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
  • A61K8/37—Esters of carboxylic acids
• • 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
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
  • C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
  • C07C49/84—Ketones containing a keto group bound to a six-membered aromatic ring containing ether groups, groups, groups, or groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
  • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
  • C07C69/73—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids
  • C07C69/738—Esters of keto-carboxylic acids or aldehydo-carboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2601/00—Systems containing only non-condensed rings
  • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
  • C07C2601/14—The ring being saturated

Definitions

• the invention relates to the use of certain benzylidene- ⁇ -dicarbonyl compounds as UV filters (UV absorbers) in cosmetic and dermatological formulations such as sunscreens, day care and hair care products.
• the invention further relates to corresponding cosmetic and dermatological formulations.
• the invention also relates to certain novel benzylidene- ⁇ -dicarbonyl compounds which can be used as UV-B filters.
• UV rays are subdivided according to their wavelength into UV-A rays (320-400nm) and UV-B rays (280-320nm).
• the damaging effect, the occurrence of sunburn (erythema) is mainly caused by the UV-B radiation.
• Dermatological studies have shown that the UV-A radiation causes skin damage. This area of radiation is responsible for premature skin aging and skin cancer. From this insight it is essential for a modern cosmetic sunscreen to cover both areas, both UV-A and UV-B.
• UV-B absorbents such as camphor derivatives, salicylic acid derivatives, benzophenones, cinnamates, benzimidazoles and triazines
• new UV-A absorbers have been developed.
• One of the most important representatives is 4-dimethylethyl-4'-methoxydibenzoylmethane.
• UV filters UV absorbers
• UV-B filters which are photostable not only on their own, but moreover with respect to photostability compatible cosmetic formulations with others Form UV filters.
• the solubility of the UV filters should be high in conventional cosmetic oils.
• R j1-R ⁇ 3 J is independently hydrogen, CC 8 alkyl or -C 8 alkoxy, R 4 is COR, CO 2 R, CONR 2 where R is CC 8 alkyl (preferred) or C 3 -C 8 cycloalkyl
• R 5 is H or C 1 -C 8 -alkyl
• R 6 aryl with up to three d-Ca-alkyl or -CC 8 -alkoxy-substituted aryl, or C 3 -C 8 -cycloalkyl, as a UV filter (preferably UV-B filter) in cosmetic or dermatological formulations.
• a UV filter preferably UV-B filter
• the proviso is that R 5 is H when R 4 is COR.
• each formula image encompasses all possible configuration isomers of the stated compound and mixtures thereof;
• the possible E / Z isomers (and mixtures thereof) are included, in the case of the presence of chiral centers in each case the R and S enantiomers (and mixtures thereof) are included.
• This use according to the invention corresponds to a process for the preparation of a cosmetic or dermatological formulation, wherein an effective amount of one or more compounds of the formula I (as defined above) is mixed with further components of a cosmetic or dermatological formulation.
• the use according to the invention also corresponds to a method for protecting skin or hair against UV radiation, in particular UV-B radiation, wherein an effective amount of one or more compounds of the formula I (as defined above) in the form of a cosmetic or dermatological Formulation containing other ingredients is applied to the skin or hair.
• the compounds of the formula I to be used according to the invention are particularly suitable for combination with UV filters from the group of methoxycinnamate derivatives and / or dibenzoylmethane derivatives; such combinations have proven to be surprisingly photostable.
• DE 19755650 A1 discloses substituted alpha-methyl-styrene derivatives which can be used as photostable UV filters.
• the disclosed compounds always comprise an alpha-methyl group and two identical terminal groups (designated R 3 and R 4, respectively).
• R 3 and R 4 respectively.
• the disclosed compounds are UV-A filters.
• UV filters are compounds of the above formula I, where R 1 -R 3 independently of one another are hydrogen, C 1 -C 8 -alkyl or C 1 -C 8 -alkoxy,
• R 4 C0 2 R where R is CC 8 alkyl
• R 5 is H or CC 8 -alkyl
• R 6 are aryl or substituted with up to three -CC-alkyl or CC 8 -alkoxy-substituted aryl.
• the said compounds to be used preferably are readily soluble in cosmetic oils. While the solubility of the preferred compounds to be used in cosmetic oils such as isopropyl myristate, Miglyol-812 or Witconol TN regularly greater than 10 wt .-%, based on the total mass of the resulting mixture (solution), the solubility for the compounds with R 4 equal to COR or CONR 2 regularly lower than 10% by weight.
• R 6 are phenyl or substituted with up to three -CC 8 alkyl or dC 8 -alkoxy-substituted phenyl.
• R 1 is methoxy which is located in the para-position to the radical carrying the substituents R j R 5 and Re, R 2 and R 3 are hydrogen,
• R 4 CO 2 R with R is C 4 -C 5 -alkyl (preferably n-butyl),
• R 5 is H or CC 8 alkyl
• R 6 are phenyl. In contrast to the otherwise identical compounds with R equal to CrC 3 - Al yl those with R equal C 4 -C 5 alkyl liquids (and no solids), so that when using the particularly preferred compounds no risk of crystallization in the final cosmetic or dermatological formulation.
• UV filter for the UV-B range, the following compounds are preferred:
• UV filters are compounds of the above formula I, wherein R 6 is C 3 -C 8 -cycloalkyl, preferably cyclohexyl. When used, particularly photostable formulations result.
• R 4 is preferably CO 2 R with R being equal to C 1 -C 8 -alkyl, in particular for achieving good solubility, preferably R is methyl or ethyl. When R is ethyl, the solubility is particularly good.
• the benzylidene- ⁇ -dicarbonyl compounds to be used according to the invention can be used as UV filters (UV absorbers) in cosmetic or dermatological formulations, in particular for protection against acute (sunburn) and chronic (premature skin aging) skin damage Sunscreens, day care products and hair care products are used.
• UV filters UV absorbers
• cosmetic or dermatological formulations in particular for protection against acute (sunburn) and chronic (premature skin aging) skin damage Sunscreens, day care products and hair care products are used.
• benzylidene-.beta.-dicarbonyl compounds to be used according to the invention can be used individually or as a mixture in the corresponding formulations (preparations); You can also use them in combination with UV absorbers of other classes of substances or with these in any mixtures with each other.
• a cosmetic or dermatological formulation (preparation) according to the invention comprises one or more compounds of the formula I as defined above (with the general or a preferred meaning of the substituents), as UV absorbers.
• a preferred cosmetic or dermatological formulation further comprises: one or more further UV absorbers, in particular from the group of methoxycinnamate derivatives (p-methoxycinnamate) and / or dibenzoylmethane derivatives and / or coated or uncoated pigments of metal oxides.
• one or more further UV absorbers in particular from the group of methoxycinnamate derivatives (p-methoxycinnamate) and / or dibenzoylmethane derivatives and / or coated or uncoated pigments of metal oxides.
• the UV absorbers or pigments used are preferably selected and coordinated in their respective amounts so that they interact in such a way that the sun protection factor of the formulation is synergistically increased.
• the UV absorbers used are particularly advantageously selected and coordinated in their respective amounts such that the critical wavelength of the formulation ⁇ c rjt> 380 nm.
• the critical wavelength is the wavelength at which the integral of the spectral absorption curve reaches 90% of the 290-400 nm integral.
• UV absorbers with which the compounds of the formula I can be combined: p-aminobenzoic acid ethyl p-aminobenzoate (25 mol) ethoxylated p-dimethylaminobenzoic acid 2-ethylhexyl ester • p-aminobenzoic acid ethyl ester (2 mol) N-propoxylated p -Aminobenzoeklasted salicylic acid homomenthylester (homosalate) (Neo Heliopan ® HMS) salicylic acid 2-ethylhexyl ester (Neo Heliopan ® OS) Trietha nolami nsal icylat • 4-isopropylbenzyl menthyl anthranilate (Neo Heliopan ® MA) Diisopropylzimtklathylester p-methoxycin
• UV absorbers Particularly suitable for combination UV absorbers are p-aminobenzoic acid 3- (4'-trimethylammonium) benzylidene-boman-2-one methyl sulfate salicylic homomenthyl (Neo Heliopan ® HMS) 2-hydroxy-4-methoxy-benzophenone (Neo ® Heliopan BB) 2-phenylbenzimidazole sulfonic acid (Neo Heliopan Hydro ®) Terephthalyliden-dibornansulfonkla and salts (Mexoryl ® SX) 4-tert-butyl-4 methoxydibenzoylmethane (Neo Heliopan ® 357) 3- (4'-sulfo) benzylidene- bornan-2-one and salts 2-ethylhexyl-2-cyano-3,3-diphenylacryIat (Neo Heliopan ® 303) N - [(2 and 4) - [2- (
• polymer-bound or polymeric UV absorbers in formulations according to the invention, in particular those as described in WO-A-92/20690.
• benzylidene-.beta.-dicarbonyl compounds with finely divided inorganic and organic pigments, such as titanium dioxide, zinc oxide and iron oxide or Tinosorb ® M, in sunscreen and day care products with UV protection is possible.
• UV filters which can be used in the context of the present invention in combination with the benzylidene-.beta.-dicarbonyl compounds of the formula I, is of course not exhaustive.
• the total amount of all (singly or multiply) sulfonated water-soluble UV filter substances in the finished cosmetic or dermatological formulations for example phenylene-bis-benzimidazyl-tetrasulfonic acid dinatrium salt or salts thereof and / or the corresponding disulfonic acid or salts thereof and / or 2 Phenylbenzimidazole-5-sulfonic acid or its salts and / or 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid or its salts and / or 4- (2-oxo-3-bornyl-demethyl) -benzenesulfonic acid or their salts and / or 2-methyl-5- (2-oxo-3-bomylidene-methyl) -benzenesulfonic
• the total amount of oil-soluble UV filter substances (including the compounds of formula I) in the finished cosmetic or dermatological formulations, for example, 4 I 4 ' J 4 "- (1,3,5-triazine-2,4,6-triyltriimino) tris benzoic acid tris (2-ethylhexyl) and / or 4-tert-butyl-4'-methoxy dibenzoylmethane, and / or 4-methylbenzylidenecamphor and / or Octyidimethyl- p-aminobenzoic acid and / or Mexoryl XL ® and / or Uvasorb HEB ® and / or Tinosorb ® S and / or benzophenone-3 and / or Parsol ® SLX and / or Neo Heliopan MA ® is advantageously chosen from the range of 0.1 to 10.0 wt .-%, preferably 0, 5 to 6.0% by weight, based on the total weight of the formulations, if the presence of these
• the total amount of 2-ethylhexyl-p-methoxy-cinnamaten and / or p-Methox- cimt yarn in the finished cosmetic or dermatological preparations is advantageously from the range of 0.1 to 15.0 wt .-%, preferably 0.5 to 7.5% by weight, based on the total weight of the formulations, if the presence of these substances is desired.
• the total amount of ethylhexyl-2-cyano-3,3-diphenylacrylate in the final cosmetic or dermatological formulations, if the presence of this substance is desired, is advantageously in the range of 0.1 to 15.0 % By weight, preferably 0.5 to 10.0% by weight, based on the total weight of the formulations.
• the total amount of one or more salicylic acid derivatives in the finished cosmetic or dermatological formulations is in many cases advantageously selected from the range from 0.1 to 15.0% by weight, preferably 0.5 to 10.0% by weight on the total weight of the formulations.
• ethylhexyl salicylate it is advantageous to choose its total amount from the range of 0.1 to 5.0% by weight.
• homomenthylsalicylate it is advantageous to choose its total amount from the range of 0.1 to 10.0% by weight.
• the particularly preferred combinations of (a) p-methoxycinnamates (methoxycinnamates) and / or dibenzoylmethane derivatives and (b) compounds of the formula I can be formulated in a light-stable manner by using e.g. 0.1 to 5% by weight, preferably 1 to 3% by weight, of 4-tert-butyl-4'-methoxydibenzoylmethane, 0.1 to 10% by weight, preferably 1 to 7.5% by weight Ethylhexyl or isoamyl p-methoxycinnamate and at least 0.2% by weight, preferably from 1 to 6% by weight, of the compounds of the formula I to be used according to the invention
• a ratio is preferably set in the range of 1 part of dibenzoylmethane derivative, 2.5-3.5 parts of p-methoxycinnamic acid ester and 1.5-2.5 parts of the benzylidene- ⁇ -dicarbonyl compounds to be used according to the invention.
• Particularly preferred is the combination of 1 part of dibenzoylmethane derivative, 3 parts of p-methoxycinnamic acid ester and 2 parts of the benzylidene- ⁇ -dicarbonyl compounds to be used according to the invention.
• UV absorbers such as methyl benzylidene camphor, 2-ethylhexyl-2-cyano-S.S'-diphenyl, Octyltriazon, Uvasorb ® HEB, Tinosorb ® S, Tinosorb ® M, Ethylhexyl salicylate, homomenthyl salicylate as well
• the use of benzylidene- ⁇ -dicarbonyl compounds of the formula I in combination with other UV filters achieves a synergistic increase in the sun protection factor.
• Examples of a synergistic increase in the sun protection factor are cosmetic or dermatological emulsions which comprise both a compound of the formula I and ethylhexyl methoxycinnamate or octocrylene, or a combination of a compound of the formula I with ethylhexyl methoxycinnamate and 2-phenylbenzimidazole sulfonic acid, or ethylhexyl methoxycinnamate and methyl benzylidene camphor, or ethylhexyl contains -methoxycinnamat and 4-t-butyl-4'-methoxydibenzoylmethane, or Neo Heliopan AP ® and ethylhexyl methoxycinnamate, or a combination of compound of formula I with octocrylene, methylbenzylidene camphor and zinc oxide.
• UV filter combinations are given here by way of example only; a synergistic effect also occurs when combined with other UV filters.
• the combination of compounds of formula I with UV-A absorbers gives an optimal broadband protection performance (290-400nm).
• a combination of compounds of formula I with Neo Heliopan AP ® (UV absorber-All) and indanylidene compounds according to DE 100 55 940 (UV absorber AI) may be mentioned for this broad UV protection performance.
• UV-A-filters which are preferably used in combination with compounds of formula I, alone or in combination of compounds of formula I and Neo Heliopan ® AP and "/ or indanylidene compounds according to DE 100 55 940, are Mexoryl ® SX, Mexoryl ® XL , Tinosorb M ® ® Tinosorb S, benzophenone-3, benzophenone-4, Neo Heliopan ® 357, Neo Heliopan MA ® and Uvinul A Plus ®.
• titanium dioxide is a UV broadband protection with a critical wavelength ⁇ o ri t .> 380 nm (cf., Diffey in Int., J. Cosm., Science 16, 47 (1994)).
• benzylidene- ⁇ -dicarbonyl compounds of the formula I to be used according to the invention are (crystalline) solids under standard conditions (25 ° C., 1013 mbar) and must therefore be present in cosmetic formulations be solved sufficiently to avoid the problem of recrystallization after prolonged storage (see the above comments on particularly preferred, since liquid, compounds of formula I).
• a sufficient amount of the oil components usually used in cosmetic formulations liquid oil-soluble UV absorbers or alcohols are used, for.
• ethanol isopropanol or 1-butanol.
• Particularly preferred is the use of the following oil components and / or UV absorbers to achieve sufficient solubility of crystalline benzylidene- ⁇ -dicarbonyl compounds of the formula I to be used according to the invention:
• Propylenglykoldicapry-Iat dicaprate (Myritol PC), hexyl laurate (Cetiol A), dicapryl ether (Cetiol OE), diethylhexyl naphthalate (Hall Brite ® TQ), butyloctyl salicylate (Hall Brite ® BHB), dibutyl adipate (Cetiol B), triethyl citrate (Hydagen CAT), propylene glycol dibenzoate (Finsolv PG 22), tribuiyl citrate, dioctyl malate (Ceraphyl 45), dipropylene glycol dibenzoate (Benzoflex 245), acetyltributyl citrate (Citroflex A-4), acetyl triethyl citrate (Citroflex A-2).
• the list of said oils which can be used in the context of the present invention is of course not exhaustive.
• the total amount used of all components of the oil phase in cosmetic emulsions with compounds of the formula I is preferably in the range of 0.5 to 30%, preferably 2 to 15%. All the above-mentioned oil components or liquid oil-soluble UV filters are excellent solvents for all crystalline oil-soluble UV absorbers.
• UV absorbers on garments leave no more washable stains.
• tert-butylmethoxydibenzoylmethane is known to produce no more washable stains on fabrics.
• This disadvantage does not have the benzylidene-.beta.-dicarbonyl compounds to be used according to the invention, since any stains on textiles can be washed out very well.
• Sunscreen products should be waterproof, so that a sufficient UV protection for the user, especially children, while swimming or bathing is guaranteed.
• the compounds to be used according to the invention meet these requirements to a particular extent.
• 97% substantivity of the UV absorber was measured after washing and 95% in a W / O emulsion.
• UV absorbers according to the invention may furthermore be of considerable advantage to use the UV absorbers according to the invention with chelating substances, as are listed, for example, in EP-A 496434, EP-A 313 305 and WO-94/04128 * , or with polyaspartic acid and ethylenediamine tetramethyl to combine phosphonic acid salts.
• the invention furthermore relates to the use of the compounds of the formula I to be used according to the invention in combination with conventional UV absorbers for enhancing the protection against harmful UV radiation beyond the extent of the protection which, when using the same total amounts of conventional or the UV radiation to be used according to the invention. Filter alone is achieved (synergistic effect).
• the total amount of UV filter substances (UVA, UVB and / or broadband filters) in cosmetic or dermatological formulations according to the invention is advantageously in the range from 0.1 to 30% by weight. -%, preferably 0.1 to 10.0 wt .-%, in particular 0.5 to 5.0 wt .-%, based on the total weight of the formulations.
• Cosmetic and dermatological formulations according to the invention also advantageously contain, although not necessarily, inorganic pigments based on finely dispersed metal oxides and / or other sparingly soluble or insoluble metal compounds, in particular the oxides of titanium (1102), zinc (ZnO), iron (eg Fe 2 0 3 ), zirconium (Zr0 2 ). Silicon (Si0 2 ). Manganese (eg MnO), aluminum (A1 2 0 3 ), Cers (eg Ce 2 0 3 ), mixed oxides of the corresponding metals and mixtures of such oxides. These pigments are X-ray amorphous or non-X-ray amorphous. Particular preference is given to pigments based on TiO 2 .
• X-ray amorphous oxide pigments are metal oxides or semimetal oxides which show no or no recognizable crystal structure in X-ray diffraction experiments. Often, such pigments are obtainable by flame reaction, for example, by reacting a metal or semimetal halide with hydrogen and air (or pure oxygen) in a flame.
• Dispersion stabilization and used as a carrier for example, to increase the volume of finely divided powders or powders.
• X-ray amorphous oxide pigments are, for example, high-purity silica.
• BET active surface area
• the silica pigments are recognizable as loose, white powders.
• Aerosil ® Silicon dioxide pigment are marketed commercially under the name Aerosil ® (CAS no. 7631-85-9) or Carb-O-Sil Advantageous Aerosil ® types, for example, 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, Aerosil ® R976.
• Aerosil ® CAS no. 7631-85-9
• Aerosil ® types for example, Aerosil ® 0x50. Aerosil ® 130, Aerosil ® 150, Aerosil ® 200, Aerosil ® 300, Aerosil ® 380
• Cosmetic or dermatological sunscreen preparations according to the invention advantageously contain from 0.1 to 20% by weight, advantageously from 0.5 to 10% by weight, very particularly preferably from 1 to 5% by weight, of X-ray amorphous oxide pigments.
• the non-X-ray amorphous inorganic pigments according to the invention are advantageously present in hydrophobic form, that is to say that they are surface-treated to be water-repellent.
• This surface treatment may consist in providing the pigments with a thin hydrophobic layer according to methods known per se.
• One such method is, for example, that the hydrophobic surface layer is generated after a reaction according to nTiO 2 + m (RO) 3Si-R ' ⁇ nTiO 2 (surface), where n and m are random stoichiometric parameters to be used, R and R 'The desired organic radicals.
• nTiO 2 + m (RO) 3Si-R ' ⁇ nTiO 2 (surface) where n and m are random stoichiometric parameters to be used, R and R 'The desired organic radicals.
• RO 3Si-R ' ⁇ nTiO 2
• TiO 2 pigments marketed under the trade name T805 by Degussa.
• TiO 2 / Fe 2 O 3 mixed oxides are also available, for example, under the trade name T817 from Degussa.
• the total amount of inorganic pigments, in particular hydrophobic inorganic micropigments, in the finished cosmetic or dermatological formulations is advantageously in the range from 0.1 to 30% by weight, preferably 0.1 to 10.0, in particular 0.5 to 6.0% by weight, based on the total weight of the formulations.
• the cosmetic and / or dermatological formulations according to the invention can be composed as usual and serve for cosmetic and / or dermatological sun protection, furthermore for the treatment, care and cleansing of the skin and / or the hair and as a make-up product in decorative cosmetics. Accordingly, the formulations according to the invention, depending on their structure, can be used, for example, as skin protection cream, cleansing milk, sunscreen lotion, nutritive cream, day cream or night cream, etc.
• formulations according to the invention may be possible and advantageous to use the formulations according to the invention as a basis for pharmaceutical formulations. Preference is given in particular to those cosmetic and dermatological formulations which are in the form of a skin care or make-up product. Typical embodiments are creams, gels, lotions, alcoholic and aqueous / alcoholic solutions, emulsions or stick preparations. These agents may also be used as other auxiliaries and additives, mild surfactants, co-emulsifiers, superfatting agents, pearlescent waxes, consistency regulators, thickeners, polymers,
• Silicone compounds fats, waxes, stabilizers, biogenic agents, deodorants, antidandruff agents, film formers, swelling agents, hydrotopes, preservatives, insect repellents, tanning agents, artificial self-tanning agents (e.g., dihydroxyacetone), solubilizers, perfume oils, dyes, anti-sprouting agents, and the like.
• the cosmetic and dermatological formulations according to the invention are applied to the skin and / or the hair in a sufficient amount in the manner customary for cosmetics.
• cosmetic and / or dermatological formulations according to the invention which are in the form of a cosmetic agent for protecting the skin and hair.
• These may advantageously contain, in addition to UV-A, UV-B and / or broad-band filters used according to the invention, at least one inorganic pigment, preferably an inorganic micropigment.
• the cosmetic and / or dermatological formulations according to the invention may comprise cosmetic adjuvants conventionally used in such formulations, for example preservatives, bactericides, perfumes, foaming inhibitors, colorants, pigments which have a coloring effect, thickeners, moisturizing and / or thickening agents.
• 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 (lsolan ® GI 34), polyglyceryl-3 oleate, Polyglyceryl-Diisostearyl-3-Diisostearate (lsolan ® PDI), Polyglyceryl-3 methyl glucose distearate (Tego Carey ® 450), Polyglyceryl-3 beeswax (Gera Bellina ®), Polyglyceryl-4 caprate (polyglycerol Caprate T2010
• antioxidants An additional content of antioxidants is generally preferred. According to the invention, all antioxidants which are suitable or customary for cosmetic and / or dermatological applications can be used as favorable antioxidants.
• the antioxidants are selected from the group consisting of amino acids (eg glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazoles (eg urocanic acid) and their derivatives, peptides such as D, L-carnosine, D-carnosine, L-carnosine and their derivatives (eg anserine), carotenoids, caratins (eg a-carotene, b-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, palmito, amino
• the amount of the aforementioned antioxidants (one or more compounds) in the formulations is preferably 0.001 to 30 wt .-%, particularly preferably 0.05 to 20 wt .-%, in particular 1 to 10 wt .-%, based on the total weight of Formulation.
• vitamin E and / or its derivatives are the antioxidant (s), it is advantageous if their respective concentrations are within the range of 0.001 to 10 wt .-%, based on the total weight of the formulation to choose.
• vitamin A or vitamin A derivatives, or carotenes or derivatives thereof are the antioxidant or antioxidants, it is advantageous if their respective concentrations are in the range from 0.001 to 10% by weight, based on the total weight of the formulation, to choose.
• the lipid phase can advantageously be selected from the following substance group: mineral oils, mineral waxes; - Oils, such as triglycerides of capric or caprylic acid, also 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 fatty alcohols with alkanoic acids of low C number or with fatty acids; - alkyl benzoates; - Silicone oils such as dimethylpolysiloxane, diethylpolysiloxane, diphenylpoly- siloxane and mixed forms thereof.
• mineral oils mineral waxes
• - Oils such as triglycerides of capric or caprylic acid, also natural oils such. Castor oil
• Fats, waxes and other natural and synthetic fats preferably esters of fatty acids with lower C-
• the oil phases of the emulsions, oleogels or hydrodispersions or lipodispersions in the context of the present invention advantageously comprise substances from the group of esters of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids having a chain length of 3 to 30 carbon atoms and saturated and / or or unsaturated, branched and / or unbranched alcohols having a chain length of 3 to 30 carbon atoms, from the group of esters of aromatic carboxylic acids and saturated and / or unsaturated, branched and / or unbranched alcohols having a chain length of 3 to 30 carbon atoms.
• ester oils can then be advantageously selected from the group consisting of isopropyl myristate, palmitate, stearate, oleate, n-butyl stearate, n-hexyl laurate, n-decyl oleate, isooctyl stearate, isononyl stearate, isononyl isononanate, 2-ethylhexyl palmitate, ethylhexyl laurate, 2 Hexyl decyl stearate, 2-octyldodecyl palmitate, Oleyl oleate, oleyl erucate, erucyl oleate and synthetic, semi-synthetic and natural mixtures of such esters, eg. Jojoba oil.
• 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 also the 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 to 18 carbon atoms.
• the fatty acid triglycerides may be advantageously selected from the group of synthetic, semi-synthetic 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 cetyl palmitate, as the sole (not to the relevant extent UV-absorbing) lipid component of the oil phase.
• the oil phase comprises one or more substances from the group selected from the group 2-ethylhexyl, Ocryldodecanol, isotridecyl isononanoate, isoeicosane, 2-ethylhexyl cocoate, C ⁇ benzoate alkyl-2- i 5, caprylic capric triglyceride, dicapryl ether.
• mixtures of 2- C ⁇ ⁇ 5 alkyl benzoate and 2-ethylhexyl isostearate mixtures of 2- C ⁇ i 5 alkyl benzoate and isotridecyl isononanoate and mixtures of C 12- ⁇ 5 alkyl benzoate, 2-ethylhexyl isostearate and isotridecyl isononanoate.
• the oil phase can also advantageously have a content of cyclic or linear silicone oils, although it is preferred to use an additional content of other oil phase components in addition to the silicone oil or silicone oils.
• cyclomethicone octamethylcyclotetrasiloxane
• other silicone oils are also advantageous for the purposes of the present invention, for example hexamethyl cyclotrisiloxane, polydimethylsiloxane, poly (methylphenylsiloxane).
• mixtures of cyclomethicone and Isotridecylisononanoat and from cyclomethicone and 2-Ethylhexylisostearat are particularly advantageous.
• the aqueous phase of the formulations according to the invention optionally advantageously contains alcohols, diols or polyols (lower alkyl), and their ethers, preferably ethanol, isopropanol, propylene glycol, glycerol, ethylene glycol monoethyl or monobutyl ether, propylene glycol monomethyl, monoethyl or monobutyl ether, Diethylenglykolmonomethyl- or - monoethyl ether and analogous products, also alcohols (lower alkyl), eg Ethanol, 1, 2-propanediol, glycerol and in particular one or more thickening agents, which or which can be advantageously selected from the group of silica, aluminum silicates, polysaccharides or their derivatives, e.g.
• Hyaluronic acid, xanthan gum, hydroxypropylmethylcellulose particularly 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.
• the invention also relates to novel compounds of the formula I.
• R 1 is C 1 -C 8 -alkoxy which is located in the para position relative to the radical bearing the substituents R 4 , R 5 and R 6 , preferably methoxy,
• R 2 and R 3 are hydrogen
• R 4 C0 2 R where R is CC 8 alkyl
• R 6 is phenyl or cyclohexyl.
• R 4 is C0 2 R where R is methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, iso-amyl, preferably n-butyl, and R 6 is phenyl ,
• R 4 CO 2 R with R is methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl or tert-butyl, preferably ethyl, and R 6 is cyclohexyl.
• Part A Heat to about 85 ° C.
• Part B Weigh raw materials without Carbopol. Disperse Carbopol with Ultra Turrax. Heat to about 85 ° C. Give B to A.
• Part C Add immediately to A / B and then homogenize hot (Ultra Turrax). Allow to cool while stirring.
• Part D Add and mix.
• Part A Heat to about 85 ° C.
• Part B Weigh raw materials without Carbopol. Disperse Carbopol with Ultra Turrax. Heat to about 85 ° C. Give B to A.
• Part C Add immediately to A / B and then homogenize hot (Ultra Turrax). Allow to cool while stirring.
• Part D Add and mix.
• Part A Heat to 80-85 ° C.
• Part B Heat to 80-85 ° C, add Part B to Part A with stirring.
• Part C Disperse Carbopol into the water and neutralize with stirring while stirring with NaOH. Add part C at about 60 ° C with stirring. Allow to cool to RT (room temperature, 25 ° C).
• Part D Add and mix.
• Part A Heat to 80-85 ° C.
• Part B Heat to 80-85 ° C, add Part B to Part A with stirring.
• Part C Disperse Carbopol into the water and neutralize with stirring while stirring with NaOH.
• Part D Add and mix.
• Part A Dissolve the UV absorber according to formula 1 in the oils or liquid UV filters (heating up to approx. 70 ° C). Cool down to about 30 ° C, add remaining ingredients except Carbopol and Pemulen and mix at room temperature (stir for about 5 minutes). Stir in Carbopol and Pemulen.
• Part B Dissolve sol brole in phenoxyethanol with warming. Mix with water and glycerine, add to part A with stirring. Approximately Stir for 60 minutes.
• Part C Add to A / B, homogenize with the Ultra Turrax.
• Part A Heat to about 85 ° C.
• Part B Heat to about 85 ° C (without zinc oxide, to disperse zinc oxide with the Ultra Turrax). Give B to A. Allow to cool with stirring, then homogenize.
• Part B Heat to about 85 ° C (without zinc oxide, to disperse zinc oxide with the Ultra Turrax). Give B to A. Allow to cool while stirring.
• Part C Add and then homogenize.
• Part A Heat to about 85 ° C.
• Part B Heat to about 85 ° C. Give B to A. Allow to cool while stirring. Part C: Add and then homogenize.
• Part A Heat to 80 ° C.
• Part B Heat to 80 ° C. Add to Part A with stirring.
• Part C Disperse Carbopol in water and neutralize with sodium hydroxide solution. At 55 ° C add to part A / B.
• Method of preparation Part A Dissolve Lara Care A-200 with stirring in the other components of Part A.
• Part B Weigh out all raw materials (without pemulen) and dissolve the crystalline substances by heating. Disperse pemulen. Add part B to part A and homogenize for 1 minute. Add part C + D and homogenize with the Ultra Turrax for another 1-2 minutes. Formulation Example 11
• Part A Disperse Carbopol in water and neutralize with sodium hydroxide solution.
• Part B Add to Part A with stirring.
• Part C Dissolve crystalline constituents with warming (max. 40 ° C) in the other raw materials of Part C and add to Part A / B. Stir well and then homogenize. (Homozenta).
• Part A Heat to 80 ° C.
• Part B Heat to 80 ° C. Add to Part A with stirring.
• Part C Add at 40 ° C and cool to RT.
• Part A Heat to 80-85 ° C.
• Part B Heat to 80-85 ° C, add Part B to Part A with stirring.
• Part C Disperse Carbopol into the water and neutralize with stirring while stirring with NaOH. Add part C at about 60 ° C with stirring.
• Photostability tests were carried out with a Suntester of the company.
• the irradiance was 80 W / m 2 , based on the UV range of 290-400 nm.
• the irradiation time was 4 hours in total, the photoabsorption of the UV filters after 2 and 4 hours of irradiation being measured by HPLC analyzes.
• the irradiations of the UV filter mixtures were carried out in an isopropyl myristate solution. The percentage values refer to the measured value without irradiation (reduction of the concentration).
• DDBM 4-dimethylethyl-4'-methoxydibenzoylmethane
• DDBM 4-dimethylethyl-4'-methoxydibenzoylmethane
• R 1 is methoxy, which is located in the para-position to the radical carrying the substituents R.; R 5 and R 6 ,
• R 2 and R 3 are hydrogen
• R 6 is phenyl
• R 1 is methoxy, which is located in the para-position to the radical carrying the substituents R 4 , R 5 and R 6 , R 2 and R 3 are hydrogen, R 4 CO 2 R with R is CC 5 alkyl
• R 6 phenyl similarly good photostability values.
• DDBM 4-dimethylethyl-4'-methoxydibenzoylmethane
• DDBM 4-dimethylethyl-4'-methoxydibenzoylmethane
• DDBM 4-dimethylethyl-4'-methoxydibenzoylmethane
• DDBM 4-dimethylethyl-4'-methoxydibenzoylmethane

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