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WO2003092643A1 - Compositions photoprotectrices a base de derives d'acrylonitrile - Google Patents

Compositions photoprotectrices a base de derives d'acrylonitrile Download PDF

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Publication number
WO2003092643A1
WO2003092643A1 PCT/EP2003/004479 EP0304479W WO03092643A1 WO 2003092643 A1 WO2003092643 A1 WO 2003092643A1 EP 0304479 W EP0304479 W EP 0304479W WO 03092643 A1 WO03092643 A1 WO 03092643A1
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Prior art keywords
dimethyl
oxopentanenitrile
formula
dihydro
methylene
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.)
Ceased
Application number
PCT/EP2003/004479
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German (de)
English (en)
Inventor
Erich Dilk
Oskar Koch
Roland Langner
William Johncock
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Symrise AG
Original Assignee
Symrise AG
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Filing date
Publication date
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Priority to AU2003224139A priority Critical patent/AU2003224139A1/en
Publication of WO2003092643A1 publication Critical patent/WO2003092643A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/4906—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom
    • A61K8/4913—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom having five membered rings, e.g. pyrrolidone carboxylic acid
    • A61K8/492—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom having five membered rings, e.g. pyrrolidone carboxylic acid having condensed rings, e.g. indol
    • 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
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/4906—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom
    • 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
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/4906—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom
    • A61K8/4926—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom having six membered rings
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/04—Indoles; Hydrogenated indoles
    • C07D209/06—Preparation of indole from coal-tar
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/04—Indoles; Hydrogenated indoles
    • C07D209/08—Indoles; Hydrogenated indoles with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to carbon atoms of the hetero ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/04—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms
    • C07D215/06—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms having only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, attached to the ring nitrogen atom

Definitions

  • UV absorbers are compounds with a pronounced absorption capacity for ultraviolet radiation. They are used in particular as sunscreens in cosmetic and pharmaceutical preparations, but also to improve the light resistance of technical products such as paints, varnishes, plastics, textiles, polymers such as e.g. Polymers and copolymers of mono- and diolefms, polystyrenes, polyurethanes, polyamides, polyesters, polyureas and polycarbonates, packaging materials and rubbers are used.
  • UV rays are converted into UV-A rays (320-400 nm, UV-AI: 340-400 nm, UV-A-II: 320-340 nm) or UV-B rays (280-320 nm ) assigned.
  • UV rays can cause acute and chronic skin damage
  • UV-B radiation can cause sunburn (erythema) and serious skin burns. Reductions in enzyme activities, weakening of the immune system, disorders of the DNA structure and changes in the cell membrane as a damaging effect of UV-B rays are also known.
  • the UV-A rays penetrate into the deeper layers of the skin and can accelerate the aging process of the skin there.
  • the shorter-wave UV-A-II radiation additionally increases the formation of sunburn.
  • UV-A radiation can trigger phototoxic or photoallergic skin reactions. Selir frequent and unprotected exposure of the skin to sunlight leads to a loss of skin elasticity and increased wrinkling. In extreme cases, pathological skin changes up to skin cancer are observed.
  • UV absorbers are divided into UV-A and ÜV-B absorbers; If both UV-A and UV-B are absorbed by a UV absorber, one speaks in this case of a UV-A / B broadband absorber.
  • UV-A absorbers The number of suitable UV-A absorbers is very limited and they have significant shortcomings:
  • the filter 4-tert-butyl-4'-methoxy-dibenzoylmethane (absorption maximum at 357 nm), which is frequently used in particular for protection against UV-Al radiation, is not photostable.
  • UV-B filters p-methoxycinnamic acid 2-ethylhexyl or isoamyl ester, photo reactions are also observed.
  • it has only a limited solubility in cosmetic oils, which can lead to problems in the formulation of cosmetic preparations.
  • sunscreen products containing di-benzoyl methane derivative can leave stains that are extremely difficult to wash out on textiles.
  • UV absorbers for use in cosmetic and pharmaceutical preparations for the UV-A range.
  • the aim is that these UV absorbers also meet the following criteria for being blown away in cosmetic sunscreens:
  • UV absorbers good solubility in cosmetic solvents and liquid, oil-soluble UV absorbers, such as p-methoxy cinnamon.
  • UV absorbers should be readily miscible with other UV absorbers or cosmetic oil components
  • R 1 can denote hydrogen, C 1 -C 20 -alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 6 -C 12 aryl,
  • R 3 -R 12 have the meaning given under R 1 or also C 3 -C- 5 - cycloalkyl, C 5 -C 12 heteroaryl, C.-C. g denotes alkoxy, C 6 -C 12 aryloxy, amino, hydroxy, acetoxy, carboxy, carbalkoxy, carbamoyl, where they can be substituted by a group W or interrupted by ether oxygen, 3 with the proviso that two substituents of R -R on adjacent C atoms together can mean an optionally substituted CrC 4 alkylene group, it being possible for a methylene group to be replaced by -O-, -S- or -NH-,
  • A is a bond to the neighboring atom
  • R 15 is an open-chain or branched aliphatic, araliphatic, cycloaliphatic or optionally substituted aromatic radical, each having up to 18 carbon atoms
  • alkyl radicals are methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl , 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1,1-dimethylpropyl, 1, 2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl , 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1, 2 , 2-trimethylpropy
  • alkoxy radicals are methoxy, ethoxy, iso-propoxy, n-propoxy, 1-methylpropoxy, n-butoxy, n-pentoxy, 2-methylpropoxy, 3-methylbutoxy, 1,1-dimethylpropoxy - To name 2,2-dimethylpropoxy, hexoxy, heptoxy, octoxy.
  • R 1 is hydrogen, C.-C 12 alkyl, C 2 -C 12 alkenyl, C 12 alkynyl, can mean phenyl 2 -C,
  • R 2 COOR 13 COR 13 , where R 13 represents hydrogen, C.-C 12 alkyl, C 2 -C 12 alkenyl, C 2 -C 12 alkynyl or C 6 -C 2 aryl, which may be by Amino, hydroxy, acetoxy, carboxy, carbalkoxy, carbamoyl, a group W substituted or interrupted by ether oxygen,
  • R 3 -R 12 have the meaning given under R 1 or also C 3 -C 15 -
  • Oxygen may be interrupted
  • R -R on adjacent C atoms together can mean an optionally substituted Ci- alkylene group
  • z means 0, 1 or 2.
  • R 1 can be hydrogen, C 6 -C 6 -alkyl or phenyl
  • R 3 -R 12 are hydrogen, C.-C 12 -alkyl, C 2 -C 12 -alkenyl, C 2 -C 12 -alkynyl, phenyl, C.-C 12 -alkoxy, hydroxy, acetoxy, carboxy, carbalkoxy, carbamoyl can mean, where they can be substituted by a group W or interrupted by ether oxygen,
  • R 16, R 18 are independently hydrogen, C.-C 2 alkyl, C 2 -C 12 alkenyl, C 2 -C 12 -alkynyl, may mean these with C - C 12 alkoxy, hydroxy, Acetoxy, carboxy, carbalkoxy, carbamoyl, a group W substituted or interrupted by ether oxygen,
  • the compounds of formula (I) can be prepared by processes known per se, for example by heating NH heterocycles together with orthocarboxylic acid esters and CH-acidic compounds.
  • NH heterocycles for example indoline, 2-methyl-indoline, 2,3,3-trimethylindolm, 2,3,3-trimethyl-5-methoxy-indoline, 5-methoxy-indoline, 1,2,3,4, 5,10,11-hexahydrocarbazole and 1,2,3,4-tetrahydroquinoline can be used.
  • Possible Orthocar Examples of bonic acid esters are trimethyl orthoformate, triethyl orthoformate, triethyl orthoacetate, triethyl orthopropionate and trimethyl orthobenzoate.
  • CH-acidic compounds which can be used are ethyl cyanoacetate, 3-methylbutyl cyanoacetate, 2-ethylhexyl cyanoacetate, dinitrile malonate or pivaloylacetonitrile.
  • the higher alkyl esters of the formula (I) can also be obtained from the methyl or ethyl esters by transesterification with higher alcohols.
  • sulfonated acrylonitriles claimed in WO 97/14680 are not suitable for all applications. Due to the extreme water solubility of these compounds, it is difficult, for example, to achieve waterproof cosmetic preparations with these compounds.
  • the oil-soluble acrylonitrile derivatives of the formula (I) are notable for strong absorption in the UV-A range and also have excellent lightfastness.
  • Solvents and in liquid oil-soluble UV absorbers can be used to produce stable cosmetic preparations in all respects without any problems.
  • 3-oxo-4,4-dimethyl-pentar nitriles good protection against the longer-wave UV-A radiation can be achieved due to their strong absorption in the UV-AI range.
  • the acrylonitrile derivatives of the formula (I) can therefore be used as UV absorbers in cosmetic products, in particular for protection against acute (sunburn) and chronic (premature skin aging) skin damage, particularly in sunscreens, day care products and hair care products.
  • the acrylonitrile derivatives of the formula (I) also lead to the photostabilization of UV absorbers with less UV light stability (cf. Table 2).
  • UV-A absorber 4-tert-butyl-4'-methoxydibenzoylmethane.
  • the absorption maximum of the acrylonitrile derivatives of the formula (I) is in the UV-A-I range, these acrylonitrile derivatives surprisingly also improve the photostability e.g. the UV-B filter reaches p-methoxy cinnamic acid 2-ethylhexyl or isoamyl ester.
  • Sunscreen preparations with improved photostability are achieved by using 0.1-10% by weight, preferably 1-10% by weight, of 2-ethylhexyl p-methoxycinnamate, isoamyl p-methoxycinnamate or 4-tert-butyl-4 '-methoxy-diben-zoylmethane with 0.1-10 wt .-% of a compound Her formula (I).
  • Cosmetic formulations with increased light stability can also be prepared by a three-way combination of dibenzoylmethane derivatives and p-methoxycinnamic acid esters with acrylonitrile derivatives of the formula (I) by using, for example, 0.1-5% by weight of 4-tert-butyl-4 ' -methoxy-dibenzoylmethane, preferably 1-3% by weight, 0.1-10% by weight p-methoxycinnamic acid 2-ethylhexyl ester, preferably 1.0-7.5% by weight, and at least 0.2% by weight .-% of a compound of formula (I), preferably 1.0-6.0 wt .-%, preferably in a ratio of 1 part of dibenzoylmethane derivative, 2 parts of p-methoxycinnamate and 2 parts of the compound of formula (I).
  • UV absorbers it is also advantageous to add one or more very photostable UV absorbers to this combination of three, such as methylbenzylidene camphor, 2-ethylhexyl-2-cyano-3,3'-diphenylacrylate, octyltriazon, Uvasorb ® HEB, Tinosorb ® S, Tinosorb ® M, Ethylhexyl salicylate, homomenthyl salicylate and phenylene benzimidazole sulfonic acid or phenylene bis-benzimidazole tetrasulfonic acid disodium salt, Mexoryl ® SX, Mexoryl ® XL or Parsol ® SLX.
  • three such as methylbenzylidene camphor, 2-ethylhexyl-2-cyano-3,3'-diphenylacrylate, octyltriazon, Uvasorb ® HEB, Tinosorb ® S, Tinosorb ® M
  • UV filters achieved a synergistic increase in the sun protection factor.
  • Examples of a synergistic increase in the sun protection factor are cosmetic
  • the UN filter combinations mentioned are given as examples and are not to be understood as being limited to the combinations mentioned above.
  • all of the above-mentioned particularly suitable UN absorbers as well as all UN filters with compounds of formula (I) or the above combinations, individually or in combination, approved in the monographs or positive lists (USA, Europe, Japan, Australia, South Africa and other countries) any mixtures can be used in combination. These combinations usually achieve a synergistic increase in the UV sun protection factor.
  • UV-A absorbers especially UV-A-II absorbers
  • UV-A-II absorbers provides comprehensive protection against UV-A radiation (320-400 nm).
  • a combination of compounds of the formula (I) with ⁇ eo Heliopan ® AP (UV-AII absorber) should be mentioned for a broad UV-A protection performance.
  • UV-A filters which are preferred in combination with compounds of formula (I) alone or in combination of compounds of formula (I) and ⁇ eo Heliopan ® AP, are Mexoryl SX, Mexoryl ® XL, Tinosorb ® M, Tinosorb ® S, benzophenone-3, benzophenone-4, ⁇ eo Heliopan ® 357 and ⁇ eo Heliopan ® MA.
  • titanium dioxide becomes a UV broadband protective power with a critical wavelength ⁇ cr it. «380 nm achieved (see also Diffey in Int. J. Cosm. Science 16, 47 (1994)).
  • Sun protection products should be waterproof so that adequate UN protection for the user, especially children, is guaranteed after swimming or bathing.
  • the UV absorbers of the formula (I) meet these requirements to a particular extent on account of their hydrophobic character and are therefore particularly suitable for the formulation of water-resistant sun protection products.
  • the water resistance of sun protection products can be improved with water-soluble, single or multiple sulfonated UV filters such as ⁇ eo Heliopan ® AP,
  • Mexoryl ® SX, benzophenone-4, ⁇ eo Heliopan ® Hydro and the above-mentioned particularly suitable oil-soluble UN absorbers can be significantly increased by combination with compounds of the formula (I).
  • Liquid acrylonitrile derivatives of the formula (I) are also suitable as solvents for solid UV filters, for which the following compounds are mentioned by way of example but not by way of limitation: camphor derivatives (for example benzylidene camphor and methylbenzylidene camphor), triazine derivatives (for example octyltriazine, dioctylbutamide triazine, Bis (ethyl-hexyloxy, hydroxy) phenyl, methoxyphenyltriazine), benzophenone derivatives (eg oxybenzone), dibenzoylmethane derivatives (eg butylmethoxydibenzoylmethane).
  • camphor derivatives for example benzylidene camphor and methylbenzylidene camphor
  • triazine derivatives for example octyltriazine, dioctylbutamide triazine
  • Bis ethyl-hexyloxy,
  • Solvent properties of the acrylonitrile derivatives according to formula (I) can be increased if they are combined with other liquid constituents of cosmetic preparations, including other liquid UV filters.
  • liquid constituents of cosmetic preparations including other liquid UV filters.
  • examples include, but are not limited to: ethylhexyl p-methoxycinnamate, isoamyl p-methoxycinnamate, ethylhexyl salicylate, octocrylene, menthyl anthanilate, fatty alcohol esters, fatty acid esters, alkyl benzoates, etc.
  • Crystalline acrylonitriles of the formula (I) must be sufficiently dissolved in cosmetic preparations in order to avoid the problem of recrystallization after a long storage period.
  • the use of the following oil components and / or UV absorbers is particularly preferred in order to achieve sufficient solubility of the acrylonitrile derivatives:
  • UV absorbers leave stains that cannot be washed out on clothing.
  • the acrylonitriles according to the invention do not have this disadvantage since staining on textiles can be very easily washed out.
  • the present invention also relates to new acrylonitrile derivatives corresponding to formula (IB) and their use as UV absorbers, in particular in cosmetic preparations.
  • the UV absorbers of the formula (I) prevent the UN rays from passing through the applied film of the preparation.
  • Cosmetic and dermatological formulations in the sense of this invention contain one or more conventional UN-A, UN-B and / or broadband filters as individual substances or in any mixtures with one another, in the lipid phase and / or in the aqueous phase. They are satisfactory products in every respect, which are surprisingly characterized by a high UV-A protection performance or a high sun protection factor.
  • the preparations contain 0.5 to 15, preferably 1 to 10, in particular 2 to 7,% by weight (based on the total weight of the preparation) of a compound of the formula (I).
  • the cosmetic and / or dermatological formulations according to the invention can be composed as usual and the cosmetic and / or dermatological light protection, furthermore for the treatment, care and cleaning of the
  • cosmetic and pharmaceutical preparations which serve to protect skin and hair from UV radiation, can be in the commonly used application forms, i.e. as an oil-in-water, water-in-oil or mixed emulsion, as milk, as a lotion or cream, aerosol, hydrodispersion or oil gel (emulsifier-free), spray, foam, solution, powder, stick preparation or as any other usual cosmetic or pharmaceutical preparation.
  • preparations are preferred as shampoo,
  • the preparations according to the invention can be used, for example, as skin protection cream, cleansing milk, sun protection lotion, nutrient cream, day or night cream, etc. It is possibly possible and advantageous to use the preparations according to the invention as the basis for pharmaceutical products. to use pharmaceutical formulations. Those cosmetic and dermatological preparations which are in the form of a skin care or make-up product are particularly preferred.
  • the cosmetic and dermatological preparations according to the invention are applied to the skin and / or the hair in a sufficient amount in the manner customary for cosmetics.
  • Those cosmetic and dermatological preparations which are in the form of a sunscreen are particularly preferred.
  • the cosmetic and dermatological preparations according to the invention can contain cosmetic auxiliaries, as are usually used in such preparations. e.g .:
  • Emulsifiers surface-active compounds, lanolin, petroleum jelly, water, fats,
  • triglycerides of fatty acids polyethylene glycols, fatty alcohols, ethoxylated fatty alcohols, fatty acid esters (e.g. isopropyl palmitate, isooctyl stearate, adipic acid diisopropyl ester etc.), natural or synthetic oils or waxes, pigments, (e.g. titanium dioxide, zinc oxide, pearlescent pigments), color pigments e.g. hydroxyethyl cellulose, carboxymethyl cellulose, bentonite, etc.), foam stabilizers, film formers, dyes, electrolytes, pH regulators, preservatives, bactericides, moisturizers, vitamins and biogenic agents (e.g.
  • HALS hindered amine light stabilizers
  • Non-ionic emulsifiers or dispersants in question the group that is formed come from Polyglyceryl-2-dipolyhydroxystearate (Dehymuls ® PGPH), polyglyceryl-3-diiso-stearate (Lameform ® TGI), Polyglyceryl-4 isostearate (Isolan ® GI 34), polyglyceryl-3-oleates, diisostearyl-polyglyceryl-3-diisostearate (Isolan ® PDI), polyglyceryl-3-methylglucose distearate (Tego Carey ® 450), polyglyceryl-3-beeswax (Gera Bellina ® ), polyglyceryl-4- caprate (Polyglycerol caprate T2010 / 90), Polyglyceryl-3-cetylether (Chimexane ® NL), Polyglyceryl-3-distearate
  • Mineral oils mineral waxes
  • Oils such as triglycerides of capric or caprylic acid, as well as natural oils such as e.g. Castor oil;
  • Fats, waxes and other natural and synthetic fat bodies preferably esters of fatty acids with alcohols of low C number, e.g. with isopropanol, propylene glycol or glycerin, or esters of fatty alcohols with low C number alkanoic acids or with fatty acids;
  • Silicone oils such as dimethylpolysiloxanes, diethylpolysiloxanes, diphenylpolysiloxanes and mixed forms thereof.
  • the oil phase of the emulsions, oleogels or hydrodispersions or lipodispersions for the purposes of the present invention is advantageously selected from the group of esters from saturated and / or unsaturated, branched and / or unbranched alkane carboxylic acids with a chain length of 3 to 30 carbon atoms and saturated and / or unsaturated, branched and / or unbranched alcohols with a chain length of 3 to 30 carbon atoms, from the group of aromatic esters
  • ester oils can then advantageously be selected from the group of isopropyl myristate, isopropyl palmitate, isopropyl stearate, isopropyl oleate, n-butyl stearate, n-hexyl laurate, n-decyl oleate, isooctyl stearate, isononyl stearate, isononylisononanoate, 2-ethylhexyl-ethyl-2-ethylhexyl-ethyl-palylate Hexyldecyl stearate, 2-octyldodecyl palmitate, oleyl oleate, olerlerucate, erucyl oleate, erucyl oleate, erucy
  • the oil phase can advantageously be selected from the group of branched and unbranched hydrocarbons and waxes, the silicone oils, the dialkyl ethers, the group of saturated or unsaturated, branched or unbranched alcohols, and also the fatty acid triglycerides, especially the triglycerol esters of saturated and / or unsaturated, branched and / or unbranched alkane carboxylic acids with a chain length of 8 to 24, in particular 12 to 18, carbon atoms.
  • the fatty acid triglycerides can, for example, advantageously be selected from the group of synthetic, semisynthetic and natural oils, e.g. Olive oil, sunflower oil, soybean oil, peanut oil, rapeseed oil, almond oil, palm oil, coconut oil, palm kernel oil and the like.
  • waxes for example beeswax and its derivatives, as the sole lipid component of the oil phase.
  • the oil phase is advantageously selected from the group consisting of 2-ethylhexyl isostearate, octyl dodecanol, isotridecyl isononanoate, isoeicosane, 2-ethylhexyl cocoate, C 12 . 15 alkyl benzoate, caprylic capric acid triglyceride and dicaprylyl ether.
  • hydrocarbons paraffin oil, squalane and squalene can be used advantageously for the purposes of the present invention.
  • the oil phase can advantageously also contain cyclic or linear silicone oils or consist entirely of such oils, although it is preferred to use an additional content of other oil phase components in addition to the silicone oil or the silicone oils.
  • Cyclomethicone (octamethylcyclotetrasiloxane) is advantageously used as the silicone oil to be used according to the invention.
  • other silicone oils can also be used advantageously for the purposes of the present invention, for example hexamethylcyclotrisiloxane, polydimethylsiloxane, poly (methylphenylsiloxane).
  • monoethyl or monobutyl ether diethylene glycol monomethyl or monoethyl ether and analog products, furthermore low C number alcohols, e.g. Ethanol, isopropanol, 1,2-propanediol, glycerol and in particular one or more thickeners, which one or more can advantageously be selected from the group silicon dioxide, aluminum silicates,
  • Polysaccharides or their derivatives for example hyaluronic acid, xanthan gum, Hydroxypropylmethyl cellulose, particularly advantageously from the group of polyacrylates, preferably a polyacrylate from the group of so-called carbopoles, for example carbopoles of types 980, 981, 1382. 2984, 5984, each individually or in combination.
  • the cosmetic and dermatological preparations according to the invention advantageously contain, in addition to the UV-A, UV-B and / or broadband filters used, although not necessarily, inorganic pigments based on metal oxides and / or other metal compounds which are sparingly soluble or insoluble in water, in particular those Oxides of titanium (TiO 2 ), zinc (ZnO), iron
  • pigments are X-ray amorphous or non-X-ray amorphous. Pigments based on TiO 2 are particularly preferred.
  • X-ray amorphous oxide pigments are metal oxides or semimetal oxides which show no or no discernible crystal structure in X-ray diffraction experiments. Such pigments are often obtainable by flame reaction, for example by reacting a metal or semimetal halide with hydrogen and air (or pure oxygen) in a flame.
  • X-ray amorphous oxide pigments are used as thickening and thixotropic agents, flow aids for stabilizing emulsions and dispersions and as carriers
  • Aerosile ® available from DEGUSSA company stand out small particle size (for example between 5 and 40 nm), the particles being spherical particles of very uniform dimensions. Aerosile ® are macroscopically recognizable as loose, white powders. For the purposes of the present invention, X-ray amorphous silicon dioxide pigments are particularly advantageous, and among these, those of the Aerosil type are preferred.
  • Aerosil ® types are Aerosil ® 0X50, Aerosil ® 130, Aerosil ® 150, Aerosil ® 200, Aerosil ® 300, Aerosil ® 380, Aerosil ® MQX 80, Aerosil ® MOX 170, Aerosil ® COK 84, Aerosil ® R 202 , Aerosil ® R 805, Aerosil ® R 812, Aerosil ® R 972, Aerosil ® R 974 and Aerosil ® R976.
  • the cosmetic or dermatological light protection preparations contain 0.1 to 20% by weight, advantageously 0.5 to 10% by weight, very particularly preferably 1 to 5% by weight of X-ray amorphous oxide pigments.
  • the non-X-ray amorphous inorganic pigments are advantageously in hydrophobic form, i.e. they are treated on the surface to be water-repellent.
  • This surface treatment can consist in that the pigments are provided with a thin hydrophobic layer by methods known per se.
  • hydrophobicized pigments shown in analogy to DE-A 33 14 742 are advantageous.
  • Advantageous TiO 2 pigments are available, for example, under the trade name T 805, advantageous TiO 2 / Fe 2 O 3 mixed oxides under the trade name T 817 from Degussa.
  • the total amount of inorganic pigments, in particular hydrophilic and hydrophobic inorganic micropigments in the finished cosmetic or dermatological preparations is advantageously in the range from 0.1-30% by weight, preferably 0.1-10.0, in particular 0.5-6 , 0% by weight, based on the total weight of the preparations.
  • An additional content of antioxidants in the cosmetic and dermatological preparations according to the invention is generally preferred. According to the invention, all the antioxidants suitable or customary for cosmetic and / or dermatological applications can be used as favorable antioxidants.
  • the antioxidants are advantageously selected from the group consisting of amino acids (e.g. glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazoles (e.g. urocanic acid) and their derivatives, peptides such as D, L-carnosine, D-
  • Carnosine, L-carnosine and their derivatives e.g. anserine
  • carotenoids e.g. carotenoids
  • carotenes e.g. a-carotene, b-carotene, lycopene
  • chlorogenic acid and their derivatives e.g. dihydroliponic acid
  • aurothioglucose propylthiouracil and other ethiols
  • thioredoxin glutathione, cysteine, cystine, cystamine and their glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl, y-linoleyl -, Cholesteryl and glyceryl esters) and their salts, dilauryl thiodipropionate, distearyl thiodipropionate, thiodipropionic acid and their derivatives (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts), phenolic acid amides of phenolic benzylamines (eg homo vanillic acid, 3,4-dihydroxy acid- phenylphenylphenyl , Ferulic acid, sinapic acid, caffeic acid, dihydroferulic acid, dihydrocaffeic acid, vanillomandelic
  • ⁇ -hydroxy acids e.g. citric acid, lactic acid, malic acid
  • humic acid e.g. citric acid, lactic acid, malic acid
  • bile acid e.g. citric acid, lactic acid, malic acid
  • humic acid e.g. citric acid, lactic acid, malic acid
  • humic acid e.g. citric acid, lactic acid, malic acid
  • humic acid e.g. citric acid, lactic acid, malic acid
  • humic acid e.g. citric acid, lactic acid, malic acid
  • humic acid e.g. citric acid, lactic acid, malic acid
  • humic acid e.g. citric acid, lactic acid, malic acid
  • bile extracts e.g. citric acid, lactic acid, malic acid
  • bile extracts e.g. citric acid, lactic acid, malic acid
  • bile extracts e.g
  • zinc and its derivatives e.g. ZnO, ZnSO
  • selenium and its derivatives e.g. selenium methionine
  • stilbenes and their derivatives e.g. stilbene oxide, trans-stilbene oxide
  • the derivatives suitable according to the invention Salts, esters, ethers, sugars, nucleotides, nucleosides, peptides and lipids
  • the amount of the aforementioned antioxidants (one or more compounds) in the preparations according to the invention is preferably 0.001 to 30% by weight, particularly preferably 0.05-20% by weight, in particular 1-10% by weight, based on the total weight the preparation.
  • vitamin E and / or its derivatives represent the antioxidant (s)
  • vitamin A or vitamin A derivatives or caroline or their derivatives represent the antioxidant or antioxidants, it is advantageous to have their respective concentrations in the range from 0.001-10% by weight, based on the total weight of the formulation, to choose.
  • Skin lightening agents can also be used in the cosmetic preparations.
  • Benzaldoximes with at least one aromatic hydroxyl or alkoxy group benzo-condensed or heterocyclically condensed 2-hydrazino-1,3-thiazoles, 2-thio-1,3,4-heterodiazoles, their anionic or cationic salts and mixtures may preferably be used as skin lightening agents the same, kojic acid, kojic acid derivatives, ascorbic acid, ascorbic acid derivatives, hydroquinone,
  • Hydroquinone derivatives sulfur-containing molecules (e.g. glutathione or cysteine) or other synthetic or natural active ingredients for skin lightening, the latter also in the form of an extract from plants (for example tocopherols and derivatives, arbutin [for example from Bearberry extract], aloesine [for example from aloe extract], grapefruit extract and rice Extract) can be used.
  • plants for example tocopherols and derivatives, arbutin [for example from Bearberry extract], aloesine [for example from aloe extract], grapefruit extract and rice Extract
  • the cosmetic and dermatological preparations according to the invention advantageously also contain complexing agents (e.g. from the class of amino-polycarboxylic acids, aromatic hydroxy and amino derivatives, enolates).
  • complexing agents e.g. from the class of amino-polycarboxylic acids, aromatic hydroxy and amino derivatives, enolates.
  • the cosmetic and dermatological preparations can also have anti-inflammatory agents which come from the compound classes of the salicylic, acetic and propionic acid derivatives, the pyrazoles, fenams and oxicams.
  • the cosmetic and dermatological preparations can also contain auxiliary substances
  • Cooling and refreshing effect e.g. Menthol and derivatives derived from it.
  • the acrylonitrile derivatives of the formula (I) can be used individually or in a mixture in the corresponding preparations; they can also be used in combination with UN absorbers of other substance classes or with these in any mixtures with one another.
  • the list of UV absorbers mentioned below, which can be used for the purposes of the present invention, is of course not intended to be limiting.
  • Salicylic acid homomethyl ester (homosalates) (Neo Heliopan ® HMS)
  • Anthranile acid ethyl ester (Neo Heliopan ® MA)
  • UV absorbers are:
  • Phenylene-bis-benzimidazyl-tetrasulfonic acid disodium salt (Neo Heliopan ® AP)
  • Menthyl anthranilate (Neo Heliopan ® MA)
  • polymer-bound or polymeric UV absorbers in preparations according to the present invention, in particular those as described in WO 92/20690.
  • the total amount of all (single and multiple sulfonated) water-soluble UV filter substances in the finished cosmetic or dermatological preparations is advantageously in the range from 0.1 to 10
  • the total amount of oil-soluble UV filter substances in the finished cosmetic or dermatological preparations for example 4,4 ', 4 "- (1,3,5-triazine, 2,4,6-triyltriimino) -tris-benzoic acid-tris- ( 2-ethylhexyl ester) and / or 4-tert-butyl-4'-methoxy-dibenzoylmethane and / or 4-methylbenzylidene camphor and / or
  • Octyldimethyl-p-aminobenzoic acid and / or Mexoryl ® XL and / or Uvasorb ® HEB and / or Tinosorb ® S and / or Benzophenon-3 and / or Parsol ® SLX and / or Neo Heliopan ® MA is advantageous from the range of 0. 1 to 10.0% by weight, preferably 0.5 to 6.0% by weight, based on the total weight of the preparations, if the presence of these substances is desired.
  • the total amount of 2-ethylhexyl p-methoxy cinnamate and / or p-methoxy cinnamic acid isoamyl ester in the finished cosmetic or dermatological preparations is advantageously in the range from 0.1 to 15.0% by weight, preferably 0.5 to 7.5% by weight, based on the total weight of the preparations, if the presence of these substances is desired.
  • the total amount of ethylhexyl-2-cyano-3,3-diphenyl acrylate in the finished cosmetic or dermatological preparations, if the presence of this substance is desired, is advantageously in the range from 0.1 to 15.0% by weight, preferably 0 , 5 to 10.0 wt .-%, selected, based on the total weight of the preparations.
  • the total amount of one or more salicylic acid derivatives in the finished cosmetic or dermatological preparations is advantageously selected from the range from 0.1 to 15.0% by weight, preferably 0.5 to 10.0% by weight, based on the Total weight of the preparations. If ethylhexyl salicylate is chosen, it is advantageous to choose its total amount from the range of 0.1 to 5.0% by weight. When choosing homomethyl salad, it is advantageous to choose its total amount from the range of 0.1 to 10.0% by weight.
  • the acrylonitrile derivatives of the formula (I) according to the invention can also be combined with UV absorbers which are used for technical product protection.
  • UV absorbers correspond primarily to compounds from the series of benzotriazoles, benzophenones and malonic esters.
  • a mixture of 0.5 mol of orthocarboxylic acid ester, 0.5 mol of alkyl cyanoacetate and 0.5 mol of the corresponding NH-heterocyclic compound is heated to 120 ° C. for 2-3 hours and the alcohol which is split off is distilled off.
  • the residue obtained is purified by crystallization, distillation or column chromatography.
  • a mixture of 0.5 mol of orthocarboxylic acid ester, 0.5 mol of pivaloylacetonitrile and 0.5 mol of the corresponding NH-heterocyclic compound is heated to 120 ° C. for 2-3 hours and the alcohol which is split off is distilled off.
  • the residue obtained is purified by crystallization, distillation or column chromatography.
  • Part A Heat to approx. 85 ° C.
  • Part B Weigh raw materials without Carbopol. Disperse Carbopol with Ultra Turrax. Heat to approx. 85 ° C. Add B to A. Part C: Add immediately to A / B and then homogenize hot (Ultra
  • Part A Heat to approx. 85 ° C.
  • Part B Weigh raw materials without Carbopol. Disperse Carbopol with Ultra Turrax. Heat to approx. 85 ° C. Add B to A. Part C: Add immediately to A / B and then homogenize hot (Ultra
  • Part A Heat to 80-85 ° C.
  • Part B Heat to 80-85 ° C, add Part B to Part A while stirring.
  • Part A Heat to 80-85 ° C.
  • Part B Heat to 80-85 ° C, add Part B to Part A while stirring.
  • Part C Disperse Carbopol in the water and neutralize with NaOH while stirring.
  • Part A Dissolve UV absorber according to formula 1 in the oils or liquid UV filters (heating up to approx. 70 ° C). Allow to cool to approx. 30 ° C, add the remaining ingredients except Carbopol and Pemulen and mix at room temperature (stir for approx. 5 minutes). Stir in the Carbopol and Pemulen.
  • Part B Dissolve Solbrole in phenoxyethanol while heating. With water and
  • Part A Heat to approx. 85 ° C.
  • Part B Heat to approx. 85 ° C (without zinc oxide; disperse zinc oxide with the Ultra Turrax). Add B to A.
  • Part A Heat to approx. 85 ° C.
  • Part B Heat to approx. 85 ° C (without zinc oxide; disperse zinc oxide with the Ultra Turrax). Add B to A. Let cool while stirring. Part C: Add and then homogenize Example 20
  • Part A Heat to 80 ° C.
  • Part B Heat to 80 ° C. Add to Part A while stirring.
  • Part C Disperse Carbopol in water and neutralize with sodium hydroxide solution.
  • Part A Lara Care A-200 with stirring in the other ingredients of Part
  • Part B Weigh in all raw materials (without Pemulen) and dissolve the crystalline sub with heating. Disperse the pemules. Add part B to part A and homogenize for 1 minute. Add part C + D and homogenize again with the Ultra Turrax for 1-2 minutes.
  • Example 24 Disperse Part A Carbopol in water and neutralize with sodium hydroxide solution. Add part B to part A while stirring. Part C Detach crystalline constituents from part C while heating (max.40 ° C) in the other raw materials and add to part A / B. Mix well and then homogenize. (Homozenta).
  • Example 24 Disperse Part A Carbopol in water and neutralize with sodium hydroxide solution. Add part B to part A while stirring. Part C Detach crystalline constituents from part C while heating (max.40 ° C) in the other raw materials and add to part A / B. Mix well and then homogenize. (Homozenta). Example 24
  • Part A Heat to 80 ° C.
  • Part B Heat to 80 ° C. Add to part A while stirring.
  • Part C Add at 40 ° C and cool to RT.
  • UV absorbers such as OMC (octyl methoxy cinnamate) and / or BMDM (tert-butyl methoxy dibenzoyl methane)
  • 20 ⁇ l are uniformly distributed over 10 cm Glass plate with a roughened surface.
  • the sample is irradiated in a Suntest device with a solar standard filter and global sensor for 140 minutes with an irradiance of 765 W / m.
  • the glass plates are on the cooled bottom of the sun tester. A total of 4 glass plates are irradiated at the same time.
  • the samples are rinsed with ethanol from the glass plates into a 25 ml volumetric flask.
  • the content of light stabilizer in the samples thus obtained is determined by means of a photometer or HPLC.
  • blank samples are applied to the glass platelets as described above and then rinsed and measured like the irradiated samples.

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Abstract

Compositions cosmétiques contenant des dérivés d'acrylonitrile, qui protègent la peau humaine et les cheveux contre le rayonnement ultraviolet.
PCT/EP2003/004479 2002-05-02 2003-04-30 Compositions photoprotectrices a base de derives d'acrylonitrile Ceased WO2003092643A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2003224139A AU2003224139A1 (en) 2002-05-02 2003-04-30 Light-protection formulations using acrylonitrile derivatives

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2002119433 DE10219433A1 (de) 2002-05-02 2002-05-02 Lichtschutzzubereitungen unter Verwendung von Acrylnitril-Derivaten
DE10219433.5 2002-05-02

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2939710A1 (fr) * 2014-04-29 2015-11-04 Symrise AG Procédé pour diminuer d'adhérence de boue a causé par agents de protection contre le soleil
WO2017106930A1 (fr) 2015-12-23 2017-06-29 Commonwealth Scientific And Industrial Research Organisation Composés

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1676562B2 (fr) † 2004-12-16 2016-03-02 Kao Germany GmbH Compositions pour les cheveux contenant des filtres uv
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
FR2880801B1 (fr) * 2005-01-18 2008-12-19 Oreal Composition de traitement des fibres keratiniques comprenant un alcool aromatique, un acide carboxylique aromatique et un agent protecteur
DE102010008320A1 (de) * 2010-02-17 2011-08-18 Beiersdorf AG, 20253 Verwendung von Stoffen zur Verbesserung der Auswaschbarkeit von durch UV-Filtern verursachten Textilflecken
DE102020203988A1 (de) 2020-03-27 2021-09-30 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung eingetragener Verein Verwendung von Hydroxyzimtsäuresalzen zur Stabilisierung von organischen Materialien, stabilisiertes organisches Material, Verfahren zur Stabilisierung von organischen Materialien, spezifische Stabilisatoren sowie Stabilisatorzusammensetzungen

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1538374A (fr) * 1966-06-15 1968-09-06 Bayer Ag Nouveaux absorbeurs de lumière ultra-violette
WO1997014680A1 (fr) * 1995-10-16 1997-04-24 Haarmann & Reimer Gmbh Acides sulfoniques et leur utilisation comme absorbeurs des uv

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1538374A (fr) * 1966-06-15 1968-09-06 Bayer Ag Nouveaux absorbeurs de lumière ultra-violette
WO1997014680A1 (fr) * 1995-10-16 1997-04-24 Haarmann & Reimer Gmbh Acides sulfoniques et leur utilisation comme absorbeurs des uv

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2939710A1 (fr) * 2014-04-29 2015-11-04 Symrise AG Procédé pour diminuer d'adhérence de boue a causé par agents de protection contre le soleil
WO2017106930A1 (fr) 2015-12-23 2017-06-29 Commonwealth Scientific And Industrial Research Organisation Composés
CN107108429A (zh) * 2015-12-23 2017-08-29 联邦科学与工业研究组织 化合物
US11512042B2 (en) 2015-12-23 2022-11-29 Commonwealth Scientific And Industrial Research Organisation Enamine compounds for absorbance of electromagnetic energy

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