WO2010060513A2 - Procédé de photostabilisation de dérivés d'acide ascorbique - Google Patents

Procédé de photostabilisation de dérivés d'acide ascorbique Download PDF

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WO2010060513A2
WO2010060513A2 PCT/EP2009/007685 EP2009007685W WO2010060513A2 WO 2010060513 A2 WO2010060513 A2 WO 2010060513A2 EP 2009007685 W EP2009007685 W EP 2009007685W WO 2010060513 A2 WO2010060513 A2 WO 2010060513A2
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formula
nha
substituent
use according
radicals
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PCT/EP2009/007685
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German (de)
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WO2010060513A3 (fr
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Thomas Rudolph
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Merck Patent Gmbh
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    • 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
    • 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
    • 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
    • A61K8/67—Vitamins
    • A61K8/676—Ascorbic acid, i.e. vitamin C
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/52—Stabilizers
    • 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
    • A61Q5/065—Preparations for temporary colouring the hair, e.g. direct dyes
    • 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
    • A61Q5/10—Preparations for permanently dyeing the hair

Definitions

  • the invention relates to the use of a compound selected from the group consisting of diphenylacrylate UV filters, dibenzoylmethane UV filters, phenolic antioxidants or mixtures thereof, for improving UV radiation.
  • WO 2008/017346 describes a use of ascorbic acid derivatives for the functionalization of matrices.
  • the suitability of ascorbic acid derivatives as skin-binding UV filters is described when the ascorbic acid derivatives of the given formula I contain UV chromophores, as listed in detail.
  • the purpose of these compounds is to bind the substances to the skin as a result of oxidation of the ascorbic acid portion and hence to absorb UV light as constantly as possible via the UV chromophore.
  • the UV chromophore used in the ascorbic acid derivative it is desirable for the UV chromophore used in the ascorbic acid derivative to be as light-stable as possible.
  • UV filters can not only be structurally photoinstable, but their photostability can be considerably influenced by the composition of the surrounding medium.
  • the most prominent example is the UV filter t-butylmethoxydibenzoylmethane, which is generally considered to be photoinstable, but can be almost completely stailised in polar protic media.
  • the object of the invention is therefore to provide a process which is suitable when photostability of the UV chromophore contained in ascorbic acid derivatives occurs during UV irradiation To achieve the highest possible integral UV absorption of Ascorbinklarederivates.
  • Diphenyl cyanoacrylate UV filter for example 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate, also known as octocrylene, and derivatives thereof derived partly from polymeric compounds, for example as Polycrylene® [INCI polyester].
  • Dibenzoylmethane UV filter for example - (4-tert-butylphenyl) -3- (4-methoxyphenyl) propane-1, 3-dione, also known under the name Avobenzone;
  • Phenolic antioxidants for example bis-ethylhexylhydroxydimethoxybenzyl malonate, also known under the trade name RonaCare® AP or bis-ethylhexylhydroxydimethoxybenzylidenemalonate (Oxynex® ST) and mixtures of the three classes of substances.
  • a first aspect of the invention is therefore the use of a compound selected from the group of diphenylacrylate UV filters, dibenzoylmethane UV filters, phenolic antioxidants or mixtures thereof, for improving the UV stability of a preparation comprising at least one ascorbic acid derivative of the formula I,
  • R 1 or R 2 are each independently hydroxy, -O-alkyl, -OC (O) -
  • R 3 or R 4 are each independently hydroxy or a radical B and
  • B is a substituent of the formula II, III, IV, V, VI, VII 1 VIII, IX, X, Xl and / or XII means
  • R 5 to R 16 are each independently H, -OH 1 -OA 1 -A 1 -NH 2 , -NHA 1 -
  • A is alkyl having 1 to 20 C atoms, n is an integer from 1 to 25,
  • X is the counterion to the cations [NHA 2 ] + and [NA 3 ] + or the anion [SO 3 ] " and
  • Y and Z are each independently -ascorbyl, hydroxy, -O-2-ethylhexyl, -O-hexyl, -OA or -NH-C (CH 3 ) 3 , with the proviso that at least one of R 3 or R 3 4 for one
  • the preparations are usually either topically applicable preparations, for example cosmetic, pharmaceutical or dermatological formulations.
  • the preparations in this case contain a cosmetically, pharmaceutically or dermatologically suitable carrier and, if desired Property profile optional further suitable ingredients.
  • the topical preparations are preferably used as a cosmetic or dermatological preparation, particularly preferably as a cosmetic preparation.
  • the compounds of formula I according to the invention are typically present in amounts of from 0.01 to 20% by weight, preferably in amounts of from 0.05% by weight to 10% by weight, more preferably in amounts of 0.5% by weight. % to 3.0 wt .-% used .. It does not give the expert any difficulty to select the amounts depending on the intended effect of the preparation accordingly.
  • diphenyl acrylate UV filters are, for example, compounds of the formula A,
  • X C 1 -C 30 -alkyl, branched or unbranched or
  • Yi and Y2 in formula A are each independently H, a branched or unbranched alkyl group having 1 to 4 C atoms or a branched or unbranched alkoxy group having 1 to 8 C atoms, Y 3 in formula A is H or CN.
  • Particularly preferred compounds from the group of diphenylacrylate UV filters of the formula A are compounds in which Y 3 is CN.
  • Most particularly preferred for this group is octocrylene or, in other words, the compound 2-ethylhexyl-2-cyano-3,3-diphenylacrylate, and its derivatives in polymeric form such as, for example, Polycrylene® [INCI Polyester-8; CAS 862993-96-2]); Solasil® PSF [INCI: Undecylcrylene dimethicone] from Hallstar.
  • polymeric structures are described, for example, in US Pat. No. 6,890,521 or 6,899,866.
  • An organically modified silicone polymer is, for example, Solasil® PSF [INCI: Undecylcrylene Dimethicone] or Polysilicone 15.
  • Dibenzoylmethane derivatives are in themselves already well-known products which are described in particular in the above-mentioned publications FR-A-2 326 405, FR-A-2 440 933 and EP-A-0 114 607.
  • Preferred dibenzoylmethane derivatives correspond to the formula B
  • R 1, R 2, R 3 and R 4 which are identical or different, represent hydrogen, a linear or branched Cis-alkyl group or a straight or branched Ci -8 alkoxy group, in particular
  • Another preferred dibenzoylmethane derivative is 4-isopropyldibenzoylmethane.
  • dibenzoylmethane derivatives can be photoinstable, they can in turn be stabilized by the ascorbic acid derivatives according to the invention.
  • phenolic antioxidants are, for example, compounds of the formula C,
  • A-B denotes a single bond or a double bond
  • 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 linear or branched alkyl having 1 to 8 C atoms or linear or branched alkoxy having 1 to 8 C atoms
  • R 6 is linear or branched alkyl having 1 to 8 C atoms, preferably 2- (4-hydroxy-3 , 5-dimethoxybenzy) malonic acid-bis (2-ethylhexyl) ester (known as RonaCare ® AP) or bis (2-ethylhexyl) -2- (4-hydroxy-3,5-dimethoxybenzyl) malonate (known as Oxynex® ST).
  • C 1 -C 6 -alkyl denotes an alkyl group having 1, 2, 3, 4, 5 or 6 C atoms, for example methyl, ethyl, isopropyl, n-propyl, isobutyl, n-butyl, tert-butyl, n Pentyl or n-hexyl.
  • Aryl in formula A is phenyl which is unsubstituted or substituted by alkyl groups having 1 to 6 C atoms or alkoxy groups having 1 to 6 C atoms or alkylamino groups having 1 to 6 C atoms or dialkylamino groups having 1 to 6 C atoms.
  • suitable alkoxy radicals for R 1 or R 2 are those alkyl groups which contain 1 to 6 C atoms, preferably 1 to 4 C atoms.
  • alkoxy groups are methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy or tert-butoxy.
  • the group -OPO 3 M is preferably the -OPO 3 H group, but it is also possible to use salts of the formula I where M in formula I corresponds to an alkali metal cation, for example of Na or K, or of an alkaline earth metal cation, for example of Mg or Ca.
  • O-glycosyl in formula I can be used, for example, for monosaccharides such as ribose, arabinose xylose, lyxose, allose, altrose, glucose, mannose, gulose, idose, galactose, talose, ribulose , Xylulose, psicose, fructose, sorbose or tagatose.
  • monosaccharides such as ribose, arabinose xylose, lyxose, allose, altrose, glucose, mannose, gulose, idose, galactose, talose, ribulose , Xylulose, psicose, fructose, sorbose or tagatose.
  • isomers i. each contain the D or L forms.
  • glucose, galactose or fructose most preferably glucose, are used.
  • disaccharides are also suitable, such as sucrose (or else called sucrose), lactose, trehalose, maltose, cellobiose, gentiobiose or melibiose. This list includes both the ⁇ and ⁇ forms.
  • disaccharides are preferably sucrose or lactose, particularly preferably sucrose used.
  • the radical R 1 in formula I is hydroxy and R 2 is -O-alkyl, -OC (O) -alkyl, -OPO 3 M or O-glycosyl, as described above.
  • radical R 2 in formula I is hydroxy and R 1 is
  • both radicals R 2 and R 1 are hydroxy.
  • R 3 or R 4 are each independently hydroxy or a radical B and the radical B corresponds to a partial structure of the formula II, III, IV, V, VI, VII, VIII, IX, X 1 XI or XII, as described above.
  • the radical R 3 is hydroxy and R 4 corresponds to a radical B, as described above and preferred below.
  • B is both R 3 and R 4 , as well as R 3 or R 4 .
  • A denotes alkyl having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20 C atoms each independently represent a linear or branched alkyl group. for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or tert-butyl, and also pentyl, 1-, 2- or 3-methylbutyl, 1, 1, 1, 2 or 2 , 2-Dimethylpropyl, 1-ethylpropyl, hexyl, 1-, 2-, 3- or 4-methylpentyl, 1, 1, 1, 2, 1, 3, 2,2, 2,3 or 3 , 3-Dimethylbutyl, 1- or 2-ethylbutyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl, 1, 1, 2- or 1, 2,2-trimethylpropyl or alkyl groups and their isomers of the empirical formulas C 7 H 15
  • n is an integer from 1 to 25, preferably an integer from 1, 2, 3, 4 or 5.
  • X describes the counterion for the cations [NHA 2 ] + and [NA 3 J + , where A has one of the meanings given above, preferably Cl “ , Br “ , I “ or [SO 4 ] 2 ' or the counterion of the anion [ SO 3 ] " , preferably an ammonium ion or an alkali metal or alkaline earth metal cation such as Na + , K + , Mg 2+ or Ca 2+ .
  • compounds of the formula I can exist as a zwitterionic structure.
  • Compounds of the formula I can also be present as salts in the preparation, ie at least one hydroxy group of the ascorbic acid skeleton is present deprotonated and the charge becomes by a counter cation, for example an alkali or alkaline earth metal cation, balanced.
  • radicals R 5 to R 9 , R 11 and R 12 are preferably H and
  • R 10 is -OH 1 -OA, -A, -NH 2 , -NHA, -NA 2 , -NH- (CH 2 -CH 2 -O) n -H, -Nf (CH 2 -CH 2 -O) n -H] 2 , - [NHA 2 ] X, - [NA 3 ] X, -SO 3 H, - [SO 3 ] X or 2H-benzotriazol-2-yl.
  • R 10 in formula II is preferably -OA, -NH 2 , -NHA or -NA 2 , most preferably -OA or -NA 2 .
  • a in R 10 of the formula II is very particularly preferably methyl, ethyl, n-butyl, n-hexyl.
  • radicals R 5 , R 6 , R 8 and R 9 are preferably H and
  • R 7 is -OH, -OA, -A, -NH 2 , -NHA 1 -NA 2 , -NH- (CH 2 -CH 2 -O) n -H, -N [(CH 2 -CH 2 -O) n -H] 2 , - [NHA 2 ] X, - [NA 3 ] X 1 -SO 3 H 1 - [SO 3 ] X or 2H-benzotriazol-2-yl.
  • R 7 in formula III is preferably -OA, -NH 2 , -NHA or -NA 2 , most preferably -OA or -NA 2 , wherein A has one of the meanings given above.
  • a in R 7 of the formula III is very particularly preferably methyl, ethyl, n-butyl, n-hexyl.
  • radicals R 5 , R 6 , R 8 and R 9 are preferably H and
  • R 7 is -OH, -OA, -A, -NH 2 , -NHA, -NA 2 , -NH- (CH 2 -CH 2 -O) n -H 1 -N [(CH 2 -CH 2 -O) n -H] 2 , - [NHA 2 ] X, - [NA 3 ] X, -SO 3 H, - [SO 3 ] X or 2H-benzotriazol-2-yl.
  • R 7 in formula IV is preferably -OA, -NH 2 , -NHA or -NA 2 , most preferably -OA or -NA 2 , wherein A has one of the meanings given above.
  • a in R 7 of the formula IV is very particularly preferably methyl, ethyl, n-butyl, n-hexyl.
  • the radicals R 5 , R 8 and R 9 are preferably H, R 6 is 2H-benzotriazol-2-yl and R 7 is -OH, -OA, -A, -NH 2 , -NHA , -NA 2 , -NH- (CH 2 -CH 2 -O) n -H, -N [(CH 2 -CH 2 -O) n -H] 2 , - [NHA 2 ] X, - [NA 3 ] X, -SO 3 H or - [SO 3 ] X.
  • R 7 is more preferably OH.
  • the radicals R 6 , R 8 , R 11 and R 13 are preferably H and the substituents R 5 , R 7 , R 9 , R 10 , R 12 and R 14 are each independently H, -OH, -OA, -A, -NH 2 , -NHA, -NA 2 , -NH- (CH 2 - CH 2 -O) n -H. -Nf (CH 2 -CH 2 -O) n -H] 2 . - [NHA 2 ] X. - [NA 3 ] X. -SO 3 H, - [SO 3 ] X or 2H-benzotriazol-2-yl.
  • R 5 , R 7 , R 9 , R 10 , R 12 and R 14 in formula V are each independently preferably H, -OA, -NH 2 , -NHA or -NA 2 , most preferably H, wherein A is one of has previously given meanings.
  • the radicals R 6 , R 8 , R 9 , R 12 , R 13 and R 16 are preferably H and the substituents R 5 , R 7 , R 10 , R 11 , R 14 and R 15 are each independently each other is H, -OH, -OA, -A, -NH 2 , -NHA, -NA 2 , -NH- (CH 2 -CH 2 -O) n -H, -NI (CH 2 -CH 2 -O) n -H] 2 , - [NHA 2 ] X, - [NA 3 ] X, -SO 3 H, - [SO 3 ] X or 2H-benzotriazol-2-yl.
  • R 5 , R 7 , R 10 , R 11 , R 14 and R 15 in formula VI are each, independently of one another, preferably H, -OA, -NH 2 , -NHA or -NA 2 , very particularly preferably H, where A is one of has previously given meanings.
  • the radicals R 5 , R 6 , R 7 , R 8 , R 9 and R 10 are preferably H and Z is -ascorbyl, hydroxy, -O-2-ethylhexyl, -O-hexyl, -OA or -NH-C (CH 3 ) 3 .
  • Z in formula VII is particularly preferably OH.
  • the radicals R 5 , R 6 , R 7 and R 8 are preferably H and the substituent R 9 is preferably -OH, -OA, -A, - NH 2 , -NHA, -NA 2 , - NH- (CH 2 -CH 2 -O) n -H, -N [(CH 2 -CH 2 -O) n -H] 2 , - [NHA 2 ] X, - [NA 3 ] X, -SO 3 H, - [SO 3 ] X or 2H-benzotriazol-2-yl.
  • R 9 in formula VIII particularly preferably means -OA.
  • the radicals R 5 , R 6 , R 7 and R 8 are preferably H and the substituent R 9 is preferably -OH, -OA, -A, - NH 2 , -NHA, -NA 2 , - NH- (CH 2 -CH 2 -O) n -H, -Nf (CH 2 -CH 2 -O) n -H] 2 , - [NHA 2 ] X, - [NA 3 ] X, -SO 3 H , - [SO 3 ] X or 2H-benzotriazol-2-yl.
  • R 9 in formula IX particularly preferably means -OA.
  • the radicals R 5 , R 7 and R 8 are preferably H and the substituent R 6 is preferably -OH, -OA, -A, - NH 2 , -NHA, -NA 2 , -NH- ( CH 2 -CH 2 -O) n -H, -N [(CH 2 -CH 2 -O) n -H] 2 , - [NHA 2 ] X, - [NA 3 ] X, -SO 3 H, - [SO 3 ] X or 2H-benzotriazol-2-yl.
  • R 6 in formula X is particularly preferably -OH.
  • the radicals R 5 , R 6 , R 7 , R 8 , R 9 , R 11 and R 12 are preferably H and the substituent R 10 is preferably H, -OH, -OA, -A, - NH 2, -NHA, -NA 2, -NH- (CH 2 -CH 2 -O) n -H, -N [(CH 2 -CH 2 -O) n - H] 2, - [NHA 2] X , - [NA 3 ] X, -SO 3 H, - [SO 3 ] X or 2H-benzotriazol-2-yl.
  • R 10 in formula XI particularly preferably denotes H.
  • the radicals R 5 , R 6 , R 8 and R 9 are preferably H and the substituent R 7 is preferably -OH, -OA, -A, - NH 2 , -NHA, -NA 2 , - NH- (CH 2 -CH 2 -O) n -H, -N [(CH 2 -CH 2 -O) n -H] 2 , - [NHA 2 ] X, - [NA 3 ] X, -SO 3 H, - [SO 3 ] X or 2H-benzotriazol-2-yl.
  • R 7 in formula XII particularly preferably denotes A.
  • compounds of the formula XII which are suitable as substituent R 7 are also the partial structure
  • the substructure IVe and IIIa or the substructure IVe or IIIa for the substituent B is very particularly preferred.
  • the preparation to be stabilized containing at least one
  • Ascorbic acid derivative of the formula I or preferred compounds of the formula I contains from 0.1 to 10% by weight of the stabilizing compound selected from the group consisting of diphenylacylate UV filters, dibenzoylmethane UV filters, phenolic antioxidants or mixtures thereof, based on the total weight of the preparation.
  • the stabilizing compound as previously selected, is added in 0.5 to 3% by weight, based on the total preparation.
  • the ratio of the at least one ascorbic acid derivative to the stabilizing compound of the selected group is 5: 1 to 1: 5, preferably 2: 1 to 1: 2.
  • the stabilized preparation according to the invention containing at least one ascorbic acid derivative of the formula I or a preferred compound of the formula I and at least one stabilizing compound of the selected group, as described above, may optionally contain further active ingredients or adjuvants.
  • Preferred further active ingredients which may be present in the preparation are, for example, further UV filters, vitamins, antioxidants, anti-aging active ingredients, anti-cellulite active substances, depigmentation active ingredients or customary skin-sparing or skin-care active ingredients.
  • 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.
  • both those from the group of titanium dioxides such as coated titanium dioxide (for example Eusolex ® T-2000, Eusolex ® T-AQUA, Eusolex ® T-AVO, Eusolex ® T-OLEO), zinc oxides (eg Sachtotec® ®), iron oxides and also Cerium oxides and / or zirconium oxides are preferred.
  • coated titanium dioxide for example Eusolex ® T-2000, Eusolex ® T-AQUA, Eusolex ® T-AVO, Eusolex ® T-OLEO
  • zinc oxides eg Sachtotec® ®
  • iron oxides and also Cerium oxides and / or zirconium oxides are preferred.
  • Zinc oxide possible, wherein the particle size of these pigments are greater than or equal to 200 nm, for example Hombitec® COS.
  • the preparations contain inorganic UV filters which are prepared by customary methods, for example in Cosmetics & Toiletries, February 1990, Vol. 105, pp. 53-64, were post-treated.
  • This can be an or may be selected from among the following aftertreatment components: amino acids, beeswax, fatty acids, fatty acid alcohols, anionic surfactants, 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 further particulate UV filters are:
  • 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,
  • Iron stearates aftertreatment such as e.g. the product "Microtitanium
  • micronised titanium dioxides with silicas, alumina and silicone aftertreatment e.g. the product "Microtitanium Dioxide MT 100 SAS", the company Tayca,
  • 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 T-X from DSM,
  • Alumina and stearic acid such as. the product UV titanium M160 from Kemira,
  • Aluminum and glycerin such as. the product UV-Titan of the company Kemira,
  • Aluminum and silicone oils e.g. the product UV-Titan M262 the
  • Polydimethylsiloxanes e.g. the product 70250 Cardre UF TiO2SI3 "from the company Cardre,
  • Polydimethylhydrogensiloxanes e.g. Microtitanium Dioxide USP Grade Hydrophobie "from Color Techniques .O
  • Untreated zinc oxides such.
  • Post-treated zinc oxides such as the following products: o "Zinc Oxide CS-5" from Toshibi (ZnO aftertreated with polymethylhydrogenosiloxanes) Nanogard Zinc Oxide FN from Nanophase Technologies o "SPD-Z1" from Shin-Etsu (ZnO aftertreated with a5
  • Cyclodimethylsiloxanes o "Escalol Z100" of the company ISP (aluminum oxide aftertreated ZnO dispersed in an ethylhexyl methoxycinnamate / PVP-hexadecenes / methicone copolymer mixture) 0 o "Fuji ZNO-SMS-10" from Fuji Pigment (ZnO aftertreated with silica and polymethylsilsquioxane) ; o Untreated cerium oxide micropigment, for example with the name "Colloidal Cerium Oxide” from Rhone Poulenc o Untreated and / or post-treated iron oxides with the name Nanogar from Arnaud.
  • mixtures of various metal oxides e.g. Titanium dioxide and cerium oxide with and without Nachbenmaschine be used, such. 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. the product UV titanium M261 from Kernira can be used in combination with the UV protection agent according to the invention.
  • These inorganic UV filters are typically used in an amount of from 0.1% to 25% by weight, preferably 2% by weight to 10%
  • the preparations may of course also contain one or more additional hydrophilic or lipophilic sunscreen filters which are in the UV-A range and / or UV-B range and (/ or IR and / or VIS range ( These additional filters may in particular be derived from cinnamic acid derivatives, salicylic acid derivatives, camphor derivatives, triazine derivatives, ⁇ -diphenylacrylate derivatives, p-aminobenzoic acid derivatives and polymeric filters and silicone filters described in the application WO-93/04665. Further examples of organic filters are given 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, e.g. 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. sold under the name "Dipsal” by the company Scher,
  • TEA salicylates e.g. B. under the name "Neo Heliopan TS” from the company Haarmann and Reimer.
  • ß.ß-diphenyl acrylates derivatives Octocrylene, z. B. under the name "Uvinul N539” from BASF, Etocrylene, z. B. under the name "Uvinul N35” from 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. operated under the
  • 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 Fa.
  • 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.
  • Triazines derivatives ethylhexyltriazone, e.g. B. under the name "Uvinul T150" from the Fa. BASF, Diethylhexylbutamidotriazone, z. B. under the name “Uvasorb HEB” from the company. Sigma 3V, 2,4,6-tris (diisobutyl 4'-aminobenzalmalonate) -s-triazines.
  • menthyl anthranilate e.g. B. under the name "Neo Heliopan MA” from the company Haarmann and Reimer.
  • Imidazole derivatives Ethylhexyldimethoxybenzylidenedioxoimidazoline propionate.
  • Benzalmalonate Derivatives Polyorganosiloxanes containing functional benzalmalonate groups, e.g. Polysilicone-15, e.g. 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.
  • organic UV-protective substances suitable for combination with the ascorbic acid derivatives of the formula I 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) benzoates, 4-methylbenzylidenecamphor, terephthalylidenedicamphorsulfonic acid, disodium phenyldibenzimidazoletetrasulfonate,
  • organic UV filters are usually incorporated in formulations in an amount of from 0.01% to 20% by weight, preferably 1% to 10% by weight.
  • organic UV filters are incorporated in formulations in an amount of from 0.01% by weight to 20% by weight, preferably from 0.5% by weight to 20% by weight.
  • antioxidants eg amino acids (eg glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazoles, (eg urocaninic acid) and their derivatives, peptides such as D, L- Carnosine, D-carnosine, L-carnosine and their derivatives (eg anserine), carotenoids, carotenes (eg ⁇ -carotene, ⁇ -carotene, lycopene) and their derivatives, chlorogenic acid and its derivatives, lipoic acid and derivatives thereof (eg dihydrolipoic acid), Aurothioglucose, propylthiouracil and other thiols (eg thioredoxin, glutathione, cyst
  • vitamin C and derivatives eg ascorbyl palmitate, magnesium ascorbyl phosphate, ascorbyl acetate
  • tocopherols and derivatives eg Vitamin E acetate
  • vitamin A and derivatives eg vitamin A palmitate
  • benzylic benzylic resin rutinic acid and
  • antioxidants are also suitable for use in the compositions or preparations according to the invention.
  • Known and commercially available mixtures are, for example, mixtures containing as active ingredients lecithin, L - (+) - ascorbyl palmitate and citric acid (eg (eg)
  • antioxidants are usually used with compounds of the formula I in such compositions in ratios in the range from 1000: 1 to 1: 1000, preferably in amounts of 100: 1 to 1: 100.
  • the preparations may contain vitamins as further ingredients.
  • vitamins and vitamin derivatives are selected from
  • Vitamin A Vitamin A, Vitamin A Propionate, Vitamin A Palmitate, Vitamin A Acetate,
  • vitamin B 2 nicotinic acid amide
  • vitamin C ascorbic acid
  • vitamin D ergocalciferol
  • vitamin E DL- ⁇ -tocopherol
  • tocopherol-E-acetate tocopherol hydrogen succinate
  • vitamin Ki esculin
  • Active ingredient Active ingredient
  • thiamin vitamin B-i
  • nicotinic acid niacin
  • pyridoxine pyridoxal
  • Vitamins are included Compounds of the formula I are usually used in ratios in the range from 1000: 1 to 1: 1000, preferably in amounts of from 100: 1 to 1: 100.
  • the preparations may contain fragrances as further ingredients, such as "S. Arctander, Perfume and Flavor Materials, Vol. I and II,
  • Particularly preferred anti-aging agents are pyrimidinecarboxylic acids,
  • Aryloxime, bioflavonoids, bioflavonoid-containing extracts, chromones or retinoids Aryloxime, bioflavonoids, bioflavonoid-containing extracts, chromones or retinoids.
  • Pyrimidinecarboxylic acids occur in halophilic microorganisms and play a role in the osmoregulation of these organisms (EA Galinski et al., Eur. J. Biochem., 149 (1985) page 135-139).
  • ectoine ((S) -1, 4,5,6-tetrahydro-2-methyl-4-pyrimidinecarboxylic acid) and hydroxyectoine ((S 1 S) -1,5,6-tetrahydro-5 are among the pyrimidinecarboxylic acids
  • the preparations contain such pyrimidinecarboxylic acids preferably in amounts of up to 15% by weight.
  • the pyrimidincarboxylic acids are preferably added in proportions of from 100: 1 to 1: 100 Compounds of the formula I are used, with ratios in the range from 1:10 to 10: 1 being particularly preferred.
  • 2-hydroxy-5-methyllaurophenone oxime which is also referred to as HMLO, LPO or F5
  • HMLO 2-hydroxy-5-methyllaurophenone oxime
  • LPO 2-hydroxy-5-methyllaurophenone oxime
  • F5 2-hydroxy-5-methyllaurophenone oxime
  • the preparations preferably contain from 0.01 to
  • Preparation contains 0.05 to 5% by weight of aryloxime.
  • bioflavonoids are, for example, troxerutin, tiliroside, ⁇ -glucosylrutin, rutin or isoquercetin, the said selection not being intended to be restrictive.
  • Bioflavonoidumble extracts are for example Gingko Biloba or Emblica.
  • Known anti-aging substances are also chromones, as described, for example, in EP 1508327 or retinoids, for example retinol (vitamin A), retinoic acid, retinaldehyde or else synthetically modified compounds of vitamin A.
  • retinoids for example retinol (vitamin A), retinoic acid, retinaldehyde or else synthetically modified compounds of vitamin A.
  • the described chromones and retinoids are also effective anti-cellulite agents.
  • Another well known anti-cellulite drug is caffeine.
  • the preparations may also contain one or more further skin-lightening active ingredients or synonymously depigmentation active ingredients.
  • 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 or rucinol.
  • Suitable preparations are for an external (synonymous to topical) application, for example as a cream, lotion, gel, or as a solution that can be sprayed on the skin.
  • Inventive ascorbic acid derivatives are particularly suitable for protecting dyed hair from UV-induced fading or UV-related color changes. This protective effect for hair dyes is especially given when treating the undyed hair with the preparation and only in the subsequent step performs the hair dyeing process.
  • the protective effect is particularly formed when pretreating the hair with alcoholic solutions containing at least one ascorbic acid derivative of the formula I.
  • the color effect can be obtained by so-called permanent colors under UV irradiation.
  • Oxidation dyes are formed, for example, from dye precursors, the so-called oxidation bases (developers) and the nuancers (couplers). Under oxidizing conditions (e.g., use of hydrogen peroxide), the dye precursors on the hair react with each other to form the dye, which is incorporated into the hair.
  • preparations to be stabilized e.g. called: solutions, suspensions, emulsions, PIT emulsions, pastes, ointments, gels, creams, lotions, powders, soaps, surfactant-containing cleaning preparations, oils, aerosols and sprays.
  • Other applications are e.g. Sticks, shampoos and shower baths. Any customary carrier substances, adjuvants and optionally further active ingredients can be added to the preparation.
  • Preferable excipients come from the group of preservatives, solubilizers, colorants, odor improvers.
  • Ointments, pastes, creams and gels may contain the usual excipients, for example 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 excipients, for example lactose, talc, silicic acid, aluminum hydroxide, calcium silicate and polyamide powder or mixtures of these substances.
  • Sprays may additionally contain the customary propellants, for example chlorofluorohydrocarbons, propane / butane or dimethyl ether.
  • Solutions and emulsions may contain the usual excipients such as solvents, solubilizers and emulsifiers, e.g. Water, ethanol, isopropanol, ethyl carbonate, ethyl acetate, benzyl alcohol, benzyl benzoate, propylene glycol, 1, 3-butyl glycol, dimethyl capramide, dimethyl isosorbide.
  • solvents e.g. Water, ethanol, isopropanol, ethyl carbonate, ethyl acetate, benzyl alcohol, benzyl benzoate, propylene glycol, 1, 3-butyl glycol, dimethyl capramide, dimethyl isosorbide.
  • the ascorbic acid derivatives according to the invention are converted into an application-appropriate formulation shortly before application.
  • the substance is dissolved in a carrier as described above and applied directly to skin or preferably to hair.
  • Particularly suitable carriers in this sense are Arlasolve DMI (dimethylisosorbide), butylene glycol, Finsolv® PG-22 (dipropylene glycol dibenzoate) or Pelemol® BIP (butylphthalimide isopropylphthalimide).
  • 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 polyoxyethylene sorbitan esters, microcrystalline cellulose, aluminum metahydroxide, bentonite, agar-agar and tragacanth or mixtures of these substances.
  • liquid diluents e.g. Water, ethanol or propylene glycol
  • suspending agents e.g. ethoxylated isostearyl alcohols, polyoxyethylene sorbitol esters and polyoxyethylene sorbitan esters, microcrystalline cellulose, aluminum metahydroxide, bentonite, agar-agar and tragacanth or mixtures of these substances.
  • 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 esters, fatty acid protein hydrolysates, isothionates, imidazolinium derivatives, methyl taurates, sarcosinates, fatty acid amide ether sulfates, alkyl amidobetaines, fatty alcohols, fatty acid glycerides, fatty acid diethanolamides, vegetable and synthetic oils, lanolin derivatives, ethoxylated glycerol - Contain fatty acid esters or mixtures of these substances.
  • excipients such as salts of fatty alcohol sulfates, fatty alcohol ether sulfates, sulfosuccinic acid esters, fatty acid protein hydrolysates, isothionates, imidazolinium derivatives, methyl taurates, sarcosinate
  • Facial and body oils may contain the usual excipients such as synthetic 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.
  • synthetic 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.
  • the preferred preparation forms according to the invention include in particular emulsions.
  • Emulsions of the invention are advantageous and contain z.
  • a preferred embodiment of the invention is an emulsion, which is present as a protective cream or milk and in addition to the compounds of formula I, for example fatty alcohols, fatty acids, fatty acid esters, especially triglycerides of fatty acids, lanolin, natural and synthetic oils or waxes and emulsifiers in the presence of
  • 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 fatty acids.
  • 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 thickening agent, 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.
  • the customary propellants such as alkanes, fluoroalkanes and chlorofluoroalkanes, are generally used.
  • the difference between the measured value for the extinction after irradiation (irradiation value) and the dark value serves as a measure of the light stability of the investigated preparation.
  • Solutions are prepared as described under the general procedure, namely a) 2% solution of DAB with butanediol b) solution of a) with 2% by weight of 1- (4-tert-butylphenyl) -3- (4-methoxyphenyl ) propane-1,3-dione (Avobenzone) c) solution of a) with 2% by weight of bis-ethylhexylhydroxydimethoxybenzyl malonate (RonaCare® AP) d) solution of a) with 3% by weight of 2-ethylhexyl-2 cyano-3,3-diphenylacrylate (octocrylene).
  • Compound has no self-absorption here.
  • the ascorbic acid derivatives of the formula I are pre-dissolved in isopropanol.
  • other or alternative alcohols and glycols are used, such as ethanol, glycerol or decyl alcohol.
  • This preliminary solution is added to the other components of phase A.
  • phase A is heated to 50-60 0 C.
  • phase B heats phase B to 60 ° C., then to disperse phase C with stirring.
  • Described pre-solution may alternatively be added to the final emulsion with stirring at room temperature. Since ascorbic acid derivatives of the formula I have oxidation-sensitive groups, it is advisable to formulate or produce under conditions which are as inert as possible.
  • Component B Aqua, hydrogen peroxide, cetearyl alcohol, PPG-38-buteth-37, petrolatum, laureth-2, sodium cetearyl sulfate, salicylic acid, disodium phosphate, phosphoric acid, etidronic acid.
  • DAB Diethylaminobenzoic acid ascorbic acid ester
  • Hair dyeing is preferably carried out in the following order: First, the hair is pretreated with component C. Subsequently, components A and B are mixed and applied to the hair. Another application variant is to integrate DAB directly into component A.

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Abstract

L'invention concerne l'utilisation d'un composé sélectionné dans le groupe comprenant des filtres UV de diphénylacrylate, des filtres UV de dibenzoylméthane, des antioxydants phénoliques ou des mélanges de ceux-ci, afin d'améliorer la stabilité aux UV d'une préparation contenant au moins un dérivé d'acide ascorbique en tant que filtre UV.
PCT/EP2009/007685 2008-11-26 2009-10-28 Procédé de photostabilisation de dérivés d'acide ascorbique WO2010060513A2 (fr)

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Cited By (2)

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Publication number Priority date Publication date Assignee Title
WO2010127756A1 (fr) * 2009-05-08 2010-11-11 Merck Patent Gmbh Ascorbate d'acide cinnamique
US11891496B2 (en) 2021-03-05 2024-02-06 H.B. Fuller Company Cyanoacrylate composition with hazardless stabilizer

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EP0664290A1 (fr) * 1994-01-20 1995-07-26 L'oreal Mono-et di-esters d'acide cinnamique ou de l'un de ses dérivés et de vitamine C, leur procédé de préparation et leur utilisation comme anti-oxydants dans des compositions cosmétiques, pharmaceutiques ou alimentaires
DE10013156A1 (de) * 2000-03-17 2001-09-20 Volkhard Jenning Verwendung eines Redoxsystems zur Stabilisierung von Wirk- und Hilfsstoffen in Präparaten zur äußerlichen Anwendung
US20050154054A1 (en) * 2004-01-13 2005-07-14 Skinceuticals, Inc. Stabilized ascorbic acid compositions and methods therefor
EP1591099A2 (fr) * 2004-04-28 2005-11-02 MERCK PATENT GmbH Procéde pour stabiliser des constituants de produits cosmétiques , d'hygiène personnelle et d'entretien ménager.
WO2007048645A2 (fr) * 2005-10-24 2007-05-03 Ciba Holding Inc. Protection d'agents oxydables
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EP0664290A1 (fr) * 1994-01-20 1995-07-26 L'oreal Mono-et di-esters d'acide cinnamique ou de l'un de ses dérivés et de vitamine C, leur procédé de préparation et leur utilisation comme anti-oxydants dans des compositions cosmétiques, pharmaceutiques ou alimentaires
DE10013156A1 (de) * 2000-03-17 2001-09-20 Volkhard Jenning Verwendung eines Redoxsystems zur Stabilisierung von Wirk- und Hilfsstoffen in Präparaten zur äußerlichen Anwendung
US20050154054A1 (en) * 2004-01-13 2005-07-14 Skinceuticals, Inc. Stabilized ascorbic acid compositions and methods therefor
EP1591099A2 (fr) * 2004-04-28 2005-11-02 MERCK PATENT GmbH Procéde pour stabiliser des constituants de produits cosmétiques , d'hygiène personnelle et d'entretien ménager.
WO2007048645A2 (fr) * 2005-10-24 2007-05-03 Ciba Holding Inc. Protection d'agents oxydables
WO2008017346A2 (fr) * 2006-08-11 2008-02-14 Merck Patent Gmbh Utilisation de dérivés d'acide ascorbique pour la fonctionnalisation de matrices

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LIN F-H ET AL: "Ferulic acid stabilizes a solution of vitamin C and E and doubles its photoprotection of skin" JOURNAL OF INVESTIGATIVE DERMATOLOGY, NATURE PUBLISHING GROUP, GB, Bd. 125, Nr. 4, 1. Oktober 2005 (2005-10-01), Seiten 826-832, XP008101490 ISSN: 0022-202X *
MURRAY J C ET AL: "A topical antioxidant solution containing vitamins C and E stabilized by ferulic acid provides protection for human skin against damage caused by ultraviolet irradiation" JOURNAL OF THE AMERICAN ACADEMY OF DERMATOLOGY, C.V. MOSBY, ST. LOUIS, MO, US, Bd. 59, Nr. 3, 1. September 2008 (2008-09-01), Seiten 418-425, XP024518729 ISSN: 0190-9622 [gefunden am 2008-07-07] *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010127756A1 (fr) * 2009-05-08 2010-11-11 Merck Patent Gmbh Ascorbate d'acide cinnamique
US8598228B2 (en) 2009-05-08 2013-12-03 Merck Patent Gmbh Cinnamic acid ascorbates
US11891496B2 (en) 2021-03-05 2024-02-06 H.B. Fuller Company Cyanoacrylate composition with hazardless stabilizer

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