoos, lotions, gels, hairsprays, aerosol foam creams or emulsions in concentrations of from 0.1 to 10% by weight, preferably from 1 to 7% by weight. The respective formulations can be used, inter alia, for washing, coloring and for styling the hair.
  • [0139]
    The sunscreen combinations to be used according to the invention are readily soluble in cosmetic oils and can be easily incorporated into cosmetic formulations. The emulsions prepared with the novel sunscreen combinations are notable in particular for their high stability, the sunscreen combinations themselves for their high photos,ability, and the preparations prepared with the sunscreen combinations for their pleasant feel on the skin.
  • [0140]
    The UV filter action of the sunscreen combinations to be used according to the invention can also be utilized for stabilizing active ingredients and auxiliaries in cosmetic and pharmaceutical formulations.
  • [0141]
    The examples below illustrate the use of the novel sunscreen combinations in more detail.
  • EXAMPLES Example 1 Standardized method to determine photostability (sun test)
  • [0142]
    A 5% by weight alcoholic solution of the sunscreen to be tested is applied, using an Eppendorf pipette (20 μl), to the milled area on a small glass plate. Owing to the presence of the alcohol, the solution distributes uniformly on the roughened glass surface. The amount applied corresponds to the amount of sunscreen required to obtain an average sun protection factor in sun creams. In the test, 4 small glass plates are irradiated each time. The evaporation time and the irradiation each last for 30 minutes. The glass plates are cooled slightly during the irradiation by a water cooling system located at the base of the sun test apparatus. The temperature inside the sun test apparatus during the irradiation is 40° C. After the samples have been irradiated, they are washed with ethanol into a dark 50 ml graduated flask and measured using a photometer. The blank samples are applied in the same way to small glass plates and evaporated at room temperature for 30 minutes. Like the other samples, they are washed off with ethanol and diluted to 100 ml and measured.
  • [0143]
    General procedure for preparing emulsions for cosmetic purposes
  • [0144]
    All of the oil-soluble constituents are heated to 85° C. in a stirred vessel. When all the constituents are molten or are present as liquid phase, the aqueous phase is incorporated with homogenization. The emulsion is cooled to about 40° C. with stirring, is perfumed and homogenized, and is then cooled to 25° C. with continuous stirring.
  • [0145]
    Preparations
  • Example 2 Lip care composition
  • [0146]
    [0146]
    Mass content (% by weight)
    ad 100 Eucerinum anhydricum
    10.00  glycerol
    10.00  titanium dioxide, micronized
    5.00 compound combination of 1% of A (formula I, R =
    neopentyl), 1% of Bb (formula IVa) and 3% of Bf (formula
    VIII))
    8.00 octyl methoxycinnamate
    5.00 zinc oxide
    4.00 castor oil
    4.00 pentaerythrityl stearate/caprate/caprylate/adipate
    3,00 glyceryl stearate SE
    2.00 beeswax
    2.00 microcrystalline wax
    2.00 quaternium-18 bentonite
    1.50 PEG-45/dodecyl glycol copolymer
  • Example 3 Lip care composition
  • [0147]
    [0147]
    Mass content (% by weight)
    ad 100 Eucerinum anhydricum
    10.00  glycerol
    10.00  titanium dioxide, micronized
    5.00 compound combination of 1% of A (formula I, R =
    neopentyl) and 4% of Bd (formula VI)
    8.00 octyl methoxycinnamate
    5.00 zinc oxide
    4.00 castor oil
    4.00 pentaerythrityl stearate/caprate/caprylate/adipate
    3.00 glyceryl stearate SE
    2.00 beeswax
    2.00 microcrystalline wax
    2.00 quaternium-18 bentonite
    1.50 PEG-45/dodecyl glycol copolymer
  • Example 4 Sunblocker composition containing micropigments
  • [0148]
    [0148]
    Mass content (% by weight)
    ad 100 water
    10.00  octyl methoxycinnamate
    6.00 PEG-7 hydrogenated castor oil
    6.00 titanium dioxide, micronized
    5.00 compound combination of 1.5% of A (formula I, R =
    neopentyl), 1.5% of Bb (formula IVa) and 2% of Bd
    (formula VI)
    5.00 mineral oil
    5.00 isoamyl p-methoxycinnamate
    5.00 propylene glycol
    3.00 jojoba oil
    3.00 4-methylbenzylidenecamphor
    2.00 PEG-45/dodecyl glycol copolymer
    1.00 dimethicone
    0.50 PEG-40 hydrogenated castor oil
    0.50 tocopheryl acetate
    0.50 phenoxyethanol
    0.20 EDTA
  • Example 5 Sunblocker composition containing micropigments
  • [0149]
    [0149]
    Mass content (% by weight)
    ad 100 water
    10.00  octyl methoxycinnamate
    6.00 PEG-7 hydrogenated castor oil
    6.00 titanium dioxide, micronized
    5.00 compound combination consisting of 1.5% of A (formula I,
    R = neopentyl) and 3.5% of Bb (formula IVb)
    5.00 mineral oil
    5.00 isoamyl p-methoxycinnamate
    5.00 propylene glycol
    3.00 jojoba oil
    3.00 4-methylbenzylidenecamphor
    2.00 PEG-45/dodecyl glycol copolymer
    1.00 dimethicone
    0.50 PEG-40 hydrogenated castor oil
    0.50 tocopheryl acetate
    0.50 phenoxyethanol
    0.20 EDTA
  • Example 6 Non-greasy gel
  • [0150]
    [0150]
    Mass content (% by weight)
    ad 100 water
    8.00 octyl methoxycinnamate
    7.00 titanium dioxide, micronized
    5.00 compound combination consisting of 1% of A (formula I,
    R = neopentyl), 2% of Bf (formula VIII) and 2% of Bc
    (formula Vb)
    5.00 glycerol
    5.00 PEG-25 PABA
    1.00 4-methylbenzylidenecamphor
    0.40 acrylate C10-C30 alkyl acrylate crosspolymer
    0.30 imidazolidinylurea
    0.25 hydroxyethylcellulose
    0.25 sodium methylparaben
    0.20 disodium EDTA
    0.15 fragrance
    0.15 sodium propylparaben
    0.10 sodium hydroxide
  • Example 7 Non-greasy gel
  • [0151]
    [0151]
    Mass content (% by weight)
    ad 100 water
    8.00 octyl methoxycinnamate
    7.00 titanium dioxide, micronized
    5.00 compound combination consisting of 1.5% of A (formula I,
    R = neopentyl), 1% of Bf (formula VIII) and 2.5% of Bc
    (formula Vb)
    5.00 glycerol
    5.00 PEG-25 PABA
    1.00 4-methylbenzylidenecamphor
    0.40 acrylate C10-C30 alkyl acrylate crosspolymer
    0.30 imidazolidinylurea
    0.25 hydroxyethylcellulose
    0.25 sodium methylparaben
    0.20 disodium EDTA
    0.15 fragrance
    0.15 sodium propylparaben
    0.10 sodium hydroxide
  • Example 8 Sun cream
  • [0152]
    [0152]
    Mass content (% by weight)
    ad 100 water
    8.00 octyl methoxycinnamate
    8.00 titanium dioxide, micronized
    6.00 PEG-7-hydrogenated castor oil
    5.00 compound combination consisting of 1.5% of A (formula I,
    R = neopentyl), 1.5% of Bg (formula IX) and 2% of Bb
    (formula IVb)
    6.00 mineral oil
    5.00 zinc oxide
    5.00 isopropyl palmitate
    0.30 imidazolidinylurea
    3.00 jojoba oil
    2.00 PEG-45/dodecyl glycol copolymer
    1.00 4-methylbenzylidenecamphor
    0.60 magnesium stearate
    0.50 tocopheryl acetate
    0.25 methylparaben
    0.20 disodium EDTA
    0.15 propylparaben
  • Example 9 Sun cream
  • [0153]
    [0153]
    Mass content (% by weight)
    ad 100 water
    8.00 octyl methoxycinnamate
    8.00 titanium dioxide, micronized
    6.00 PEG-7 hydrogenated castor oil
    5.00 compound combination consisting of 2% of A (formula I,
    R = neopentyl), 1% of Be (formula VII) and 2% of Bc
    (formula Vb)
    6.00 mineral oil
    5.00 zinc oxide
    5.00 isopropyl palmitate
    0.30 imidazolidinylurea
    3.00 jojoba oil
    2.00 PEG-45/dodecyl glycol copolymer
    1.00 4-methylbenzylidenecamphor
    0.60 magnesium stearate
    0.50 tocopheryl acetate
    0.25 methylparaben
    0.20 disodium EDTA
  • [0154]
    0.15 propylparaben
  • Example 10 Water-resistant sun cream
  • [0155]
    [0155]
    Mass content (% by weight)
    ad 100 water
    8.00 octyl methoxycinnamate
    5.00 PEG-7 hydrogenated castor oil
    5.00 propylene glycol
    4.00 isopropyl palmitate
    4.00 caprylic/capric triglyceride
    5.00 compound combination consisting of 1% of A (formula I,
    R = neopentyl), 2% of Bb (formula IVa) and 2% of Bd
    (formula VI)
    4.00 glycerol
    3.00 jojoba oil
    2.00 4-methylbenzylidenecamphor
    2.00 titanium dioxide, micronized
    1.50 PEG-45/dodecyl glycol copolymer
    1.50 dimethicone
    0.70 magnesium sulfate
    0.50 magnesium stearate
    0.15 fragrance
  • Example 11 Water-resistant sun cream
  • [0156]
    [0156]
    Mass content (% by weight)
    ad 100 water
    8.00 octyl methoxycinnamate
    5.00 PEG-7 hydrogenated castor oil
    5.00 propylene glycol
    4.00 isopropyl palmitate
    4.00 caprylic/capric triglyceride
    5.00 compound combination consisting of 1% of A (formula I,
    R = neopentyl), 1% of Bb (formula IVa), 1% of Ba (formula
    III, R3 = tert-butyl, R4 = methoxy) and 2% of Bc (formula
    Vb)
    4.00 glycerol
    3.00 jojoba oil
    2.00 4-methylbenzylidenecamphor
    2.00 titanium dioxide, micronized
    1.50 PEG-45/dodecyl glycol copolymer
    1.50 dimethicone
    0.70 magnesium sulfate
    0.50 magnesium stearate
  • [0157]
    0.15 fragrance
  • Example 12 Sun milk
  • [0158]
    [0158]
    Mass content (% by weight)
    ad 100 water
    10.00  mineral oil
    6.00 PEG-7 hydrogenated castor oil
    5.00 isopropyl palmitate
    3.50 octyl methoxycinnamate
    5.00 compound combination consisting of 1% of A (formula I,
    R = neopentyl) and 4% of Bb (formula IVb)
    3.00 caprylic/capric triglyceride
    3.00 jojoba oil
    2.00 PEG-45/dodecyl glycol copolymer
    0.70 magnesium sulfate
    0.60 magnesium stearate
    0.50 tocopheryl acetate
    3.00 glycerol
    0.25 methylparaben
    0.15 propylparaben
    0.05 tocopherol
  • Example 13 Sun milk
  • [0159]
    [0159]
    Mass content (% by weight)
    ad 100 water
    10.00  mineral oil
    6.00 PEG-7 hydrogenated castor oil
    5.00 isopropyl palmitate
    3.50 octyl methoxycinnamate
    5.00 compound combination consisting of 0.5% of A (formula I,
    R = neopentyl), 1% of Bb (formula IVa) and 3.5% of Bc
    (formula Vb)
    3.00 caprylic/capric triglyceride
    3.00 jojoba oil
    2.00 PEG-45/dodecyl glycol copolymer
    0.70 magnesium sulfate
    0.60 magnesium stearate
    0.50 tocopheryl acetate
    3.00 glycerol
    0.25 methylparaben
    0.15 propylparaben
    0.05 tocopherol

Claims (12)

    We claim:
  1. 1. The use of sunscreen combinations comprising
    A) compounds absorbing essentially in the UV-A region and
    B) further compounds absorbing in the UV-A region, in the UV-B region and over both regions,
    where the constituents absorbing in the UV-A region comprise effective amounts of at least
    A) one 4,4′-diarylbutadiene of the formula I
    Figure US20020004034A1-20020110-C00032
    in which
    R1 and R2 independently of one another are hydrogen, C1-C20-alkyl, C3-C10-cycloalkyl or C3-C10-cycloalkenyl,
    and as compounds
    B) comprise effective amounts of at least one compound chosen from the group consisting of
    Ba) dibenzoylmethane compounds of the formula III
    Figure US20020004034A1-20020110-C00033
    in which
    R3 is C1-C12-alkyl and
    R4 is hydrogen, C1-C12-alkyl or C1-C12-alkoxy,
    Bb) triazine derivatives of the formula IV
    Figure US20020004034A1-20020110-C00034
    in which
    R5 to R7 independently of one another are optionally substituted C1-C20-alkyl, C5-C10-aryl, C5-C10-heteroaryl or SpSil, where Sp is a spacer and Sil is a silane, oligosiloxane or polysiloxane radical,
    X is the divalent radical —O— or
    Figure US20020004034A1-20020110-C00035
    where
    R8 is hydrogen or optionally substituted C1-C20-alkyl, C5-C10-aryl or C5-C10-heteroaryl,
    Bc) triazine derivatives of the formula V
    Figure US20020004034A1-20020110-C00036
    in which at least one o-hydroxyl group and at least one p-alkoxy group having 1 to 20 carbon atoms are bonded to the phenyl rings,
    Bd) the benzotriazole derivative of the formula VI
    Figure US20020004034A1-20020110-C00037
    Be) the benzimidazole derivative of the formula VII
    Figure US20020004034A1-20020110-C00038
    Bf) the benzotriazole derivative of the formula VIII
    Figure US20020004034A1-20020110-C00039
    Bg) o, o′, p, p′-tetrahydroxybenzophenone of the formula IX
    Figure US20020004034A1-20020110-C00040
    Bh) an organosiloxane benzalmalonate of the formula Xa
    Figure US20020004034A1-20020110-C00041
    in which
    V1′ is the group
    Figure US20020004034A1-20020110-C00042
    V1 is a methyl group or V1′, or of the formula Xb
    Figure US20020004034A1-20020110-C00043
    in which V2′ is the group of the structure
    Figure US20020004034A1-20020110-C00044
    V2 is a methyl group or V2
    or mixtures of compounds of the formulae Xa and Xb,
    where t is a value up to 100 and u is a value up to 20, with the proviso that u=0 when V1=V1′ and/or V2=V2′, and u is a value from 1 to 20 when V1=CH3 and/or V2=CH3,
    as photostable UV filters in cosmetic and pharmaceutical preparations for protecting human skin or human hair against solar rays, optionally together with further compounds which absorb in the UV region and which are known per se for cosmetic and pharmaceutical preparations.
  2. 2. The use of sunscreen combinations as claimed in claim 1, which comprise compounds of the formula I in which R1 and/or R2 is neopentyl.
  3. 3. The use of sunscreen combinations as claimed in claim 1, which comprise, as constituent Bb) triazine derivatives of the formula IV in which the radicals —X—R5 to —X—R7 are 2-ethylhexyloxy.
  4. 4. The use of sunscreen combinations as claimed in claim 1, which comprise, as constituent Bb) triazine derivatives of the formula IV in which the radical —X—R5 is t-butylamino and —X—R6 and —X—R7 are the radical 2-ethylhexyloxy.
  5. 5. The use of sunscreen combinations as claimed in claim 1, which comprise the constituent A) of the formula I in amounts of at least 5% by weight, based on the sunscreen combination.
  6. 6. The use of sunscreen combinations as claimed in claim 1, which, in addition to B), comprise pigments in the form of zinc oxide or titanium dioxide.
  7. 7. A cosmetic or pharmaceutical preparation comprising sunscreen combinations for the protection of the human epidermis or human hair against UV light in the range from 280 to 400 nm, which comprises, in a cosmetically and pharmaceutically suitable carrier, as photostable UV filters, effective amounts of sunscreen combinations which have
    A) compounds absorbing essentially in the UV-A region and
    B) further compounds absorbing in the UV-A region, in the Uv-B region and over both regions,
    where the constituents absorbing in the UV-A region comprise effective amounts of at least
    A) one 4,4′-diarylbutadiene of the formula I
    Figure US20020004034A1-20020110-C00045
    in which
    R1 and R2 independently of one another are hydrogen, C1-C20-alkyl, C3-C10-cycloalkyl or C3-C10-cycloalkenyl, and the constituents
    B) have an effective amount of at least one compound chosen from the group consisting of
    Ba) dibenzoylmethane compounds of the formula III
    Figure US20020004034A1-20020110-C00046
    in which
    R3 is C1-C12-alkyl and
    R4 is hydrogen, C1-C12alkyl or C1-C12-alkoxy,
    Bb) triazine derivatives of the formula IV
    Figure US20020004034A1-20020110-C00047
    in which
    R5 to R7 independently of one another are optionally substituted C1-C20-alkyl, C5-C10-aryl, C5-C10-heteroaryl or SpSil, where Sp is a spacer and Sil is a silane, oligosilane or polysiloxane radical,
    X is the divalent radical —O— or
    Figure US20020004034A1-20020110-C00048
    where
    R8 is hydrogen or optionally substituted C1-C20-alkyl, C5-C10-aryl or C5-C10-heteroaryl,
    Bc) triazine derivatives of the formula V
    Figure US20020004034A1-20020110-C00049
    in which at least one o-hydroxyl group and at least one p-alkoxy group having 1 to 20 carbon atoms are bonded to the phenyl rings,
    Bd) the benzotriazole derivative of the formula VI
    Figure US20020004034A1-20020110-C00050
    Be) the benzimidazole derivative of the formula VII
    Figure US20020004034A1-20020110-C00051
    Bf) the benzotriazole derivative of the formula VIII
    Figure US20020004034A1-20020110-C00052
    Bg) o, o′, p, p′-tetrahydroxybenzophenone of the formula IX
    Figure US20020004034A1-20020110-C00053
    Bh) an organosiloxane benzalmalonate of the formula Xa
    Figure US20020004034A1-20020110-C00054
    in which
    V1′ is the group
    Figure US20020004034A1-20020110-C00055
    V1 is a methyl group or V1′, or of the formula Xb
    Figure US20020004034A1-20020110-C00056
    in which V2′ is the group of the structure
    Figure US20020004034A1-20020110-C00057
    V2 is a methyl group or V2
    or mixtures of compounds of the formulae Xa and Xb,
    where t is a value up to 100 and u is a value up to 20, with the proviso that u=0 when V1=V1′ and/or V2=V2′ and u is a value from 1 to 20 when V1=CH3 and/or V2=CH3,
    as photostable UV filters in cosmetic and pharmaceutical preparations for protecting human skin or human hair against solar rays, optionally together with further compounds which absorb in the UV region and which are known per se for cosmetic and pharmaceutical preparations.
  8. 8. A cosmetic or pharmaceutical preparation comprising sunscreen combinations as claimed in claim 7, wherein the sunscreen combinations comprise compounds of the formula I in which R1 and/or R2 is neopentyl.
  9. 9. A cosmetic or pharmaceutical preparation comprising sunscreen combinations as claimed in claim 7, wherein the sunscreen combinations comprise, as constituent Bb), triazine derivatives of the formula IV in which the radicals —X—R5 to —X—R7 are 2-ethylhexyloxy.
  10. 10. A cosmetic or pharmaceutical preparation comprising sunscreen combinations as claimed in claim 7, wherein the sunscreen combinations comprise, as constituent Bb), triazine derivatives of the formula IV in which the radical —X—R8 is t-butylamino and —X—R9 and —X—R10 are the radical 2-ethylhexyloxy.
  11. 11. A cosmetic or pharmaceutical preparation comprising sunscreen combinations as claimed in claim 7, wherein the sunscreen combinations comprise the constituent of the formula I in amounts of at least 5% by weight, based on the sunscreen combination.
  12. 12. A cosmetic or pharmaceutical preparation comprising sunscreen combinations as claimed in claim 7, wherein the sunscreen combinations, in addition to B) comprise pigments in the form of zinc oxide or titanium dioxide.
US09805238 2000-03-15 2001-03-14 Use of sunscreen combinations comprising, as essential constituent, 4,4′-diarylbutadienes as photostable UV filters in cosmetic and pharmaceutical preparations Expired - Fee Related US6391289B2 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
DE10012413 2000-03-15
DE2000112413 DE10012413A1 (en) 2000-03-15 2000-03-15 Use of sunscreen combinations which contain as an essential ingredient 4,4'-diarylbutadienes as photostable UV filters in cosmetic and pharmaceutical preparations
DE10012413.5 2000-03-15

Publications (2)

Publication Number Publication Date
US20020004034A1 true true US20020004034A1 (en) 2002-01-10
US6391289B2 US6391289B2 (en) 2002-05-21

Family

ID=7634694

Family Applications (1)

Application Number Title Priority Date Filing Date
US09805238 Expired - Fee Related US6391289B2 (en) 2000-03-15 2001-03-14 Use of sunscreen combinations comprising, as essential constituent, 4,4′-diarylbutadienes as photostable UV filters in cosmetic and pharmaceutical preparations

Country Status (5)

Country Link
US (1) US6391289B2 (en)
EP (1) EP1133981A3 (en)
JP (1) JP2001348318A (en)
CN (1) CN1328815A (en)
DE (1) DE10012413A1 (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040047820A1 (en) * 2000-12-18 2004-03-11 Societe L'oreal S.A. Synergistically high SPF photoprotective UV-screening compositions comprising insoluble organic sunscreen particles/diarylbutadiene compounds
US20040052738A1 (en) * 2000-12-18 2004-03-18 Societe L'oreal S.A. Photostable UV-screening compositions comprising dibenzoylmethane/diarylbutadiene compounds
FR2853536A1 (en) * 2003-04-14 2004-10-15 Oreal Photoprotective composition, used for the protection or care of the skin, lips, hair and scalp, based on metallic oxide nanopigments and a 4,4-diarylbutadiene, is obtained by phase inversion
US20040228813A1 (en) * 2003-04-14 2004-11-18 L'oreal Phase inverted oil-in-water photoprotective emulsions comprising nanopigments of metal oxides and 4,4-diarylbutadiene UV-A sunscreens
US7998464B2 (en) 2005-09-29 2011-08-16 L'oreal S.A. Process for the photoprotective treatment of artificially dyed keratin fibers by application of a liquid water/steam mixture

Families Citing this family (42)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2818129B1 (en) * 2000-12-18 2004-02-27 Oreal photostable screening composition containing a UV filter of the type derived dibenzoylmethane, p-methyl-benzylidene camphor and a compound 4,4-diarylbutadiene
FR2818145B1 (en) * 2000-12-18 2003-11-28 Oreal Sunscreen cosmetic compositions based on a synergistic blend of filters and uses
FR2818126B1 (en) * 2000-12-18 2003-02-07 Oreal photostable screening composition containing a derivative of 1,3,5-triazine, a dibenzoylmethane derivative and a compound 4,4-diarylbutadiene
EP1302199A3 (en) 2001-10-16 2004-07-28 L'oreal Compositions for giving the skin a natural sun tan colouration based on a monascus type pigment and its uses
DE10155965A1 (en) * 2001-11-09 2003-05-22 Beiersdorf Ag Cosmetic and dermatological sunscreen formulations with a content of hydroxybenzophenones and iminodisuccinic acid and / or their salts
FR2853538B1 (en) * 2003-04-14 2006-06-23 Oreal Water in oil emulsion containing a surfactant derived from a polyolefin and a 4,4-diarylbutadiene, uses
CN1781476B (en) * 2004-03-22 2013-10-16 莱雅公司 Cosmetic composition containing silicone elastomer bound to polyglycerol
FR2872413B1 (en) 2004-07-02 2008-06-27 Oreal Process for photostabilization a dibenzoylmethane derivative of a derivative arylalkyl benzoate compositions and photoprotective
FR2879456B1 (en) 2004-12-20 2007-05-04 Oreal antisun composition comprising at least one lipophilic UV filter and at least one hydroxyalkylurea
FR2879445B1 (en) 2004-12-20 2007-02-23 Oreal Self-tanning product has two components, multi-compartment devices, skin staining method.
FR2880801B1 (en) 2005-01-18 2008-12-19 Oreal keratinous fiber treatment composition comprising an aromatic alcohol, an aromatic carboxylic acid and a protective agent
US8790623B2 (en) 2005-01-18 2014-07-29 Il'Oreal Composition for treating keratin fibers, comprising at least one aromatic alcohol, at least one aromatic carboxylic acid, and at least one protecting agent
US8216554B2 (en) 2005-04-20 2012-07-10 L'oreal Stable transfer-resistant self-tanning gel containing a water-soluble or water-dispersible gelling agent
FR2885797B1 (en) * 2005-05-17 2007-07-27 Oreal oil gelled particles comprising at least one hydrophobic sunscreen
US20070251026A1 (en) * 2006-04-12 2007-11-01 Boris Lalleman Unsaturated fatty substances for protecting the color of artificially dyed keratin fibers with respect to washing; and dyeing processes
FR2915376B1 (en) 2007-04-30 2011-06-24 Oreal Use of a multi-carbo multi-site moieties coupling agent to protect the color vis-a-vis the washing keratin fibers artificially dyed; staining methods
EP2100585A1 (en) 2008-03-11 2009-09-16 L'Oréal Cosmetic composition comprising an ascorbic acid or salicylic acid compound
FR2939036B1 (en) 2008-12-01 2010-12-17 Oreal Process for artificially coloring the skin using a mixture of carotenoid and lidophile green dye; new mixture of lipophilic dyes; composition
FR2939315B1 (en) 2008-12-08 2011-01-21 Oreal Cosmetic composition containing a dibenzoylmethane derivative and a compound ester of 2-pyrrolidinone-4-carboxy; PROCESS photostabilization the dibenzoylmethane derivative
FR2949330B1 (en) 2009-08-28 2012-08-10 Oreal Cosmetic composition comprising a derivative diphenylmethane hydroxyl
US8241615B2 (en) 2009-10-19 2012-08-14 L'oreal S.A. Water-resistant sunscreen composition
DE102009044891A1 (en) 2009-12-14 2011-06-16 Gabriele Dr. Blume Support system for inclusion of lipophilic active ingredients and oils in high concentration
FR2982147B1 (en) 2011-11-07 2014-03-21 Oreal Composition a continuous oil phase containing at least one lipophilic UV filter and organic airgel particles of hydrophobic silica.
FR2986422B1 (en) 2012-02-06 2014-02-21 Oreal non-dusting composition comprising a solar polar oil phase and hydrophobic silica airgel particles
US8486425B1 (en) 2012-08-08 2013-07-16 L'oreal Two-phase sunscreen composition
WO2014111563A3 (en) 2013-01-21 2014-11-20 L'oreal Cosmetic or dermatological composition comprising a merocyanine and a lipophilic benzotriazole uv-screening agent and/or a bis-resorcinyl triazine compound
FR3001136B1 (en) 2013-01-21 2015-06-19 Oreal Cosmetic or dermatological emulsion comprising a merocyanine and an emulsifying system containing an amphiphilic polymer comprising at least one acrylamido-2-methylpropane acid unit
FR3001137B1 (en) 2013-01-21 2015-02-27 Oreal Emulsion Cosmetic or dermatological water-in-oil emulsion comprising a merocyanine polymer and at least one emulsifier of the type fatty acid ester and polyoxyalkylene glycol
FR3001133B1 (en) 2013-01-21 2015-03-20 Oreal Cosmetic or dermatological composition comprising a merocyanine and an oily phase comprising at least one compound particular amide
FR3001128B1 (en) 2013-01-21 2015-06-19 Oreal Cosmetic or dermatological emulsion comprising a merocyanine and an emulsifying system containing an alkali metal salt of phosphoric acid ester and fatty alcohol
FR3001138B1 (en) 2013-01-21 2015-06-19 Oreal Anhydrous cosmetic or dermatological composition comprising a merocyanine and an oil phase
FR3001131B1 (en) 2013-01-21 2015-06-19 Oreal Cosmetic or dermatological emulsion comprising a merocyanine and an emulsifying system containing a gemini surfactant.
CN105307631A (en) 2013-01-21 2016-02-03 莱雅公司 Cosmetic or dermatological composition comprising a merocyanine and a uva-screening agent of the amino-substituted 2-hydroxybenzophenone type and/or a hydrophilic organic uva-screening agent
JP2016505034A (en) 2013-01-21 2016-02-18 ロレアル Merocyanine, cosmetic or dermatological composition comprising an organic uvb blocking agent and additional organic uva screening agents
FR3001216B1 (en) 2013-01-21 2015-02-27 Oreal Cosmetic or dermatological composition comprising a merocyanine, an oil phase and a mono-C1-C4 alkanol
FR3006176B1 (en) 2013-05-29 2015-06-19 Oreal composite particles based on inorganic UV filter and perlite; cosmetic or dermatological compositions containing
US9579276B2 (en) 2013-12-12 2017-02-28 L'oreal Clear sunscreen composition for application onto wet or dry skin
US20150352035A1 (en) 2014-06-04 2015-12-10 L'oreal High uv protection alcohol-free anhydrous clear system
US9820920B2 (en) 2014-09-30 2017-11-21 L'oreal High UV protection alcohol-free emulsion system, that is clear on application
WO2016119028A1 (en) 2015-01-29 2016-08-04 L'oreal Transparent sunscreen composition
US20160367470A1 (en) 2015-06-19 2016-12-22 L'oreal Water-in-oil sunscreen composition having organic sunscreen actives
WO2017000050A1 (en) 2015-06-29 2017-01-05 L'oreal Oil controlling sunscreen composition

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL190101C (en) 1978-11-13 1993-11-01 Givaudan & Cie Sa Dibenzoylmethaanverbinding and from light protection composition.
DE3206398A1 (en) 1982-02-23 1983-09-01 Basf Ag S-triazine derivatives and their use as light protection agents
DE3781048D1 (en) 1986-06-27 1992-09-17 Procter & Gamble Chromophores sonnenschutzpraeparate and procedures to prevent the sun brandes.
US5087445A (en) 1989-09-08 1992-02-11 Richardson-Vicks, Inc. Photoprotection compositions having reduced dermal irritation
FR2658075B1 (en) * 1990-02-14 1992-05-07 Oreal Photostable screening cosmetic composition containing a UV-A filter and a beta, beta-diphenylacrylate or alpha-cyano-beta, beta-diphenylacrylate alkyl.
US5587150A (en) 1990-02-14 1996-12-24 L'oreal Photostable cosmetic screening composition containing a UV-A screening agent and an alkyl β, β-diphenylacrylate or α-cyano-β,β-diphenylacrylate
US5801244A (en) 1996-03-22 1998-09-01 3V Inc. Sunscreens
EP0850935A3 (en) 1996-12-23 1999-09-29 3V SIGMA S.p.A Concentrated solutions of a 1,3,5-triazine derivative sunscreen and their use for the preparation of cosmetic compositions
DE19726121A1 (en) 1997-06-20 1998-12-24 Beiersdorf Ag Oil-in-water or multiple emulsion with high concentration of suspended ultra-violet B filter
ES2231925T3 (en) * 1997-08-13 2005-05-16 Basf Aktiengesellschaft Cosmetic and pharmaceutical preparations containing photostable UV filters.
EP0933376B1 (en) 1998-01-02 2003-08-20 F. Hoffmann-La Roche Ag Silanyl-triazines as light screening compositions
DE69907454D1 (en) 1998-06-22 2003-06-05 Ciba Sc Holding Ag Sunscreen formulations
FR2785540B1 (en) * 1998-11-10 2002-09-20 Oreal Process for photostabilizer derived sunscreens 1,3,5-triazine
DE10007017A1 (en) * 2000-02-16 2001-08-23 Cognis Deutschland Gmbh Sunlight protection composition with 4,4-diarylbutadiene UV-A filter solubilized and stabilized by presence of polar cosmetic oil and/or non-alkoxylated polyglycerol compound as nonionic emulsifier

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040047820A1 (en) * 2000-12-18 2004-03-11 Societe L'oreal S.A. Synergistically high SPF photoprotective UV-screening compositions comprising insoluble organic sunscreen particles/diarylbutadiene compounds
US20040052738A1 (en) * 2000-12-18 2004-03-18 Societe L'oreal S.A. Photostable UV-screening compositions comprising dibenzoylmethane/diarylbutadiene compounds
US6994844B2 (en) 2000-12-18 2006-02-07 L'oreal Photostable UV-screening compositions comprising dibenzoylmethane/diarylbutadiene compounds
US7166274B2 (en) 2000-12-18 2007-01-23 L'oreal Synergistically high SPF photoprotective UV-screening compositions comprising insoluble organic sunscreen particles/diarylbutadiene compounds
FR2853536A1 (en) * 2003-04-14 2004-10-15 Oreal Photoprotective composition, used for the protection or care of the skin, lips, hair and scalp, based on metallic oxide nanopigments and a 4,4-diarylbutadiene, is obtained by phase inversion
EP1468671A1 (en) * 2003-04-14 2004-10-20 L'oreal O/w emulsion obtainable by phase inversion comprising nanopigments of metal oxides and a 4,4'-diarylbutadiene, process for preparation and use
US20040228813A1 (en) * 2003-04-14 2004-11-18 L'oreal Phase inverted oil-in-water photoprotective emulsions comprising nanopigments of metal oxides and 4,4-diarylbutadiene UV-A sunscreens
US7316808B2 (en) 2003-04-14 2008-01-08 L'oreal Phase inverted oil-in-water photoprotective emulsions comprising nanopigments of metal oxides and 4,4-diarylbutadiene UV-A sunscreens
US7998464B2 (en) 2005-09-29 2011-08-16 L'oreal S.A. Process for the photoprotective treatment of artificially dyed keratin fibers by application of a liquid water/steam mixture

Also Published As

Publication number Publication date Type
DE10012413A1 (en) 2001-09-20 application
EP1133981A3 (en) 2003-11-05 application
US6391289B2 (en) 2002-05-21 grant
EP1133981A2 (en) 2001-09-19 application
CN1328815A (en) 2002-01-02 application
JP2001348318A (en) 2001-12-18 application

Similar Documents

Publication Publication Date Title
US6060042A (en) Use of cholesteric, liquid-crystalline compositions as UV filters in cosmetic and pharmaceutical preparations
US5672337A (en) Amido photostabilization of dibenzoylmethane sunscreens
US6355230B2 (en) Cosmetic and dermatological light protection formulations with a content of benzotriazole derivatives and alkyl naphthalates
US6518451B2 (en) Diesters of naphthalene dicarboxylic acid
US6093385A (en) 4,4-diarylbutadienes as water-soluble photostable UV filters for cosmetic and pharmaceutical preparations
US6607713B1 (en) Method for improving UV radiation stability of photosensitive sunscreen filters
US5945091A (en) Photo-stable cosmetic and pharmaceutical formulations containing UV-filters
US20030157035A1 (en) Photo stable organic sunscreen compounds with antioxidant properties and compositions obtained therefrom
WO1999033439A1 (en) Composition with high efficiency skin protection from damaging effects of ultraviolet light
US20020127252A1 (en) Use of chroman derivatives in cosmetic or dermatological preparations
US6159455A (en) Dimeric α-alkylstyrene derivatives as photostable UV filters in cosmetic and pharmaceutical preparations
US6869597B2 (en) Cosmetic care or makeup composition for a keratin material comprising at least one photoprotective agent and at least one ester comprising an aromatic group
WO2006125676A1 (en) Method for photostabilizing a dibenzoylmethane derivative using a merocyanine sulphone derivative; photoprotective cosmetic compositions containing said combination
US6545174B2 (en) Cosmetic and pharmaceutical preparations containing photostable UV filters
US20050136012A1 (en) Sunscreen compounds and compositions containing same and methods for use thereof
WO2002038537A1 (en) Novel indanylidene compounds
US20080145324A1 (en) UV-photoprotective compositions comprising diebenzoylmethane screening agents and silicon-containing s-triazine compounds substituted with two aminobenzoate or aminobenzamide groups
US7182938B2 (en) Cosmetic formulations comprising ZnO nanoparticles
US6746666B1 (en) Micropigment mixture
FR2800991A1 (en) Photo-stabilization of butyl-methoxy-dibenzoyl methane, for use in cosmetic compositions for solar protection, involves association with phenyl or preferably benzyl salicylate
WO2006015954A1 (en) Alpha-benzoyl-cinnamic acid nitrile as novel uv-absorbers
US5951968A (en) UV-photoprotective dibenzoylmethane compositions comprising photostabilizing amounts of benzalmalonate silanes
US20050065251A1 (en) Composition containing an amino acid n-acylated ester and a polyamide-structured uv filter
EP1046391A2 (en) Use of aminosubstituted hydroxybenzophenones as photostable UV-filters in cosmetic and pharmaceutical preparations
WO2005107692A1 (en) BENZYLIDENE-β-DICARBONYL COMPOUNDS AS NOVEL UV-ABSORBERS

Legal Events

Date Code Title Description
AS Assignment

Owner name: BASF AKTIENGESELLSCHAFT, GERMANY

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:HEIDENFELDER, THOMAS;HABECK, THORSTEN;WUENSCH, THOMAS;REEL/FRAME:011612/0837

Effective date: 20010108

REMI Maintenance fee reminder mailed
LAPS Lapse for failure to pay maintenance fees
FP Expired due to failure to pay maintenance fee

Effective date: 20060521