EP2569055A2 - Photostabilisateurs - Google Patents

Photostabilisateurs

Info

Publication number
EP2569055A2
EP2569055A2 EP11714495A EP11714495A EP2569055A2 EP 2569055 A2 EP2569055 A2 EP 2569055A2 EP 11714495 A EP11714495 A EP 11714495A EP 11714495 A EP11714495 A EP 11714495A EP 2569055 A2 EP2569055 A2 EP 2569055A2
Authority
EP
European Patent Office
Prior art keywords
compound
formula
radicals
use according
branched
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.)
Withdrawn
Application number
EP11714495A
Other languages
German (de)
English (en)
Inventor
René Peter SCHEURICH
Thomas Rudolph
Junyou Pan
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.)
Merck Patent GmbH
Original Assignee
Merck Patent GmbH
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
Application filed by Merck Patent GmbH filed Critical Merck Patent GmbH
Priority to EP11714495A priority Critical patent/EP2569055A2/fr
Publication of EP2569055A2 publication Critical patent/EP2569055A2/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/35—Ketones, e.g. benzophenone
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/41—Amines
    • A61K8/411—Aromatic amines, i.e. where the amino group is directly linked to the aromatic nucleus
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/58—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing atoms other than carbon, hydrogen, halogen, oxygen, nitrogen, sulfur or phosphorus
    • A61K8/585—Organosilicon compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00—Barrier 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
    • A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair

Definitions

  • the present invention relates to the use of a compound of formula I as a photostabilizer for at least one to be stabilized
  • the invention relates to a method for
  • photoactive ingredients may include compounds such as e.g. Pigments, UV filters, polymers, antioxidants, plastics, vitamins, fragrances or other photoactive compounds. Due to the absorption of radiation by such photoactive ingredients, however, they can undergo a structural reaction by a photochemical reaction
  • Photochemical degradation of such photoactive ingredients for example, in the case of dyes lead to fading or loss of gloss, in cosmetic products to discoloration or the emergence of unpleasant odors.
  • photoactive ingredients for example, in the case of dyes lead to fading or loss of gloss, in cosmetic products to discoloration or the emergence of unpleasant odors.
  • Packaging materials can make the respective packaging material brittle and lose its protective function.
  • Photodegradation can proceed according to various reaction mechanisms and in different numbers of steps.
  • a photoactive ingredient will absorb the radiation, whereby the respective photoactive compound can be converted into an excited electronic state by the absorbed radiation energy.
  • Such a photoactive compound can in turn be converted from this excited state into further excited electronic states of equal or different spin multiplication (inter system crossing). pass over or be returned to the ground state (relaxation). If such a relaxation to the electronic ground state does not take place sufficiently fast and if the respective photoactive compound is unstable in at least one of the excited higher energy levels also due to the higher energy content of the molecule, then the molecule of the respective photoactive compound may undergo a photochemical reaction, thereby its chemical structure can be changed.
  • UV filters Through the use of UV filters in preparations, the photoactive compounds or
  • Photoactive compounds are exposed, at least reduced, so that the photoactive compounds are less frequently excited to a higher energy level and thus reduced reduced by a photochemical reaction.
  • a preparation containing photoactive compounds can be at least partially protected from destructive UV radiation.
  • the UV filters are also photoactive compounds, which may also tend to photodegradation.
  • EP 1 406 582 discloses UV filters which additionally have antioxidant properties. According to the invention compounds such. As cinnamic acid derivatives and Phenylethenylmalonate used as such UV filters with antioxidant properties.
  • this photostabilization occurs through a triplet-triplet energy transfer from such a dibenzoylmethane to a diester or polyester of a dicarboxynaphthalene such that the triplet level dibenzoylmethane falls back to ground state while one of the photostabilizing compounds repeats the triplet energy of the dibenzoylmethane and even raised to a triplet state.
  • Admixtures of arylalkyl benzoates and at least one compound capable of accepting the triplet energy of an excited dibenzoylmethane by triplet-triplet energy transfer are provided.
  • the compounds which can take up the triplet energy of the excited dibenzoylmethane have an energy level of a first excited triplet state of 1.73 to 3.03 eV.
  • the present invention addresses the problem of providing an alternative solution for photostabilization of photoactive compounds.
  • Formula I photostabilizers are, especially for photoactive, photosensitive or photoin stable compounds.
  • An object of the invention is therefore the use, in particular the non-therapeutic use, of a compound according to formula I.
  • radical Y 1 represents a single bond or the radicals Y 1 and Y 2 represent a CR 8 R 9 group
  • R 5 to R 5 are each independently of one another H, Hal, CN, OH, C (OO) R 10 , NH 2 , R 11 or OR 1 1 ,
  • R 6 , R 8 and R 9 are each, independently of one another, H or R 11 ,
  • R 7 is H, Si (R 12) 3 or R 1 1,
  • R 10 is OH, Hal, NH 2 or OR 1 1 ,
  • radicals R 11 are each independently a straight-chain or branched C to C 2 o-alkyl group or a straight-chain or branched C 2 - to C 20 -alkenyl group having at least one double bond which is at least one of a primary or secondary
  • C-atom tethered OH may have or
  • radicals R 12 in each case independently of one another represent a straight-chain or branched C 1 to C 6 -alkyl group
  • Another core idea of the invention is to select the energy levels of the first triplet state of the compound of formula I and of a compound to be stabilized by the compound of formula I in pairs so that the energy levels of the first
  • Such a compound to be stabilized constitutes a photoactive, photosensitive or photoinstable compound which may optionally be excite by e.g. UV rays or sunlight may at least partially tend to decay.
  • a stabilizing agent e.g. UV rays or sunlight may at least partially tend to decay.
  • the energy level of the first triplet state of the compound of formula I and / or the compound to be stabilized is preferably arranged in the range from 2.8 to 3.2 eV.
  • the energy level of the first triplet state of the compound of formula I and / or of the compound to be stabilized is particularly preferably arranged in the range from 2.9 to 3.2 eV.
  • the molecules By irradiating molecules of the compound (s) to be stabilized with UV rays, they can absorb the radiation energy.
  • the molecules usually change from a ground state S 0 to an excited first singlet state Si or higher
  • Singlet state S x raised. From such a singlet state, the molecules can be transformed into one by "intersystem crossing (ISC)" Change triplet state, and fall back from this by eg thermal relaxation or radiation relaxation in the ground state.
  • ISC intersystem crossing
  • compounds to be stabilized preferably in the first excited triplet state Ti, have a tendency to decompose. This is especially the case when it is a long-lived triplet state and there is no way to remedy by rapid triplet-triplet transfer with a suitable Quenchmolekül.
  • a corresponding compound to be stabilized can already decay due to the energy content of the first excited triplet state Ti or due to absorption of further energy by means of the UV radiation.
  • An example of such a photochemical reaction is the Norrish type I reaction of the photochemical cleavage of aldehydes and ketones.
  • the first excited triplet state of the respective compound is particularly susceptible to a spontaneous chemical decomposition reaction, it is advisable to leave this first excited triplet state Ti as quickly as possible so that the statistical probability of the decomposition of the compound is as low as possible.
  • This can be achieved by using a compound according to formula I as a photostabilizer, it being precisely this compound of formula I which can receive the triplet energy of the compound to be stabilized, which tends to photochemically decompose.
  • the second compound is relaxed from its first excited triplet state Ti to its ground state So, while the first compound absorbs the triplet energy released in the process first triplet state Ti is raised.
  • Such a triplet-triplet energy transfer can be after the
  • Ranger mechanism or proceed according to the Dexter mechanism, wherein the triplet-triplet energy transfer according to the Förster mechanism by dipole-dipole interaction is achieved, while the triplet-triplet energy transfer takes place by the Dexter mechanism by electron exchange between the respective molecules in collision of the same.
  • the energy level of the first excited triplet state Ti is usually about 0.5 eV below the energy level of the first excited singlet state S- t .
  • compounds such as avobenzone are also known in which the energy level of the first excited triplet state Ti is less than 0.5 eV below the energy level of the first excited singlet state Si.
  • an "intersystem crossing (ISC)" that is, a transition of the molecule from the first excited singlet state Si to the first excited triplet state Ti, is particularly simple
  • a triplet state usually has a non-radical character.
  • a triplet-triplet energy transfer between in each case one molecule of the compound according to formula I and the compound to be stabilized takes place the easier the closer the two Ti energy levels of the two interacting molecules are to one another.
  • a compound according to formula I is preferably used for the photostabilization of a compound to be stabilized if the energy levels of the two first triplet states Ti are at most +/- 5% apart.
  • a triplet-triplet energy transfer is preferably carried out when the triplet states Ti of the compound of formula I and the compound to be stabilized are at most +/- 5% apart.
  • Organic compounds can be formed by the frontier orbitals HOMO (highest occupied molecular orbital) and LUMO
  • the energies can be determined experimentally, eg by CV (cyclic voltammetry), XPS (X-ray photoelectron spectroscopy) or UPS (ultra-violet photoelectron spectroscopy) by the "band gap" (the amount of the energetic difference between HOMO and LUMO)
  • the values can also be calculated by means of quantum mechanical methods, for example by means of time-dependent density functional theory (DFT).
  • DFT time-dependent density functional theory
  • the energy levels of the respective singlet or triplet states of the respective first or second compound are determined by a calibrated calculation method.
  • Gaussian 03W from Gaussian Inc. is used.
  • Density Functional Theory Method B3PW91 and the functional basis set 6-31G (d) the energy calculations for the HOMO / LUMO energy levels and the energy levels for the excited triplet and singlet states are performed.
  • the calculated HOMO and LUMO energy levels are corrected by cyclic voltammetry.
  • selected compounds are measured cyclovoltametrically and calculated in parallel with the software Gaussian 03W according to the previously described method including the density functional theory method B3PW91 using the same function basis set 6-31G (d).
  • the calculated values of these selected compounds are compared with the cyclovoltametrically measured values and calibration factors are determined from the deviations. These calibration factors are used for future calculations of compounds that have similar structures to the compounds selected.
  • the ⁇ energy levels were also measured by means of time-resolved spectroscopy at lower temperatures.
  • an approximately 100 nm thick film, the organic compound of interest is embedded in quartz gas and then excited with a YAG laser or an N 2 laser at 10 Kelvin and the emitted photoluminescence spectrum after 10 ⁇
  • radical R 7 is preferably Si (R 12 ) 3 and R 2 each independently has a meaning as described above.
  • all three radicals R 12 are identical and are selected from a straight-chain or branched alkyl group having 1 to 4 C atoms.
  • the radical R 7 particularly preferably represents a trimethylsilyl group (TMS) or a tri-tert-butylsilyl group (TBDMS).
  • radicals R 11 in formula I are each independently
  • radicals R 11 are each independently
  • Ci- to C 8 -alkyl group each other for a straight-chain or branched Ci- to C 8 -alkyl group, very particularly preferably for a straight-chain or branched C 1 to C 4 -alkyl group.
  • the radicals R 11 may also be a C 5 or C 6 cycloalkyl group.
  • radicals Y and Y 2 in formula I are CR 8 R 9 , wherein R 8 and R 9 are each independently H or R 11 , wherein R 11 has one of the meanings given above or preferably indicated meanings.
  • Y 1 in formula I is preferably a single bond and R 6 is H.
  • radicals R 6 and R 8 in the compounds of the formula I are preferably H.
  • R 9 is preferably R 11 or H, where R 11 has one of the meanings given above or preferably indicated meanings.
  • Acetophenones, propiophenones or benzaldehydes according to formula I are preferably used according to the invention.
  • R 8 is H
  • R 9 is H
  • R 6 is H
  • X is Y
  • Y is CR 8 R 9
  • R 8 is H
  • R 9 is methyl
  • R 6 is H.
  • X is Y
  • Y is a
  • radicals R 1 to R 5 of the benzene ring it is preferred if at least two of the radicals are an H atom.
  • radical R 3 is R 11 or OR 11 , where R 11 has one of the meanings given above or preferably indicated meanings.
  • radicals R 1 , R 2 , R 4 , R 5 H are also preferred.
  • acetophenones or propiophenones according to formula I, as described above, in which the radicals R 1 , R 2 , R 4 and R 5 stand for an H atom.
  • acetophenones or propiophenones according to formula I, as described above, in which the radical R 3 is OCH 3 , OC 2 H 5 , CH (CH 3 ) 2 or C (CH 3 ) 2 .
  • R 3 is OCH 3 , OC 2 H 5 , CH (CH 3 ) 2 or C (CH 3 ) 2 .
  • radical R 3 is OCH 3> OC 2 H 5
  • Butyl-acetophenone 4-methyl-acetophenone, 3-methyl-acetophenone, 2-methyl-acetophenone, 4- ' so-propyl-acetophenone, 3- / ' so propyl-acetophenone, 4-hydroxy-acetophenone, 3-hydroxy acetophenone, 2-hydroxyacetophenone, 6-amino-2-hydroxy-acetophenone, 2,4-dimethylacetophenone, 2,3-dihydroxy-acetophenone, 2,4-dihydroxyacetophenone, 2,5-dihydroxa-acetophenone, 2-amino acetophenone, 3-aminoacetophenone, 4-aminoacetophenone, 4-methoxybenzaldehyde, 3-methoxybenzaldehyde, 2-methoxybenzaldehyde, 3,4-dimethoxbenzaldehyde, 3,5-dimethoxybenzaldehyde, 3,4 , 5-trimethoxy, 4- so-propyl-benzal
  • Benzaldehyde 2-methylbenzaldehyde, 3-methylbenzaldehyde, 4-methylbenzaldehyde, 2-hydroxybenzaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, 2-aminobenzaldehyde, 3-aminobenzaldehyde, 4-aminobenzaldehyde, 2,6-dimethylbenzaldehyde, 2,4-dimethylbenzaldehyde, 4-ethylbenzaldehyde, 2,5-dimethylbenzaldehyde, 3,4-dimethylbenzaldehyde.
  • a compound to be stabilized which is to be photostabilized by a compound of formula I, is characterized by photostability, in particular a first triplet state of one of them
  • a compound to be stabilized can also be understood as meaning a plastic which tends to photostability and has the properties of the substance to be stabilized previously and subsequently described
  • such a compound to be stabilized preferably has an energy level, calculated according to the calibrated calculation method, of the first triplet state Ti, which lies between 2.8 eV and 3.2 eV or particularly preferably between 2.9 eV and 3.2 eV.
  • photochemical decomposition of the compound to be stabilized can be at least reduced.
  • an appearance of the compound to be stabilized which tends to undergo photochemical decomposition may be an isomeric structure of the respective compound to be stabilized. wherein the isomeric structures or the manifestations of this compound to be stabilized are usually present side by side in a predetermined relationship to each other and in a
  • keto-enol tautomers can simply merge into each other, as e.g. in keto-enol tautomers.
  • possible manifestations are e.g. the tautomers of keto-enol tautomerism, ketol-endiol tautomerism, amide-imidic acid tautomerism, imine-enamine tautomerism, lactam-lactime tautomerism, thiolactam-thiolactone tautomerism, oxy-cyclo tautomerism , Cyclopropyl homo-allyl tautomerism or tropanol-cycloheptanone tautomerism.
  • protonated or deprotonated compounds may also be such an appearance, e.g. Enolates or protonated amines.
  • Dibenzoylmethane derivatives are already well-known products which are described in particular in the above-mentioned references FR-A-2 326 405, FR-A-2 440 933 and EP-A-0 114 607. preferred
  • Dibenzoylmethane derivatives correspond to the formula C.
  • R3 wherein R1, R2, R3 and R4 are identical or different, represent hydrogen, a linear or branched C ⁇ s-alkyl group or a linear or branched Ci mean -8 alkoxy group, in particular
  • Another preferred dibenzoylmethane derivative is 4-isopropyldibenzoylmethane.
  • Y 1 , Y 2 and Y 3 each independently represent a single bond or NH
  • X 1 , X 2 and X 3 are each independently of one another Alk 1 or a substituent of the formula II or III
  • R 1 to R 5 are each independently
  • Alk 1 are each independently a straight-chain or branched Ci- to C 2 o alkyl group or a straight or branched C2-C2o-alkenyl group which has at least one double bond, or a straight or branched C 2 - to C 2 o-alkynyl, which has at least one triple bond, and / or in which at least one or more non-adjacent C atoms of the alkyl, alkenyl or alkynyl group can be replaced by O or trimethylsilyl / and / or at least one of a primary or secondary carbon atom can have tethered OH,
  • each Cyc 1 independently represents a C3 to C 8 - cycloalkyl group which may have at least one double bond, and / or in which at least one CH 2 may be replaced by O or NH, wherein Arl 1 are each independently
  • each Het 1 is independently an unsubstituted, mono- or poly-substituted C 5 - to C 20 -aryl group in which at least one CH 2 is replaced by O, S or NH,
  • R 6 ' is Alk 1
  • R 7 and R 8 are each independently
  • each Eth 1 is independently
  • Hai is F, CI, Br or I
  • Kt + is Li + , Na + or K + ,
  • Preferred individual compounds of the triazine derivatives of the formula II are compounds of the formulas X ', XI', II ', II', XIV, XV, XVI ', XVII', XVIII ', XIX', XX ', XXI' or XXII '
  • Formula XVI corresponds to the Uvasorb® Heb UV filter from Sigma.
  • Formula X corresponds to the UV filter Tinosorb® S.
  • Formula XVII corresponds to the UV filter Uvinul T 150 from BASF.
  • the UV filters Uvasorb Heb, Tinosorb S, Uvinul T 150 or avobenzone are particularly preferably photostabilized. Most preferably avobenzone is stabilized. Very particularly preferred is the
  • Another general idea of the invention is a method for photostabilizing a compound to be stabilized by a first compound, in particular of formula I or one of the compounds of formula I described as preferred, wherein the compound to be stabilized by radiation, in particular from a wavelength range of 280 wavelength nm to 400 nm, excited to a first excited triplet state, may tend to decompose in this state, whereby the same is stabilized by a triplet-triplet energy transfer between the compound of formula I and in the first excited triplet state Ti to be stabilized compound ,
  • Another object of the present invention are preparations containing at least one for cosmetic, pharmaceutical
  • Household products or packaging materials suitable carrier and at least one compound of formula I or one of the preferred compounds.
  • an object of the invention is a preparation which comprises at least one compound to be stabilized together with at least one of those described above or as preferred
  • compositions according to formula I or the listed individual compounds Contain compounds according to formula I or the listed individual compounds.
  • Several compounds to be stabilized can be photostabilized by one or more compounds according to formula I.
  • the preparations are usually topically applicable preparations, for example cosmetic or cosmetic preparations
  • preparations contain a cosmetic or
  • dermatologically suitable carrier and as desired
  • compositions in this case contain a pharmaceutically acceptable carrier and optionally further pharmaceutical active ingredients.
  • Preparation must be suitable, for example, to be applied to the skin can.
  • Preferred preparations are cosmetic preparations.
  • agent or formulation is used synonymously in addition to the term preparation.
  • compositions may comprise or contain, consist essentially of or consist of said necessary or optional ingredients. Any compounds or components which may be used in the compositions are either known and commercially available or may be synthesized by known methods.
  • the invention also provides a process for preparing a preparation as described above, wherein at least one compound of the formula I is reacted with a carrier and optionally with further active compounds. or excipients is mixed. Suitable carriers and active or auxiliary substances are described in detail in the following part.
  • Substituents or preferred individual compounds in the preparations according to the invention typically in amounts of 0.05 to 20% by weight, preferably in amounts of 0.1 wt .-% to 20 wt .-% and particularly preferably in amounts of 0.5 to 20 Wt .-%, used.
  • the expert does not have any difficulties in selecting the quantities according to the intended effect of the preparation.
  • Color pigments may be included, wherein the layer structure of the pigments is not limited.
  • the color pigment should be skin-colored or brownish at a level of from 0.1 to 5% by weight.
  • the selection of a corresponding pigment is familiar to the person skilled in the art.
  • preferred formulations comprise further organic UV filters, so-called hydrophilic or lipophilic sunscreen filters which are in the UVA range and / or UVB range and / or IR and / or or VIS area
  • UV filters are effective. These substances can be selected in particular from cinnamic acid derivatives, salicylic acid derivatives, camphor derivatives, ⁇ , ⁇ -diphenylacrylate derivatives, p-aminobenzoic acid derivatives and polymeric filters and silicone filters, which are described in the application WO-93/04665. Other examples of organic filters are in the Patent Application EP-A 0 487 404. In the following, the named UV filters are usually named according to the INCI nomenclature.
  • PABA para-aminobenzoic acid and its derivatives: PABA, ethyl PABA, ethyl dihydroxypropyl PABA, ethylhexyl dimethyl PABA, e.g. B. under the name "Escalol 507" from the company.
  • ISP glyceryl PABA, PEG-25 PABA, z. B. under the name "Uvinul P25” from BASF.
  • Salicylates Homosalates are sold under the name "Eusolex HMS” by Merck; Ethyl hexyl salicylates, e.g. B. under the name “Neo Heliopan OS” from the company. Haarmann and Reimer, Dipropylene glycol salicylate, z. B. under the name “Dipsal” from the company. Scher, TEA salicylate, z. B. under the name “Neo Heliopan TS” from the company Haarmann and Reimer. ⁇ , ⁇ -diphenylacrylate derivatives: octocrylenes, e.g. For example, sold under the name "Eusolex® OCR” by Merck, "Uvinul N539" by BASF, Etocrylene, for example, marketed under the name "Uvinul N35” by BASF.
  • Benzophenone Derivatives Benzophenone-1, e.g. B. operated under the name "Uvinul 400"; Benzophenone-2, e.g. B. operated under the name “Uvinul D50”; Benzophenone-3 or oxybenzone, e.g. B. sold under the name “Uvinul M40” Benzophenone-4, z. B. operated under the name "Uvinul MS40"; Benzophenone-9, e.g. B. under the name "Uvinul DS-49" from the company. BASF, Benzophenone-5, Benzophe- none-6, z. B. operated under the name "Helisorb 11" from the Fa.
  • Benzophenone-8 e.g. Sold under the name "SpectraSorb UV-24” from American Cyanamid, benzophenone-12 n-hexyl 2- (4-diethylamino-2-hydroxybenzoyl) benzoate or 2-hydroxy-4- methoxybenzophenone, sold by Merck, Darmstadt under the name Eusolex® 4360.
  • Benzylidene camphor derivatives 3-benzylidenecamphor, e.g. B. under the name "Mexoryl SD” from the company. Chimex, 4-Methylbenzylidene- camphor, z. B. under the name “Eusolex 6300” from the company Merck, Benzylidenecamphorsulfonklare, z. B. under the name “Mexoryl SL” from the company Chimex, Camphor benzalkonium methosulfate, z. B. under the name "Mexoryl SO” from the company Chimex,
  • Terephthalylidenedicamphorsulfonic acid e.g. B. under the name "Mexoryl SX” from the Fa Chimex
  • Polyacrylamidomethylbenzylidene- camphor operated under the name "Mexoryl SW” from the company Chimex.
  • Phenylbenzimidazole derivatives phenylbenzimidazolesulfonic acid, e.g. B.
  • Phenylbenzotriazole derivatives Drometrizole trisiloxanes, e.g. B. under the name "Silatrizole” from the Fa. Rhodia Chimie, Methylenebis (benzotriazolyl) tetramethylbutylphenol in solid form, eg. B. under the name "MIXXIM BB / 100" from the company. Fairmount Chemical, or in micronized form as an aqueous dispersion, eg. B. under the name "Tinosorb M” from the company. Ciba Specialty Chemicals.
  • Anthraniline derivatives menthyl anthranilate, e.g. B. operated under the
  • Imidazole derivatives ethylhexyldimethoxybenzylidenedioxoimidazoline propionate.
  • Benzalmalonate Derivatives Polyorganosiloxanes containing functional benzalmalonate groups, such as polysilicone-15, z. B. sold under the name "Parsol SLX" by Hoffmann LaRoche.
  • 4,4-Diarylbutadiene derivatives 1,1-dicarboxy (2,2'-dimethylpropyl) -4,4-diphenylbutadiene.
  • Benzoxazole derivatives 2,4-bis [5- (1-dimethylpropyl) benzoxazol-2-yl (4-phenyl) imino] -6- (2-ethylhexyl) imino-1,3,5-triazines, e.g. B. sold under the name Uvasorb K2A from the company. Sigma 3V and mixtures thereof containing.
  • Suitable organic UV-protective substances are preferably to be selected from the following list: ethylhexyl salicylate,
  • Phenylbenzimidazolesulfonic acid benzophenone-3, benzophenone-4, benzophenone-5, n-hexyl 2- (4-diethylamino-2-hydroxybenzoyl) benzoate, 4-methylbenzylidenecamphor, terephthalylidenedicamphorsulfonic acid, disodium phenyldibenzimidazoletetrasulfonate,
  • Preferred preparations contain, in addition to the compounds of the formula I and optionally other organic UV filters, as described above, further inorganic UV filters, so-called particulate UV filters.
  • coated titanium dioxide for example Eusolex ® T-2000, Eusolex ® T-AQUA,
  • Eusolex ® T-AVO Eusolex ® T-OLEO
  • zinc oxides for example Sachtotec® ®
  • Iron oxides or else cerium oxides and / or zirconium oxides are preferred.
  • pigmentary titanium dioxide or zinc oxide are also possible, the particle size of these pigments being greater than or equal to 200 nm, for example Hombitan® FG or Hombitan® FF-Pharma.
  • the preparations may further be preferred if the preparations contain inorganic UV filters which are prepared by customary methods, such as, for example, in US Pat
  • Lecithin phospholipids, sodium, potassium, zinc, iron or aluminum salts of fatty acids, polyethylenes, silicones, proteins (especially Collagen or elastin), alkanolamines, silica, alumina, other metal oxides, phosphates, such as sodium hexametaphosphate or glycerol.
  • Preferably used particulate UV filters are:
  • untreated titanium dioxides e.g. the products Microtitanium Dioxide MT 500 B from Tayca; Titanium Dioxide P25 from Degussa,
  • micronised titanium dioxides with alumina and / or aluminum stearates / laurate aftertreatment e.g. Microtitanium Dioxide MT 100 T from Tayca, Eusolex T-2000 from Merck,
  • micronised titanium dioxides with iron oxide and / or iron stearates aftertreatment such as e.g. the product "Microtitanium Dioxide MT 100 F" from Tayca,
  • Alumina and silicone aftertreatment such as e.g. the product
  • micronised titanium dioxides with sodium hexametaphosphates e.g. the product "Microtitanium Dioxide MT 150 W” from Tayca.
  • the treated micronized titanium dioxides used for combination may also be post-treated with:
  • Octyltrimethoxysilane such as. the product Tego Sun T 805 from Degussa,
  • silica such as the product Parsol TX from DSM, Alumina and stearic acid; such as the product UV titanium M160 Fa. Sachtleben,
  • Aluminum and glycerin such as. the product UV-Titan from the company Sachtleben,
  • Aluminum and silicone oils e.g. the product UV-Titan M262 of the company Sachtleben,
  • Polydimethylsiloxanes e.g. the product 70250 Cardre UF TiO2SI3 "from the company Cardre,
  • Untreated zinc oxides such as the product Z-Cote from BASF (Sunsmart), Nanox from the company Elementis
  • Post-treated zinc oxides such as the following products:
  • mixtures of various metal oxides e.g. Titanium dioxide and cerium oxide with and without aftertreatment, e.g. the product Sunveil A of the company Ikeda.
  • mixtures of alumina, silica, and silicon aftertreated titanium dioxide may also be used.
  • Zinc oxide mixtures such as e.g. the product UV titanium M261 of the company Sachtleben in combination with the
  • UV protectants according to the invention are used.
  • inorganic UV filters are incorporated usually in an amount of 0.1 weight percent to 25 weight percent, preferably 2 wt .-% - 10 wt .-%, in the preparations.
  • the mentioned UV filters can also be used in encapsulated form. It is advantageous if the capsules are so small that they can not be observed with the naked eye. To achieve the above-mentioned effects, it is furthermore necessary for the capsules to be sufficiently stable and not or only to release the encapsulated active substance (UV filter) to the environment to a limited extent.
  • Suitable capsules may have walls of inorganic or organic polymers.
  • Capsule walls can also consist of PMMA.
  • Capsules which are particularly preferred for use have walls which are formed by a SolGel process as described in US Pat Applications WO 00/09652, WO 00/72806 and WO 00/71084
  • capsules whose walls are made up of silica gel are preferred.
  • silica gel silicon, undefined silicon oxide hydroxide
  • the production of corresponding capsules is known to the person skilled in the art, for example, from the cited patent applications, whose content is expressly also the subject of the present invention
  • the capsules are used in accordance with the invention.
  • Preferred preparations may also comprise at least one further cosmetic active ingredient, for example selected from
  • Antioxidants anti-aging, anti-cellulite, self-tanning, skin lightening, antimicrobials or vitamins.
  • the protective effect of preparations against oxidative stress or against the action of radicals can be improved if the preparations contain one or more antioxidants, wherein the skilled person has no difficulty in selecting suitable fast or delayed-acting antioxidants.
  • antioxidants eg, amino acids (eg, glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazoles and their derivatives, peptides such as D, L-carnosine, D-carnosine , L-carnosine and their derivatives (eg anserine), carotenoids, carotenes (eg a-carotene, ß-carotene, lycopene) and their derivatives, chlorogenic acid and their Derivatives, lipoic acid and its derivatives (eg dihydrolipoic acid), aurothioglucose, propylthiouracil and other thiols (eg thioredoxin, glutathione, cysteine, cystine, cystamine and their glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, Butyl and lauryl, palm
  • Dilauryl thiodipropionate, distearyl thiodipropionate, thiodipropionic acid and its derivatives esters, ethers, peptides, lipids, nucleotides, nucleosides and salts
  • sulfoximine compounds for example buthionine sulfoximines
  • Homocysteinsulfoximin, Buthioninsulfone, penta-, hexa-, heptathionine sulfoximine) in very low tolerated dosages eg contents of pmol to ⁇ / kg
  • also (metal) chelators eg a-hydroxy fatty acids, palmitic acid, phytic acid, lactoferrin), ⁇ -hydroxy acids (eg citric acid, lactic acid, malic acid), humic acid, bile acid, bile extracts, bilirubin, biliverdin, EDTA, EGTA and their derivatives, unsaturated
  • Fatty acids and their derivatives, vitamin C and derivatives e.g.
  • Ascorbyl palmitate magnesium ascorbyl phosphate, ascorbyl acetate), tocopherols and derivatives (for example vitamin E acetate), vitamin A and derivatives (eg vitamin A palmitate) and benzylic resin coniferyl benzoate, rutinic acid and derivatives thereof, ⁇ -glycosyl rutin, ferulic acid , Furfurylideneglucitol, carnosine, butylhydroxytoluene, butylhydroxyanisole, nordihydrogaja rietic acid, trihydroxybutyrophenone, quercitin, uric acid and its derivatives, mannose and derivatives thereof, zinc and its derivatives (eg ZnO, ZnS0 4 ), selenium and its derivatives (eg selenomethionine), stilbenes and their derivatives (eg stilbene oxide, trans-stilbene oxide).
  • rutinic acid and derivatives thereof Furfurylideneglucitol, carnosine, butyl
  • Suitable antioxidants are also compounds of the formulas A or B.
  • R 1 can be selected from the group -C (O) CH 3 , -CO 2 R 3 , -C (O) NH 2 and -C (O) N (R 4 ) 2 ,
  • X is O or NH
  • R 2 is linear or branched alkyl having 1 to 30 C atoms
  • R 3 is linear or branched alkyl having 1 to 20 C atoms
  • R 4 are each independently of one another H or linear or branched alkyl having 1 to 8 C atoms,
  • R 5 is H or linear or branched alkyl having 1 to 8 C atoms or linear or branched alkoxy having 1 to 8 C atoms and
  • R 6 denotes linear or branched alkyl having 1 to 8 C atoms, preferably derivatives of 2- (4-hydroxy-3,5-dimethoxybenzylidene) malonic acid and / or 2- (4-hydroxy-3,5-dimethoxybenzyl) - malonic acid, particularly preferably 2- (4-hydroxy-3,5-dimethoxybenzylidene) malonic acid bis- (2-ethylhexyl) ester (for example Oxynex ® ST Liquid) and / or 2- (4-hydroxy-3,5-dimethoxybenzyl ) malonic acid-bis (2-ethylhexyl) ester (example RonaCare ® AP).
  • R 1 to R 6 and X apply here only for the radicals of the formulas A and B and have no relation to the radicals of the formula I.
  • Mixtures of antioxidants are also suitable for use in the cosmetic preparations according to the invention.
  • Known and commercial mixtures mixtures are, for example comprising, as active ingredients, lecithin, L - (+) - ascorbyl palmitate and citric acid, natural tocopherols, L - (+) - ascorbyl palmitate, L - (+) - ascorbic acid and citric acid (for example Oxynex ® K LIQUID) , Tocopherol extracts from natural sources, L - (+) - ascorbyl palmitate, L - (+) - ascorbic acid and citric acid (eg Oxynex ® L LIQUID), DL-a-tocopherol, L - (+) - ascorbyl palmitate, citric acid and lecithin (eg Oxynex ® LM) or butyl
  • Compounds of the invention in such compositions usually in weight percent ratios ranging from 1000: 1 to 1: 1000, preferably used in weight percent ratios of 100: 1 to 1: 100.
  • the flavonoids known mainly as plant dyes or
  • Bioflavonoids often have an antioxidant potential. Effects of the substitution pattern of mono- and dihydoxy flavones are dealt with by K. Lemanska, H. Szymusiak, B. Tyrakowska, R. Zielinski,
  • Sophoretine, ericin, 3,3 ', 4', 5,7-pentahydroxyflavone as a particularly effective antioxidant (e.g., CA. Rice-Evans, N.J. Miller,
  • Suitable anti-aging agents especially for skin care
  • Preparations are preferably so-called compatible solutes. These are substances that are involved in the osmosis regulation of plants or microorganisms and can be isolated from these organisms. Under the generic term compatible solutes also the described in the German patent application DE-A-10133202 osmolytes are taken. Suitable osmolytes are, for example, the polyols, methylamine compounds and amino acids and in each case their precursors. As osmolytes are in the sense of the Germans
  • Patent application DE-A-10133202 especially substances from the group of polyols, such as myo-inositol, mannitol or sorbitol and / or understood one or more of the following osmolytically active substances: taurine, choline, betaine,
  • Phosphorylcholine glycerophosphorylcholine, glutamine, glycine, a-alanine, glutamate, aspartate, proline, and taurine.
  • Precursors of these substances are, for example, glucose, glucose polymers, phosphatidylcholine,
  • Phosphatidylinositol inorganic phosphates, proteins, peptides and polyamic acids.
  • Precursors are z. B. compounds by
  • Metabolic steps are converted into osmolytes.
  • compatible solute substances selected from the group consisting of Pyrimidincarbonklaren (such as ectoine and hydroxyectoine), proline, betaine, glutamine, cyclic
  • Diphosphoglycerate N. acetylornithine, trimethylamine N-oxide di-myo-inositol phosphate (DIP), cyclic 2,3-diphosphoglycerate (cDPG), 1, 1-diglycerol phosphate (DGP), ⁇ -mannosylglycerate (Firoin) , ⁇ -Mannosylglyceramide (Firoin-A) or / and di-mannosyl-di-inositol phosphate (DMIP) or an optical isomer, derivative, eg an acid, a salt or ester of these compounds or combinations thereof.
  • DIP di-oxide di-myo-inositol phosphate
  • cDPG cyclic 2,3-diphosphoglycerate
  • DGP 1, 1-diglycerol phosphate
  • ⁇ -mannosylglycerate Firoin
  • ⁇ -Mannosylglyceramide Firoin-A
  • ectoine ((S) -1,5,6-tetrahydro-2-methyl-4-pyrimidinecarboxylic acid) and hydroxyectoine ((S, S) -1,4,5,6-tetrahydro-5 are among the pyrimidinecarboxylic acids hydroxy-2-methyl-4-pyrimidinecarboxylic acid) and their derivatives.
  • preparations according to the invention may contain at least one self-tanner as further ingredient.
  • Advantageous self-tanning agents which can be used include: 1,3-dihydroxyacetone, glyceraldehyde, hydroxymethylglyoxal, ⁇ -dialdehyde, erythrulose, 6-aldo-D-fructose, ninhydrin, 5-hydroxy-1,4-naphthoquinone (juglone) or 2- Hydroxy-1, 4-naphthoquinone (Lawson).
  • the preparations may also contain one or more other skin lightening agents.
  • skin-lightening active ingredients can be all active ingredients known to the person skilled in the art. Examples of compounds with skin-lightening activity are hydroquinone, kojic acid, arbutin, aloesin, niacinamide, emblica, licorice root exract, vitamin C, magnesium ascorbyl phosphate or rucinol.
  • the preparations to be used may contain vitamins as further ingredients.
  • vitamins and vitamin derivatives selected from vitamin A, vitamin A propionate, vitamin A palmitate, vitamin A acetate, retinol, vitamin B, thiamin chloride hydrochloride (vitamin Bi), riboflavin (vitamin B2), nicotinamide, vitamin C (ascorbic acid), vitamin D, ergocalciferol (vitamin D 2 ), vitamin E, DL-a-tocopherol, tocopherol-E-acetate, tocopherol hydrogen succinate, vitamin esculin (vitamin P active ingredient), thiamine (vitamin Bi), nicotinic acid (niacin ), Pyridoxine, pyridoxal, pyridoxamine, (vitamin B 6 ), pantothenic acid, biotin, folic acid and cobalamin (vitamin B 12 ), particularly preferably vitamin A palmitate, vitamin C and its derivatives, DL- ⁇ -tocopherol, tocopherol -E-acetate, nicot
  • the retinoids described are also effective anti-cellulite agents.
  • Another well-known anti-cellulite drug is caffeine.
  • Suitable preparations for external use for example as a cream or milk (O / W, W / O, O / W / O, W / O / W), as a lotion or emulsion, in the form of oily-alcoholic, oily-aqueous or aqueous alcoholic gels or solutions can be sprayed onto the skin. They can be in the form of solid pegs, packaged as patches or as aerosols.
  • Dosage formulations such as capsules, dragees, powders, tablet solutions or solutions suitable.
  • solutions solutions, suspensions, emulsions, PIT emulsions, pastes, ointments, gels, creams, lotions, powders, soaps, surfactant-containing cleaning preparations, oils, aerosols and sprays.
  • Preferred excipients come from the group of preservatives, stabilizers, solubilizers, colorants, odor improvers.
  • Ointments, pastes, creams and gels may contain the usual excipients suitable for topical administration, e.g. animal and vegetable fats, waxes, paraffins, starch, tragacanth,
  • Cellulose derivatives Polyethylene glycols, silicones, bentonites, silicic acid, talc and zinc oxide or mixtures of these substances.
  • Powders and sprays may contain the usual carriers, e.g. Lactose, talc, silicic acid, aluminum hydroxide, calcium silicate and polyamide powder or mixtures of these substances.
  • Sprays may additionally contain the usual volatilized, liquefied propellants, e.g. Propane / butane or dimethyl ether. Also, compressed air is advantageous to use.
  • Solutions and emulsions may contain the customary carriers such as solvents, solubilizers and emulsifiers, for example water, ethanol, isopropanol, ethyl carbonate, ethyl acetate, benzyl alcohol, benzyl benzoate, propylene glycol, 1,3-butylglycol, oils, in particular cottonseed oil, peanut oil, maize germ oil, olive oil, Castor oil and sesame oil, Glycerinfett- acid esters, polyethylene glycols and fatty acid esters of sorbitol or mixtures of these substances.
  • a preferred solubilizer in general is 2-isopropyl-5-methylcyclohexanecarbonyl-D-alanine methyl ester.
  • Suspensions may include the usual carriers such as liquid diluents, e.g. Water, ethanol or propylene glycol, suspending agents, e.g. ethoxylated isostearyl alcohols, polyoxyethylene sorbitol esters and
  • Soaps may contain the usual excipients such as alkali metal salts of fatty acids, salts of fatty acid monoesters, fatty acid protein hydrolysates, isothionates, lanolin, fatty alcohol, vegetable oils, plant extracts, glycerol, sugars or mixtures of these substances.
  • excipients such as alkali metal salts of fatty acids, salts of fatty acid monoesters, fatty acid protein hydrolysates, isothionates, lanolin, fatty alcohol, vegetable oils, plant extracts, glycerol, sugars or mixtures of these substances.
  • Surfactant-containing cleaning products may include the usual excipients such as salts of fatty alcohol sulfates, fatty alcohol ether sulfates, sulfosuccinic acid monoesters, fatty acid hydrolysates, isothionates, imidazolinium derivatives, methyltauate, sarcosinates, fatty acid amide ether sulfates, alkyl amidobetaines, fatty alcohols, fatty acid glycerides, fatty acid diethanolamides, vegetable and synthetic oils, lanolin derivatives, ethoxylated Glycerine fatty acid esters or mixtures of these substances.
  • excipients such as salts of fatty alcohol sulfates, fatty alcohol ether sulfates, sulfosuccinic acid monoesters, fatty acid hydrolysates, isothionates, imidazolinium derivatives, methyltauate, sarcosinates, fatty acid
  • Facial and body oils can be the usual carriers such as
  • oils such as fatty acid esters, fatty alcohols, silicone oils, natural oils such as vegetable oils and oily vegetable extracts, paraffin oils, lanolin oils or mixtures of these substances.
  • Sunscreen, pre-sun and after-sun preparations include, in particular, emulsions.
  • Emulsions are advantageous and contain z.
  • Oils such as triglycerides of capric or caprylic, further natural oils such. Castor oil;
  • Fats, waxes and other natural and synthetic fats preferably esters of fatty acids with lower C-number alcohols, e.g. with isopropanol, propylene glycol or glycerol, or esters of
  • Silicone oils such as dimethylpolysiloxanes, diethylpolysiloxanes,
  • the oil phase of the emulsions, oleogels or hydrodispersions or lipodispersions in the context of the present invention is advantageously selected from the group of esters of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids
  • unsaturated, branched and / or unbranched alcohols having a chain length of 3 to 30 carbon atoms from the group of esters of aromatic carboxylic acid and saturated and / or unsaturated, branched and / or unbranched alcohols having a chain length of 3 to 30 carbon atoms.
  • ester oils can then advantageously be selected from the group isopropyl myristate, isopropyl palmitate, isopropyl stearate, isopropyl oleate, n-butyl stearate, n-hexyl laurate, n-decyl oleate, isooctyl stearate, isononyl stearate, isononyl isononanoate, 2-ethylhexyl palmitate, 2-ethylhexyl laurate, 2-hexadecyl stearate, 2-octyl dodecyl palmitate,
  • the oil phase can advantageously be selected from the group of branched and unbranched hydrocarbons and waxes, silicone oils, dialkyl ethers, the group of saturated or unsaturated, branched or unbranched alcohols, and fatty acid triglycerides, in particular the triglycerol esters of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids of a chain length of 8 to 24, in particular 12-18 C-atoms.
  • the fatty acid triglycerides can be selected, for example, advantageously from the group of synthetic, semi-synthetic and natural oils, for. For example, olive oil, sunflower oil, soybean oil, peanut oil, rapeseed oil, almond oil, palm oil, coconut oil, palm kernel oil and the like.
  • any mixtures of such oil and wax components are also advantageous to use in the context of the present invention. It may also be advantageous, if appropriate, to use waxes, for example cetyl palmitate, as the sole lipid component of the oil phase.
  • the aqueous phase of the preparations to be used contains
  • alcohols, diols or polyols of low carbon number, and their ethers preferably ethanol, isopropanol, propylene glycol, glycerol, ethylene glycol, ethylene glycol monoethyl or monobutyl ether, propylene glycol monomethyl, monoethyl or monobutyl ether, diethylene glycol monomethyl or -monoethylether and analogous products, furthermore low C-number alcohols, e.g. As ethanol, isopropanol, 1, 2-propanediol, glycerol, and in particular one or more thickeners, which or which can be advantageously selected from the group
  • Silica aluminum silicates, polysaccharides or their derivatives, for example hyaluronic acid, xanthan gum, hydroxypropylmethylcellulose, especially advantageous from the group of polyacrylates, preferably a polyacrylate from the group of so-called carbopols, for example Carbopols types 980, 981, 1382, 2984, 5984, each individually or in combination.
  • carbopols for example Carbopols types 980, 981, 1382, 2984, 5984, each individually or in combination.
  • mixtures of the abovementioned solvents are used.
  • alcoholic solvents water can be another ingredient.
  • Emulsions are advantageous and contain z.
  • the preparations to be used contain hydrophilic surfactants.
  • the hydrophilic surfactants are preferably selected from the group of alkylglucosides, acyl lactylates, betaines and cocoamphoacetates.
  • the cosmetic and dermatological preparations can be in various forms. So they can z.
  • Oil-in-water (W / O / W) a gel, a solid stick, an ointment or even an aerosol.
  • Ectoine in encapsulated form, e.g. In collagen matrices and other common encapsulating materials, e.g.
  • wax matrices As encapsulated cellulose, in gelatin, wax matrices or liposomally encapsulated.
  • wax matrices as described in DE-A-43 08 282 have been described, have turned out to be favorable. Preference is given to emulsions. O / W emulsins are especially preferred.
  • Emulsions, W / O emulsions and O / W emulsions are available in the usual way.
  • emulsifiers for example, the known W / O and O / W emulsifiers can be used. It is advantageous to use other conventional co-emulsifiers in the preferred O / W emulsions.
  • O / W emulsifiers are selected as co-emulsifiers, principally from the group of substances with HLB values of 11-16, very particularly advantageously with HLB values of 14.5-15.5, provided that the O / W Emulsifiers have saturated radicals R and R '. If the O / W emulsifiers have unsaturated radicals R and / or R ', or if isoalkyl derivatives are present, the preferred HLB value may be such
  • Emulsifiers also lower or above.
  • fatty alcohol ethoxylates from the group of the ethoxylated stearyl alcohols, cetyl alcohols, cetylstearyl alcohols (cetearyl alcohols).
  • Polyethylene glycol (12) isostearate, polyethylene glycol (3) isostearate,
  • Polyethylene glycol (14) isostearate, polyethylene glycol (15) isostearate,
  • Polyethylene glycol (22) isostearate, polyethylene glycol (23) isostearate, Polyethylene glycol (24) isostearate, polyethylene glycol (25) isostearate,
  • Polyethylene glycol (20) oleate Polyethylene glycol (20) oleate.
  • the sodium laureth-11-carboxylate can be advantageously used.
  • the alkyl ether sulfate sodium laureth-4 sulfate can be advantageously used.
  • the Polyethylenglycolglycerinfettklander from the group polyethylene glycol (20) glyceryl laurate, polyethylene glycol (21) - glyceryl laurate, polyethylene glycol (22) glyceryl laurate, polyethylene glycol
  • sorbitan esters from the group of polyethylene glycol (20) sorbitan monolaurate, polyethylene glycol (20) sorbitan monostearate, polyethylene glycol (20) sorbitan monoisostearate, polyethylene glycol (20) sorbitan monopalmitate, polyethylene glycol (20) sorbitan monooleate.
  • W / O emulsifiers can be used:
  • W / O emulsifiers are glyceryl monostearate, glyceryl, glyceryl monomyristate, glyceryl, diglyceryl monostearate, Diglycerylmonoisostearat, propylene glycol monostearate, propylene glycol monoisostearate, propylene glycol monocaprylate, propylene glycol, sorbitan, sorbitan, sorbitan, Sorbitanmonoisooleat, sucrose, cetyl alcohol, stearyl alcohol, arachidyl, behenyl, Isobehenyl alcohol, selachyl alcohol, chimyl alcohol, polyethylene glycol (2) stearyl ether (steareth-2), glyceryl monolaurate, glyceryl monocaprinate, glyceryl mono- caprylate or PEG-30 dipolyhydroxystearate.
  • the preparation may contain cosmetic adjuvants which are commonly used in this type of preparations, e.g.
  • Thickeners emollients, moisturizers,
  • surfactants such as soaps, emulsifiers, preservatives, antifoaming agents, perfumes, waxes, lanolin, propellants, dyes and / or pigments, and other ingredients commonly used in cosmetics.
  • dispersion or solubilizing agent an oil, wax or other fatty substance, a low monoalcohol or a low polyol or mixtures thereof.
  • preferred monoalcohols or polyols include ethanol, i-propanol, propylene glycol, glycerin and sorbitol.
  • a preferred embodiment of the invention is an emulsion which is present as a protective cream or milk and contains, for example, fatty alcohols, fatty acids, fatty acid esters, in particular triglycerides of fatty acids, lanolin, natural and synthetic oils or waxes and emulsifiers in the presence of water.
  • oily lotions based on natural or synthetic oils and waxes, lanolin,
  • Fatty acid esters in particular triglycerides of fatty acids, or oily alcoholic lotions based on a lower alcohol, such as ethanol, or a glycerol, such as propylene glycol, and / or a polyol, such as glycerol, and oils, waxes and fatty acid esters, such as triglycerides of
  • the preparation may also be in the form of an alcoholic gel comprising one or more lower alcohols or polyols, such as ethanol, propylene glycol or glycerin, and a thickener, such as silica.
  • the oily alcoholic gels also contain natural or synthetic oil or wax.
  • the solid sticks consist of natural or synthetic waxes and oils, fatty alcohols, fatty acids, fatty acid esters, lanolin and other fatty substances. If a preparation is formulated as an aerosol, the customary propellants, preferably alkanes, are generally used.
  • Figure 1 illustrates the effect of adding 4-methoxyacetophenone as the compound of formula I to a solution of avobenzone as to stabilizing compound in dimethyl isosorbide, commercially available under the name Arlasolv® DMI from Uniqema.
  • FIG. 1 shows in an absorption / wavelength diagram 1 several absorption curves of a 2% strength by weight solution of avobenzone in FIG. 1
  • Arlasolv® DMI Arlasolv® DMI.
  • the absorption in% is removed, while on the X-axis 3 the wavelength is plotted in nm.
  • the absorption maximum of avobenzone at 357 nm is characterized in the form of a straight line 4 parallel to the Y-axis 2 in the absorption / wavelength diagram 1. This straight line 4 can be used to make a statement about the amount of avobenzone present, since at a wavelength of 357 nm, the radiation of this wavelength in the used
  • Absorption curve 6 of an irradiated two wt .-% solution of avobenzone in Arlasolv DMI an absorption curve 7 of an unirradiated each two wt .-% solution of avobenzone and 4-methoxyacetophenone and an absorption curve 8 of an irradiated two wt .-% solution of avobenzone and 4-methoxyacetophenone in Arlasolv DMI.
  • the absorption curves 5 and 7 of the unirradiated solutions in particular in the absorption maximum of the avobenzone of 357 nm and in the region of the straight line 4 each have a higher absorption than the absorption curves 6 and 8 of the irradiated solutions . Furthermore, it can be seen by comparing the absorption curves 5 and 7 of the unirradiated solutions that by adding 4-methoxyacetophenone, the absorption capacity of the solution is slightly reduced.
  • Photochemical decay of the avobenzone upon irradiation with sunlight or sun-like light at least in part, but significantly lower compared to a pure avobenzone solution.
  • Example 4 containing several exemplary cosmetic preparations
  • Example 1 photochemical decomposition of dibenzoylmethanes, in particular avobenzone
  • R 1 and R 2 are here R 11 or OR 11 , as previously described in detail or described as preferred.
  • Dibenzoylmethane derivatives such as avobenzone, as an example of a compound to be stabilized, are usually less Normal conditions in their enolic form.
  • these Dibenzoylmethanderivate can be converted into the diketoform, as a manifestation.
  • the diketoform can be returned to the enol form.
  • the diketoform absorbs further radiant energy, it may react to a benzoyl radical (A) and a phenacyl radical (B) according to a Norish type I reaction, these radicals passing through
  • the diketo the dibenzoylmethane is raised by adding other radiant energy to their first excited triplet state T ⁇ .
  • This excited first triplet state of the diketo form tends to Norish type I cleavage.
  • the energy level of the first excited triplet state Ti of the diketoform can be determined to be 3.10 eV.
  • the energy level of the first excited triplet state of 4-methoxacetophenone can be calculated to be 3.15 eV.
  • the two energy levels of the respective first excited triplet state are so close to each other (1.6% difference) that the compound to be stabilized avobenzone in its diketoform with the first compound 4-methoxyacetophenone can perform a triplet triplet energy exchange, so that to be stabilized Compound Avobenzon can be photostabilized in its prone to photodegradation diketo manifestation by the compound 4-methoxyacetophenone.
  • the compound of Formula I, 4-methoxyacetophenone, as a photostabilizer is specifically designed for that form, the diketoform, of the avobenzone stabilizing compound whose first excited triplet state tends to photoinstability.
  • Example 2 and TV energy levels of several selected first compounds,
  • formulations for cosmetic preparation which contain at least one compound of formula I and at least one compound to be stabilized.
  • stabilizing compound may also be further cosmetic
  • the following preparation examples may further contain the following stabilizers (each 0, 1-10% in single component or in mixtures): Benzotriazolyl dodecyl p-cresol (Tinoguard TL), Butyloctyl salicylate, diethylhexyl 2,6-naphthalates, diethylhexyl Syringylidene malonate, polyester-8 (Polyacrylenes), bis-ethylhexyl hydroxydimethoxy benzyl malonates.
  • stabilizers each 0, 1-10% in single component or in mixtures
  • stabilizers each 0, 1-10% in single component or in mixtures
  • phase A The components of phase A are combined at room temperature and stirred. Subsequently, phase B is mixed and added with stirring to phase B and stirred.
  • phase III Pump Hairspray
  • Preparation Pre-dissolve phase A. Add phase B to phase A with stirring. Premix phase C and add to the rest, stirring until a homogeneous mixture has formed.
  • Example IV W / O Emulsions
  • Vitamin E acetate 0.2 02 0.3 0.1 0.5
  • TinosorbA2B 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 Content in g component per 100 g formulation
  • Citric acid 0.015 0 0 0 0 0 0 0
  • Titanium dioxide 0.604 0.604 0.604
  • Vitamin E acetate 0.2 0.2 0.3 0.1 0.5
  • Vitamin E acetate 0.2 0.5 0.5 0.5
  • Vitamin E acetate 0.2 0.3 0.8 0.5
  • Example X Hydrodisperions (lotions and sprays)
  • Vitamin E acetate 0.50 0.25 0 50 0.25 0.75 1, 00 a-glycosyl rutin 0.25
  • Example XI aqueous and aqueous / alcoholic formulations
  • Vitamin E acetate 0.3 0.2 0.5
  • Vitamin E acetate 0.6 0.5 0.2
  • Phenylbenzimidazole 1 1 Emulsion DEFG sulfonic acid
  • Vitamin E acetate 0.2 03 0.3

Abstract

L'invention concerne l'utilisation comme photostabilisateurs, d'aldéhydes ou de cétones particuliers de formule I, pour au moins un composé à stabiliser. L'invention concerne également un procédé de photostabilisation d'un second composé par un composé de formule I, ainsi que des préparations contenant au moins un tel composé de formule I.
EP11714495A 2010-05-12 2011-04-13 Photostabilisateurs Withdrawn EP2569055A2 (fr)

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PCT/EP2011/001871 WO2011141110A2 (fr) 2010-05-12 2011-04-13 Photostabilisateurs
EP11714495A EP2569055A2 (fr) 2010-05-12 2011-04-13 Photostabilisateurs

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