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CN101095648A - Dibenzoylmethane sunscreens photostabilized with arylalkyl amide or ester compounds - Google Patents

Dibenzoylmethane sunscreens photostabilized with arylalkyl amide or ester compounds Download PDF

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Publication number
CN101095648A
CN101095648A CNA2007101388353A CN200710138835A CN101095648A CN 101095648 A CN101095648 A CN 101095648A CN A2007101388353 A CNA2007101388353 A CN A2007101388353A CN 200710138835 A CN200710138835 A CN 200710138835A CN 101095648 A CN101095648 A CN 101095648A
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compositions
acid
dibenzoyl methane
derivatives
title
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Inventor
D·坎多
K·卢塞特-勒芬尼尔
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LOreal SA
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LOreal SA
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/4906Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom
    • A61K8/4926Cosmetics 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
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/35Ketones, e.g. benzophenone
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/37Esters of carboxylic acids
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/04Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/52Stabilizers

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  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
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  • Cosmetics (AREA)

Abstract

The present invention relates to cosmetic sunscreen compositions comprising the combination of a dibenzoylmethane derivative and of a specific arylalkyl amide or ester compound of formula (I), (II) or (III), as defined below. This invention also relates to a process for photostabilizing, with regard to radiation, at least one dibenzoylmethane derivative by at least one specific arylalkyl amide or ester compound of formula (I), (II) or (III). The present invention also relates to the formulation of the said specific arylalkyl amide or ester compound of formula (I), (II) or (III) into a composition comprising, in a cosmetically acceptable carrier, at least one screening agent of the dibenzoylmethane derivative type for improving the effectiveness of the said composition with regard to UV-A rays.

Description

The cosmetic composition and the light that contain dibenzoylmethane derivative and arylalkyl amide or ester compounds are stablized the dibenzoylmethane derivative method
Technical field
The present invention relates to contain the cosmetic composition of dibenzoylmethane derivative and general formula (I), (II) or specific arylalkyl amide (III) or ester compounds combination, provide below general formula (I), (II) or being defined in (III).
The invention still further relates to by at least a general formula (I), (II) or specific arylalkyl amide (III) or ester compounds makes dibenzoylmethane derivative to the stable method of radiant light.
The invention still further relates to the purposes in the compositions of general formula (I), (II) or specific arylalkyl amide (III) or ester compounds sunscreen of acceptable carrier, at least a dibenzoylmethane derivative type on containing cosmetic, its target is to be used to improve the effect of described compositions for the UV-A ray.
Background technology
People know, the light radiation of wavelength between 280nm and 400nm can make people's epidermis overstrike, and particularly the light radiation (be referred to as uv b radiation) of wavelength between 280nm and 320nm causes skin erythema and burn, and these have adverse effect to tanned naturally formation.With the reason of improving looks, it is this tanned naturally to exist the demand that continues to control for these reasons, thus the color of control skin; Therefore this uv b radiation is covered in suggestion.
Also known, the wavelength that causes the skin overstrike 320 and 400nm between the UV-A ray can cause subsequently and harmful variation of skin especially be exposed under the sun-exposed situation continuously at allergic skin or skin.The UV-A ray especially causes the appearance of skin elasticity forfeiture and wrinkle, causes too early ageing.These radiation trigger the generation or this reaction of enhancing in some object of erythematous response, even may become the source of phototoxic reaction or optic hyperesthesia reaction.Therefore based on the reason of beauty treatment and cosmetic, for example keep the natural elasticity of skin for instance, people thirst for controlling the influence of UV-A ray to skin more.Therefore also wish to cover the UV-A radiation.
In order the radiating protection to skin and keratin substances antagonism UV to be provided, to use usually the sunscreen composition that contains the organic sunscreen agent of working and working in the UV-B scope in the UV-A scope.These sunscreen great majority are fat-soluble.
Therein, present useful especially UV-A sunscreen family comprises dibenzoylmethane derivative, the 4-tert-butyl group-4 '-methoxy dibenzoyl methylmethane particularly, and this is because it shows very high intrinsic absorbability (intrinsic absorbency).These dibenzoylmethane derivatives itself are known as the product in the effect of UV-A scope sunscreen, particularly are described in french patent application FR-A-2 326 405 and FR-A-2 440 933 and European patent application EP-A-0 114 607; In addition, the 4-tert-butyl group-4 '-methoxy dibenzoyl methane is provided by DSM Nutritional Products with trade name " Parsol 1789 " now.
Unfortunately, confirmed that the dibenzoylmethane derivative product is responsive relatively for ultraviolet radiation (particularly UV-A radiation), promptly more particularly, they are in afterwards the bad trend that shows rapid decomposition on more or less.Therefore; this dibenzoylmethane derivative lacks photochemical stability basically in the face of ultraviolet radiation (their original expections can meet with) time; cause to guarantee the lasting protection between long-time in the sun exposure period, so that user must be by well-regulated and reuse near interval and to obtain skin to the radiating effective protection of UV.
Known in EP 717 982, amide compound has the light stablizing effect for dibenzoylmethane derivative, amide oil particularly, and the compound N of following structure for example, N-diethyl-3-methyl benzamide:
Figure A20071013883500111
Or the n-butyl of following formula and N-acetylamino ethyl propionate:
In order to address this problem, in patent application EP 1 618 870, used aryl alkyl benzoate derivatives, particularly 2-ethylphenyl benzoate, for example ISP is with the commodity of title X-Tend 226  sale., the light maintenance level of dibenzoylmethane derivative after the UV radioactive exposure is also insufficient.
Summary of the invention
In point of fact, applicant's company finds now unexpectedly, by with the making up with dibenzoylmethane derivative above-mentioned of effective dose at general formula (I), (II) or the special arylalkyl amide (III) described in detail after a while or ester compounds, can essence and photochemical stability (or light stability) and the effectiveness in the UV-A scope of further improving these identical diphenylmethane derivatives significantly.The compositions that contains this combination also causes using more uniform distribution of back UV sunscreen.
These find to form basis of the present invention.
Therefore,, provide and contain the compositions that acceptable carrier and the sun-proof system of at least a UV are gone up in beauty treatment, it is characterized in that containing according to a theme of the present invention:
(a) the UV-A sunscreen of at least a dibenzoylmethane derivative type and
(b) at least a general formula (I), (II) or arylalkyl amide (III) or ester compounds, it is defined in hereinafter and provides.
Another theme of the present invention also relates to the UV-A sunscreen that the improves at least a dibenzoylmethane derivative type method for the radiating chemical stability of UV, and this method is described dibenzoylmethane derivative and at least a general formula (I), (II) or specific arylalkyl amide (III) or ester compounds (it is defined in the back and provides) combination.
At last, another theme of the present invention is general formula (I), (II) or specific arylalkyl amide (III) or the application of ester compounds in compositions, wherein said composition contains at least a dibenzoylmethane derivative in the acceptable carrier in beauty treatment, and its target is to improve the effectiveness of described compositions antagonism UV-A ray.
By reading following detailed description, further feature of the present invention, aspect and advantage will be self-evident.
Term " it is acceptable to improve looks " can be understood as compatible with skin and/or its body surface growth-gen, show pleasant color, pleasant taste and pleasant sensation, and can not cause unacceptable discomfort (painful, tight, erythema), these discomforts might cause consumer not use this compositions.
In dibenzoylmethane derivative, that can mention especially enumerates without limitation:
-2-methyldiphenyl formyl methane,
-4-methyldiphenyl formyl methane,
-4-isopropyl diphenyl formyl methane,
-4-tert-butyl group dibenzoyl methane
-2,4-dimethyl dibenzoyl methane,
-2,5-dimethyl dibenzoyl methane,
-4,4 '-diisopropyl dibenzoyl methane,
-4,4 '-dimethoxy dibenzoyl methane,
-4-the tert-butyl group-4 '-methoxy dibenzoyl methane,
-2-methyl-5-isopropyl-4 '-methoxy dibenzoyl methane,
-2-methyl-5-the tert-butyl group-4 '-methoxy dibenzoyl methane,
-2,4-dimethyl-4 '-methoxy dibenzoyl methane,
-2, the 6-dimethyl-4-tert-butyl group-4 '-methoxy dibenzoyl methane.
In the mentioned in the above dibenzoylmethane derivative, what use especially is 4-isopropyl diphenyl formyl methane, is sold with title " Eusolex 8020 " by Merck, meets following general formula:
Figure A20071013883500131
What preferably use is the 4-tert-butyl group-4 '-methoxy dibenzoyl methane or butyl methoxydibenzoylmethise, is sold with trade name " Parsol 1789 " by DSM Nutritional Products; Corresponding general formula below this sunscreen meets:
Figure A20071013883500132
The amount of one or more derivants in compositions of the present invention of dibenzoyl methane with respect to the gross weight of compositions preferably in 0.01 to 10% weight, more preferably change in the scope of 0.1 to 6% weight.
Be selected from according to arylalkyl amide of the present invention or ester and meet following general formula (I), (II) and (III) those:
Figure A20071013883500141
Wherein:
-R 1Be straight or branched C 1-C 4Alkyl group,
-a is 0-2,
-m is 0-4,
-b is 1 or 2,
-R 2Be H, straight or branched C 1-C 20Alkyl or Acetyl Groups,
-R 3Be H or methyl independently,
-p is 0-4,
-q is 0-3,
-X is O, NH or NR 5,
-Y is CH or N,
-R 4And R 5Be straight or branched C 1-C 20Alkyl group,
Condition below general formula (III) satisfies: if Y=CH, R 3=H, m=0, n=2, a is not 0 and R so 1It is not methyl.
Superincumbent general formula (I), (II) and (III) in alkyl group can mention especially methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, 2-ethylhexyl, dodecyl or hexadecyl group arranged.
In the amide compound of general formula (I) useful especially be below (a) to the product of (k):
Figure A20071013883500151
Figure A20071013883500161
In the amide compound of general formula (II) useful especially be below (l) to the product of (r):
Figure A20071013883500162
Figure A20071013883500171
In the aryl alkyl ester compounds of general formula (III) useful especially be below (s) to the product of (x):
Figure A20071013883500172
Figure A20071013883500181
The alcohol that the ester compounds of general formula (III) can pass through the acid derivative of general formula (2) and general formula (3) is at acid catalyst for example in the presence of the concentrated sulphuric acid, for example reacts in the toluene at solvent medium to prepare, and carries out according to following flow chart:
Figure A20071013883500182
Radicals R wherein 1, R 2, R 3, a, b, m and p have identical meanings recited above.
The ester amine that the amide compound of general formula (I) can pass through the acid chloride of general formula (3) and general formula (4) is in HCl scavenger (scavenger) for example in the presence of the triethylamine, for example reacts in the acetonitrile at solvent medium to prepare, and carries out according to following flow chart:
Figure A20071013883500183
Radicals R wherein 1, R 2, R 3, a, m and p have identical meanings recited above.
The alcohol that the amide compound of general formula (II) can pass through the acid derivative of general formula (5) and general formula (6) is at acid catalyst for example in the presence of the concentrated sulphuric acid, for example reacts in the toluene at solvent medium to prepare, and carries out according to following flow chart:
Figure A20071013883500184
Described one or more arylalkyl amides or the amount of ester compounds in compositions, in composition total weight, general content is between 0.01% to 20% weight, and preferred content is between 0.1% to 10% weight.
According to the present invention, general formula (I), (II) and chemical compound (III) use to obtain the significant and important improvement of light stability of dibenzoylmethane derivative in given compositions with enough amounts.Employed minimum light stabilizer can change according to the amount of initial dibenzoyl methane in compositions with for the characteristic of the selected beauty treatment acceptable carrier of compositions.It can use the test of general measure light stability to measure without difficulty.
In addition, can be included in according to compositions of the present invention and to have active other additional organic or inorganic UV sunscreen in UV-A and/or the UV-B zone, described sunscreen can be water miscible or fat-soluble or be insoluble in the normally used beauty treatment solvent.
Other organic uv filter especially is selected from: the o-aminobenzoa class; Cinnamic acid derivative; Salicyclic acid derivatives; Camphor derivatives; Benzophenone derivates; β, β-diphenylacrylate; Pyrrolotriazine derivatives; Benzotriazole derivatives; Toluenyl malonic ester derivant, particularly those that in patent US 5 624 663, quote; Benzimidizole derivatives; Imidazolidine derivatives; Two benzoxazolyl groups (bis-benzoazolyl) derivant, for example disclosed in patent EP 669 323 and US2 463 264; Para-amino benzoic acid (PABA) derivant; Di-2-ethylhexylphosphine oxide (hydroxy-phenyl benzotriazole) derivant is as disclosed in application US 5 237 071, US 5 166355, GB 2 303 549, DE 197 26 184 and EP 893 119; The benzoxazol derivant is as disclosed in patent application EP 0 832 642, EP 1 027 883, EP 1 300 137 and DE 10162844; Sun-proof polymer and sun-proof silicone, as especially the application WO 93/04665 in those disclosed; By two polymer of alpha-alkyl phenylethylene generation, as those disclosed in patent application DE 19855649; 4,4-diaryl base butadiene is as disclosed in application EP 0 967 200, DE 19746654, DE 19755649, EP-A-1008 586, EP 1 133 980 and EP 133 981; With their mixture.
As the example of other organic uv filter, can mention following those that represent with their INCI title:
The para-amino benzoic acid derivant:
PABA,
Ethyl PABA,
Ethyl dihydroxypropyl PABA,
The ethylhexyl dimethyl PABA is especially sold with title " Escalol 507 " by ISP,
Glyceryl PABA,
PEG-25 PABA is sold with title " Uvinul P25 " by BASF,
Salicyclic acid derivatives:
Heliophan is sold with title " Eusolex HMS " by Rona/EM Industries,
Ethylhexyl salicylate is sold with title " Neo Heliopan OS " by Haarmann and Reimer,
Dipropylene glycol salicylate is sold with title " Dipsal " by Scher,
The TEA salicylate is sold with title " Neo Heliopan TS " by Haarmann and Reimer,
Cinnamic acid derivative:
Ethylhexyl methoxy cinnamate is especially sold with trade name " Parsol MCX " by Hoffmann-LaRoche,
The methoxy cinnamic acid isopropyl ester,
The methoxy cinnamic acid isopentyl ester is sold with trade name " Neo Heliopan E1000 " by Haarmann and Reimer,
Cinoxate,
The DEA Methoxycinnamate,
-methyl cinnamic acid diisopropyl ester,
Thylhexoic acid dimethoxy-cinnamic acid glyceride,
β, β-diphenylacrylate:
Octocrylene is especially sold with trade name " Uvinul N539 " by BASF,
Etocryene is especially sold with trade name " Uvinul N35 " by BASF,
Benzophenone derivates:
Benzophenone-1 is sold with trade name " Uvinul 400 " by BASF,
Benzophenone-2 is sold with trade name " Uvinul D50 " by BASF,
Benzophenone-3 or oxybenzone are especially sold with trade name " Uvinul M40 " by BASF,
Benzophenone-4 is sold with trade name " Uvinul MS40 " by BASF,
Benzophenone-5,
Benzophenone-6 is sold with trade name " Helisorb " by Norquay,
Benzophenone-8 is sold with trade name " Spectra-Sorb UV-24 " by American Cyanamid,
Benzophenone 9 is sold with trade name " Uvinul DS-49 " by BASF,
Benzophenone-12,
The just own ester of 2-(4-lignocaine-2-hydroxy benzoyl) benzoic acid,
The benzylidene camphor derivant:
The 3-benzylidene camphor is produced with title " Mexoryl SD " by Chimex,
4 methyl benzylidene camphor is sold with title " Eusolex 6300 " by Merck,
Benzylidene camphor sulfonic acid is produced with title " Mexoryl SL " by Chimex,
Camphora benzalkonium sulphuric acid dimethyl esters is produced with title " Mexoryl SO " by Chimex,
The Terephthalidene Dicamphor Sulfonic Acid is produced with title " Mexoryl SX " by Chimex,
Polyacrylamide amino methyl benzylidene camphor is produced with title " Mexoryl SW " by Chimex,
Benzimidizole derivatives:
Phenylbenzimidazolesulfonic acid is especially sold with trade name " Eusolex 232 " by Merck,
Phenyl bisbenzimidazole tetrasulfonic acid disodium is sold with title " Neo HeliopanAP " by Haarmann and Reimer,
The phenyl benzotriazole derivatives:
The drometrizole trisiloxanes is sold with title " Silatrizole " by Rhodia Chimie,
Di-2-ethylhexylphosphine oxide-benzotriazole base tetramethyl butyl phenol, sell with trade name " Mixxim BB/100 " with solid form by Fairmount Chemical, or sell with trade name " Tinosorb M " with the micropowder form in the aqueous dispersion by Ciba Specialty Chemicals
Pyrrolotriazine derivatives:
Two-ethylhexyl oxy phenol anisyl triazine, sell with trade name " Tinosorb S " by Ciba-Geigy,
The ethylhexyl triazinone is especially sold with trade name " Uvinul T1 50 " by BASF,
Diethylhexyl butyramide triazinone is sold with trade name " Uvasorb HEB " by Sigma 3V,
2,4,6-three (4 '-amino benzal malonic acid two peopentyl esters)-s-triazine,
2,4,6-three (4 '-amino benzal malonic acid diisobutyl ester)-s-triazine,
Symmetric triazine sunscreen is at patent US 6 225 467, application WO2004/085412 (referring to chemical compound 6 and 9) or document " Symmetrical Triazine Derivatives ", IP.COM Journal, IP.COMINC, WEST HENRIETTA, NY, on the books among the US (on JIUYUE 20th, 2004), particularly 2,4,6-three (xenyl)-1,3,5-triazine (especially 2,4,6-three (xenyl-4-yl)-1,3, the 5-triazine) and 2,4,6-three (terphenyl)-1,3, the 5-triazine, they also are absorbed into patent application WO 06/035000, WO 06/034982, WO 06/034991, WO 06/035007, among WO 2006/034992 and the WO 2006/034985.
Anthranilic acid derivative:
Antisolaire is sold with trade name " Neo HeliopanMA " by Haarmann and Reimer,
Imidazolidine derivatives:
Dimethoxybenzylidenegroup group dioxo imidazoline propanoic acid Octyl Nitrite,
The benzal malonic acid derivant:
4 '-methoxyl group benzal malonic acid, two peopentyl esters,
The polysiloxane that comprises benzal malonic acid functional group, for example Polysilicone-15 is sold with trade name " Parsol SLX " by Hoffmann-LaRoche,
4,4-diaryl butadiene derivatives:
1,1-dicarboxyl (2,2 '-dimethyl propyl)-4, the 4-diphenyl diethylene,
Benzene  Zole derivatives:
2, two [5-1 (dimethyl propyl) benzoxazol-2-base-(4-phenyl) imino group]-6-(2-ethylhexyl) imino group-1,3,5-triazines of 4-are sold with title " Uvasorb K2A " by Sigma 3V
And their mixture.
Preferred additional organic bright protective agent is selected from:
Ethylhexyl methoxy cinnamate,
Heliophan,
Ethylhexyl salicylate,
Octocrylene,
Phenylbenzimidazolesulfonic acid,
Benzophenone-3,
Benzophenone-4,
Benzophenone-5,
The just own ester of 2-(4-lignocaine-2-hydroxy benzoyl) benzoic acid,
4 methyl benzylidene camphor,
The Terephthalidene Dicamphor Sulfonic Acid,
Phenyl bisbenzimidazole tetrasulfonic acid disodium,
Methylene dibenzo triazolyl tetramethyl butyl phenol,
The ethylhexyl triazinone,
It is two-ethylhexyl oxy phenol anisyl triazine,
Diethylhexyl butyrylamino triazinone,
2,4,6-three (4 '-amino benzal malonic acid two peopentyl esters)-s-triazine,
2,4,6-three (4 '-amino benzal malonic acid diisobutyl ester)-s-triazine,
2,4,6-three (xenyl-4-yl)-1,3,5-triazines,
2,4,6-three (terphenyl)-1,3,5-triazines,
The drometrizole trisiloxanes,
Polysilicone-15,
4 '-methoxyl group benzal malonic acid, two peopentyl esters,
1,1-dicarboxyl (2,2 '-dimethyl propyl)-4, the 4-diphenyl diethylene,
2, two [5-1 (dimethyl propyl) benzoxazol-2-base-(4-phenyl) imino group]-6 (2-ethylhexyl) imino group-1,3,5-triazines of 4-,
And their mixture.
Inorganic The UV sunscreenBe selected from the pigment of the metal-oxide formation that can coat or can not coat, the average-size of primary particle: generally at 5nm between the 100nm, preferably at 10nm between the 50nm, the pigment that is formed by the titanium dioxide crystal of rutile and/or acute cone stone form (amorphous or), ferrum oxide, zinc oxide or cerium oxide for example, they itself all are known UV photoprotective agents.
Pigment can coat or can not coat.
To be those carried out the pigment of chemistry, electronics, mechanochemistry and/or mechanical treatment with chemical compound to the pigment that coats on one or more surfaces, and wherein chemical compound is for example at Cosmetics ﹠amp; Toiletries, February nineteen ninety, Vol.105, description is arranged, as sodium, potassium, zinc, ferrum or aluminum salt, metal alkoxide (titanium or aluminium-alcohol salt), polyethylene, silicone, protein (collagen, elastin laminin), alkanolamine, silicon oxide, metal-oxide or the six inclined to one side sodium sulfate of aminoacid, Cera Flava, fatty acid, aliphatic alcohol, anion surfactant, lecithin, fatty acid among the pp.53-64.
In known method, silicone is organosilicon polymer or the oligomer that contains straight chain or ring-type and side chain or cross-linked structure, has variable molecular weight, obtain also to constitute by multiple formant basically by suitable functional silane polymerization or polycondensation, wherein silicon atom is connected to each other (siloxane bond) by oxygen atom, and the optional alkyl that replaces directly is connected with described silicon atom by carbon atom.
Term " silicone " also comprises for it and prepares necessary siloxanes, particularly alkylsiloxane.
The silicone that is suitable for coating pigment of the present invention is preferably selected from alkyl silane, polydialkysiloxane and poly-alkyl hydride siloxane.Also more preferably silicone is selected from octyl trimethyl silane, polydimethylsiloxane and poly-hydrogenated methyl siloxanes.
Certainly, the pigment that is formed by metal-oxide is handled with other surface reagent, particularly cerium oxide, Alumina, tripoli, aluminium compound, silicon compound or their mixture before it uses by silicone-treated.
The titanium dioxide that the pigment that coats more particularly coats with following material:
-tripoli, as from the product " Sunveil " of Ikeda with from the product " Eusolex T-AVO " of Merck,
-tripoli and ferrum oxide, as product " Sunveil F " from Ikeda,
-tripoli and Alumina, as product " Microtitanium Dioxide MT 500 SA " and " Microtitanium Dioxide MT 100 SA " from Tayca, from Tioxide " Tioveil " with from " the Mirasun TiW 60 " of Rhodia,
-Alumina, as from the product " Tipaque TTO-55 (B) " of Ishihara and " Tipaque TTO-55 (A) " with from " UVT 14/4 " of Kemira,
-Alumina and aluminium stearate, as from the product " Microtitanium Dioxide MT 100TV, MT 100 TX, MT 100 Z or MT-01 " of Tayca with from product " Solaveil CT-10W ", " the Solaveil CT 100 " and " Solaveil CT 200 " of Uniqema
-tripoli, Alumina and alginic acid, as product " MT-100 AQ " from Tayca,
-Alumina and Aluminum trilaurate, as product " Microtitanium Dioxide MT 100 S " from Tayca,
-ferrum oxide and ferric stearate, as product " Microtitanium Dioxide MT 100F " from Tayca,
-zinc oxide and zinc stearate, as product " BR351 " from Tayca,
-tripoli and Alumina, and use silicone-treated, as product " Microtitanium DioxideMT 600 SAS ", " Microtitanium Dioxide MT 500 SAS " or " Microtitanium DioxideMT 100 SAS " from Tayca,
-tripoli, Alumina and aluminium stearate, and use silicone-treated, as product " STT-30-DS " from Titan Kogyo,
-tripoli, and use silicone-treated, as from the product " UV-Titan X 195 " of Kemira or from the product SMT-100 WRS of Tayca,
-Alumina, and use silicone-treated, as from the product " Tipaque TTO-55 (S) " of Ishihara or from " the UV Titan M 262 " of Kemira,
-triethanolamine, as product " STT-65-S " from Titan Kogyo,
-stearic acid, as product " Tipaque TTO-55 (C) " from Ishihara,
-sodium hexameta phosphate is as the product " Microtitanium Dioxide MT 150 W " from Tayca.
Other TiO 2 pigment with silicone-treated is preferably used handle and the TiO of average-size between 25 to 40nm individual particle of octyl group trimethyl silane 2, as being sold with trade name " T 805 " by Degussa Silices, that handle and average-size individual particle is the TiO of 21nm with polydimethylsiloxane 2, as being sold with trade name " 70250 Cardre UF TiO2S13 " by Cardre, processing and average-size individual particle is acute cone stone/rutile TiO of 25nm with the poly dimethyl hydride siloxane 2, as selling with trade name " Microtitanium Dioxide USP Grade Hydrophobic " by Color Techniques.
Not the TiO 2 pigment of Bao Fuing for for example by Tayca with trade name " Microtitanium Dioxide MT500 B " or " Microtitanium Dioxide MT 600 B ", by Degussa with title " P 25 ", by Wacker with title " Oxyde de titane transparent PW ", by Miyoshi Kasei with title " UFTR ", sell with title " Tioveil AQ " with title " ITS " with by Tioxide by Tomen.
The zinc oxide pigment of Bao Fuing is not for for example:
-sell with title " Z-cote " by Sunsmart those;
-sell with title " Nanox " by Elementis those;
-sell with title " Nanogard WCD 2025 " by Nanophase Technologies those.
The zinc oxide pigment that coats is for for example:
-by Sunsmart those (ZnO that polydimethylsiloxane coats) with title " Z-cote HP1 " sale;
-by Toshibi those (ZnO that poly-hydrogenated methyl siloxanes coats) with title " Oxide zinc CS-5 " sale;
-sell with title " Nanogard Zinc Oxide FN " by Nanophase Technologies those (as at Finsolv TN, C 12-C 1540% dispersion in the alkyl benzoate);
-those (dispersion in the polydimethylsiloxane/cyclopolymethyl siloxane of ethoxylation contains the nano zine oxide of 30% or 50% usefulness tripoli and poly-hydrogenated methyl siloxanes coating) of selling with title " Datiopersion Zn-30 " and " Datiopersion Zn-50 " by Daito;
-those (, being the dispersion form in D5) of selling with title " NFD Ultrafine ZnO " by Daikin with the phosphate of perfluoroalkyl with based on the ZnO that the copolymer of perfluor alkyl ethide coats;
-by Shin-Etsu those (being dispersed in the ZnO that the polysiloxane grafted acrylate copolymer of usefulness in the ring dimethyl siloxane coats) with title " SPD-Z1 " sale;
-by ISP those (being dispersed in the ZnO that the Alumina in ethylhexyl methoxy cinnamate/PVP-hexadecylene copolymer/dimethyl polysiloxane mixture was handled) with title " Escalol Z100 " sale;
-by Fuji Pigment those (ZnO that tripoli and poly methyl silsesquioxane (polymethylsilsesquioxane) coat) with title " Fuji ZnO-SMS-10 " sale;
-sell with title " Nanox Gel TN " by Elementis those (55% ZnO is dispersed in the C of the hard ester acid of hydroxyl condensation polymer 12-C 15In the alkyl benzoate).
The cerium oxide pigment of Bao Fuing is not for example sold with title " Colloidal CeriumOxide " by Rh  ne-Poulenc.
The iron oxide pigment of Bao Fuing not, for example by Arnaud with title " Nanogard WCD 2002 (FE45B) ", " Nanogard Iron FE 45 BL AQ ", " Nanogard Iron FE 45 R AQ " or " Nanogard WCD 2006 (FE 45R) ", or sell with title " TY-220 " by Mitsubishi.
The iron oxide pigment that coats, for example by Arnaud with title " Nanogard WCD 2008 (FE 45BFN) ", " Nanogard WCD 2009 (FE 45B 556) ", " Nanogard FE 45 BL 345 " or " Nanogard FE 45 BL ", or sell with title " Oxyde de fer transparent " by BASF.
Also can mention mixture, the especially titanium oxide of metal-oxide and the mixture of cerium oxide, the mixture of the cerium oxide that titanium oxide that heavy tripoli coats and tripoli coat such as comprise, sell with title " Sunveil A " by Ikeda, and titanium dioxide and TwoThe mixture of zinc oxide coats with Alumina, tripoli and silicone, the product " M 261 " sold of Kemia for example, or coat with Alumina, tripoli and glycerol, for example product " M 211 " of Kemira sale.
According to the present invention, there is ratio in additional bright protective agent in compositions, and with respect to composition total weight, scope is 0.01 to 20% weight usually, and preferable range is in 0.1 to 10% weight.
Can also comprise the reagent (self-tanning agent) of the artificial tanned and/or browning that is used for skin according to compositions of the present invention, and dihydroxy acetone (DHA) particularly.The amount of its existence is 0.1 to 10% weight with respect to the preferable range of composition total weight.
Can comprise beauty treatment adjuvant commonly used in addition according to waterborne compositions of the present invention, it especially is selected from: lipoid material, organic solvent, ion or nonionic and hydrophilic or lipophilic thickening agent, softening agent, wetting agent, opacifier, stabilizing agent, emollient, silicone, defoamer, spice, antiseptic, anion, cation, nonionic, amphion or amphoteric surfactant, active component, filler, polymer, propellant, alkalization or acidulant or anyly be generally used for improving looks and/or other component of dermatological field.
Lipoid material can be made up of oil or wax (being different from nonpolar wax defined above) or their mixture.Term " oil " is interpreted as and is the chemical compound of liquid at ambient temperature.Term " wax " is interpreted as at ambient temperature to solid or is essentially solid and its fusing point generally is higher than 35 ℃ chemical compound.
As oils, can mention mineral oils (liquid alkanes); Plant oil (Semen pruni armeniacae oil, macadimia nut oil, Black Currant Seed Oil or simmondsia oil); Synthetic oils, as perhydro-squalene, aliphatic alcohol, fatty acid amide (as the isopropyl Hamposyl L ester of selling with title " Eldew SL-205 " by Ajinomoto), fatty acid or ester class (as the benzoic acid C that sells with trade name " Finsolv TN " or " Witconol TN " by Witco 12-C 15Arrcostab, octyl palmitate, lanoceric acid isopropyl ester (isopropyl lanolate) or triglyceride, comprise those of capric acid/sad or two caprylyl carbonic esters (dicaprylyl carbonate), sell with title " Cetiol CC " by Cognis), or the fatty esters and the ethers of oxyethylation or oxypropylation; Silicone oil (cyclomethicone, polydimethylsiloxane class or PDMS); Fluoridize oils or TPO.
What can mention as waxy compound is Brazil wax, Cera Flava, castor oil hydrogenated, Tissuemat E and polymethylene wax, is for example sold with title Cirebelle 303 by Sasol.
What can mention in organic solvent is lower alcohol and polyhydric alcohol.The latter can be selected from two pure and mild glycol ethers, for example ethylene glycol, propylene glycol, butanediol, dipropylene glycol or diethylene glycol.
What can mention as the hydrophilic thickening agent is carboxy vinyl polymer, for example carbopol (Carbopol) (carbomer) and Pemulens (acrylate/C 10-C 30-alkyl acrylate copolymer); Polyacrylamide, for example for instance by Seppic polyacrylamide/C13-14 isoparaffin/Laureth 7) or Simulgel 600 (CTFA title: the cross-linked copolymer of Chu Shouing acrylamide/sodium acryloyldimethyl taurate copolymers/2-Methylpentadecane/polysorbate80) with title Sepigel 305 (CTFA title:; Randomly crosslinked and/or the neutral polymer and the copolymer of 2-acrylamido-2-methyl propane sulfonic acid, for example by Hoechst with trade name " Hostacerin AMPS " (CTFA title: polyacrylamide dimethyl taurine ammonium) or by Seppic with Simulgel 800 (CTFA title: poly-(the 2-acrylamido-2-methyl propane sulfonic acid) of polyacrylamide dimethyl sodium taurocholate/anhydrous sorbitol polyoxyethylene (80) oleic acid ester/sorbitan monooleate) selling; The copolymer of 2-propionamido-2-methyl propane sulfonic acid and hydroxy ethyl methacrylate is for example sold with Simulgel NS and Sepinov EMT 10 by Seppic; Cellulose derivative, for example hydroxyethyl-cellulose; Polysaccharide and especially natural gum, for example xanthan gum; And their mixture.
What can mention as the lipotropy thickening agent is synthetic polymer, for example poly-(the C that is sold with title " IntelimerIPA 13-1 " and " Intelimer IPA 13-6 " by Landec 10-C 30Alkyl acrylate) or modified clay, for example Strese Hofmann's hectorite. and its derivant are as the product of selling with title Bentone.
That can mention in active component has:
-vitamin (A, C, E, K, PP etc.) and their derivant or precursor are separately or with the form of mixture;
-be used for to resistant to pollution reagent and/or to the reagent of free radical resisting;
-the depigmentation and/or chromogen reagent;
-anti-gfycation agent;
-soothing agent;
-NO-synthetase inhibitors;
-stimulate corium or epidermis macromole to synthesize and/or prevent the reagent of their decomposition;
The reagent of-stimulation fibroblast proliferation;
The outgrowth reagent of-stimulation cutin shaped cell;
-muscle relaxant;
-tensioning agent;
-control oil preparation (matifying agent; )
-keratolytic agent;
-decorticating agent;
-wetting agent;
-antiinflammatory;
-act on the metabolic reagent of cellular energy;
-anthelmintic;
-P material or CRGP substance antagonist;
The reagent of-antagonism alopecia and/or hair restoration;
-anti-wrinkle agent.
Certainly, those skilled in the art should note selecting above-mentioned additional optional compound of mentioning and/or their amount, make relevant with compositions of the present invention basically favourable character, not or basically be not subjected to above-mentioned one or more and consider the adverse effect of adding.
These compositionss of the present invention can be prepared according to technology well known to those skilled in the art.These compositionss specifically can be single or compound emulsion (oil/water, water/oil, oil/water/oil or water/oil/water), for example cream or Emulsion or cream gel; The aqueous gel form; Lotion form.They can be randomly with aerosol packaging, or provides with the form of foam or spray.
Preferably, be oil-in-water or water-in-oil emulsion form according to compositions of the present invention.
Described emulsion contains at least a emulsifying agent, is selected from both sexes, anion, cation or nonionic emulsifier, and is independent or use as mixture.Suitably select emulsifying agent according to the emulsion that will obtain (Water-In-Oil or O/w emulsion).
Emulsion also can contain the stabilizing agent of other type, for example filler, gelation or thickening polymer for instance.
Can mention as the emulsifying surfactant that can be used for preparing water-in-oil emulsion, as sorbitan, glycerol or sugared Arrcostab or ether; Silicone surfactant, as dimethicone copolyol, for example the cyclohexyl methyl siloxanes of selling with title " DC 5225 C " by DowCorning and the mixture of dimethicone copolyol, and alkyl dimethicone copolyol, for example by the lauryl dimethicone copolyol of Dow Corning with title " Dow Corning 5200 Formulation Aid " sale, the cetyl dimethicone copolyol, as the product of selling with title Abil EM 90R by Goldschmidt, and by the cetyl dimethicone copolyol of Goldschmidt with title Abil WE O9 sale, the mixture of polyglycereol (4mol) isostearate and lauric acid hexyl ester.Can also be to wherein adding one or more coemulsifiers, it can advantageously be selected from the polyhydric alcohol Arrcostab.
As what the polyhydric alcohol Arrcostab can be mentioned especially macrogol ester arranged, PEG-30 dimerization hydroxy stearic acid ester for example is as the product of being sold with title Arlacel P135 by ICI.
Ester as glycerol and/or sorbitan can be mentioned for example polyglyceryl-isostearate, as the product of being sold with title Isolan GI 34 by Goldschmidt; The sorbitan isostearate is as the product of being sold with title Arlacel 987 by ICI; Glycerol sorbitan isostearate, as the product of selling with title Arlacel986 by ICI, and their mixture.
The example that can mention as emulsifying agent in O/w emulsion has nonionic emulsifier, for example the oxyalkylene hydrocarbonylation of fatty acid and glycerol (more preferably polyoxyethyleneization) ester; The oxyalkylene hydrocarbonylation ester of fatty acid and sorbitan; Oxyalkylene hydrocarbonylation (oxyethylation and/or oxypropylation) fatty acid ester, for example PEG-100 stearate/tristerin mixture of selling with title Arlacel 1 65 by ICI; Oxyalkylene hydrocarbonylation (oxyethylation and/or oxypropylation) fatty alcohol ether; Sugar ester, for example sucrose stearate; The ether of aliphatic alcohol and sugar, especially alkyl polyglucoside (APG), decyl glucoside and the lauryl glucoside of selling with title Plantaren 2000 and Plantaren 1200 respectively by Henkel for example, 16/octadecyl glucoside, it randomly is form of mixtures with 16/octadecanol, as selling with title Montanov 68 by Seppic, by Goldschmidt with title Tegocare CG90 with sell with title Emulgade KE3302 by Henkel, and eicosyl glucoside, for example eicosyl of selling with title Montanov 202 by Seppic and the form of mixtures of tadenan and eicosyl glucoside.According to specific embodiment of the present invention, can be the form of self-emulsifying composition as the mixture of above-mentioned alkyl polyglucoside and corresponding aliphatic alcohol, for example disclosed in document WO-A-92/06778.
In other emulsion stabilizer, especially preferably use the polymer of isophthalic acid or sulfo-isophthalic acid, and phthalic acid ester/sulfo-isophthalate/glycerol copolymer particularly, for example by diethylene glycol/phthalic acid ester/isophthalate/1 of Eastman Chemical with title " Eastman AQ polymer " (AQ35S, AQ38S, AQ55S, AQ48 Ultra) sale, 4-cyclohexanedimethanol copolymer (INCI name: Polyester-5).
When relating to a kind of emulsion, the water of emulsion can contain the nonionic blister dispersion liquid (Bangham, Standish and Watkins, JMol.Biol., 13,238 (1965), FR 2 315 991 and FR 2 416 008) of with good grounds known method preparation.
Compositions according to the present invention all can used aspect many processing, particularly skin, lip and hair is comprised the cosmetic treatments of scalp, in particular for protection and/or nursing skin, lip and/or hair and/or be used for cosmetic skin and/or lip.
Another theme of the present invention comprises by compositions of the present invention defined above protects the purposes in product and the cosmetic product at product, especially care product, light that manufacturing is used for the cosmetic treatments of skin, lip, fingernail, eyelashes, eyebrow and/or scalp.
Can for example use according to cosmetic composition of the present invention as cosmetic product.
Can be for example use according to cosmetic composition of the present invention as care product and/or solar protection product to face and/or health, for liquid or semiliquid continuous, example emulsion, level and smooth relatively cream, gel or pasty state cream.They can be randomly with aerosol packaging, or provides with foam or spray form.
Passable according to the compositions that is in transpirable liquid lotion form of the present invention, rely on pressue device to be applied to skin or hair with fine particulate form.According to device of the present invention is well known to those skilled in the art, and comprises non-aerosol pump or " aerosol apparatus ", comprises the aerosol container of propellant and use the aerosol pump of compressed air as propellant.The latter is open in patent US 4 077 441 and US 4 850 517 (constituting the intact part of this description).
Generally contain conventional propellant according to the present invention with the compositions of pressurized package, for example for instance, hydrofluorocompounds, dichlorodifluoromethane, Difluoroethane, dimethyl ether, iso-butane, normal butane, propane or Arcton 11.Their amount preferably accounts for 15 to 50% weight of composition total weight.
The specific embodiment
Now provide concrete but the embodiment of indefiniteness illustrates the present invention.
Synthetic embodiment:
Embodiment 1:1, the preparation of 3-dimethylbutyl (benzamido) acetas:
Figure A20071013883500311
With hippuric acid (8g, 0.0446mol), 4-methyl-2-amylalcohol (6.8ml, 0.0536mol) and 98% sulphuric acid (0.41ml, 0.00446mol) mixture in 100ml toluene is 80 ℃ of heating 17 hours down.Carry out 4-methyl-2-amylalcohol (6.8ml, 0.0536mol) and 98% sulphuric acid (0.41ml, add second time 0.00446mol), and with reaction mixture refluxed 7 hours.Reactant mixture is evaporate to dryness under reduced pressure.Residue absorbs in ethyl acetate and washes with water twice.Isolating organic facies dried over sodium sulfate.Behind filtration and evaporating solvent, the yellow oil of acquisition is at the enterprising circumstances in which people get things ready for a trip spectrum of tripoli (eluant: heptane/ethyl acetate 80: 20), obtain the pure fraction of embodiment 1 chemical compound of 3g (productive rate 22%) light yellow oil form.
The preparation of embodiment 2:2-ethylhexyl (benzamido) acetas:
Figure A20071013883500312
With hippuric acid (6.25g, 0.0349mol), 2-ethyl-1-hexanol (6ml, 0.0384mol) and 98% sulphuric acid (0.18ml, 0.00349mol) mixture heated in 20ml toluene refluxed 17 hours.Reactant mixture is evaporate to dryness under reduced pressure.Residue absorbs in ethyl acetate and washes with water twice.Isolating organic facies dried over sodium sulfate.Behind filtration and evaporating solvent, the yellow oil of acquisition is at the enterprising circumstances in which people get things ready for a trip spectrum of tripoli (eluant: CH 2Cl 2), obtain the pure fraction of embodiment 2 chemical compounds of 8.8g (productive rate 87%) light yellow oil form.
The preparation of embodiment 3:2-ethylhexyl [(3-hydrocinnamoyl) amino] acetas:
Figure A20071013883500313
The first step: the preparation of 2-ethylhexyl aminoacetate
With glycine (4.36g, 0.0582mol), 2-ethyl-1-hexanol (10ml, 0.0639mol) and 98% sulphuric acid (0.311ml, 0.00581mol) mixture heated in 20ml toluene refluxed 17 hours.In the suspension that obtains, add 50ml toluene, add the 0.5ml concentrated sulphuric acid, then the mixture that merges is kept refluxing 24 hours.Reactant mixture is evaporate to dryness under reduced pressure.Residue is at the enterprising circumstances in which people get things ready for a trip spectrum of tripoli (eluant: CH 2Cl 2/ methanol 98: 2), obtain the pure fraction of the 2-ethylhexyl aminoacetate of 7g (productive rate 87%) orange oil form, it is used for following step.
Second step: the preparation of embodiment 3 products
(4.81g adds 3.4ml oxalyl chloride (0.0384mol) in 0.032mol) 0 ℃ of 3-phenylpropyl alcohol acyl acid in the mixture that is dissolved in 20ml anhydrous acetonitrile and 1ml dry DMF in following 15 minutes.Mixture keeps stirring 3 hours under laboratory temperature.The solvent vapourisation under reduced pressure, and the yellow oil that obtains absorbs in the 20ml acetonitrile.Be cooled to-5 ℃, (6g 0.032mol), adds the diisopropylethylamine of 16ml subsequently to drip the product that is dissolved in the back in the 10ml acetonitrile then.Reactant mixture stirred 17 hours.Its evaporate to dryness under reduced pressure then.Residue absorbs in ethyl acetate and cleans with saturated nacl aqueous solution, washes with water then twice.Isolating organic facies dried over sodium sulfate.Behind filtration and evaporating solvent, the yellow oil of acquisition is at the enterprising circumstances in which people get things ready for a trip spectrum of tripoli (eluant: heptane/ethyl acetate 90: 10), obtain the pure fraction of embodiment 3 chemical compounds of 3.25g (productive rate 31%) light yellow oil form.
The preparation of embodiment 4:N-(2-ethylhexyl)-3-phenyl-N-(2-phenylethyl) propionic acid amide.:
Figure A20071013883500321
The preparation of the first step: N-(2-ethylhexyl)-N-(2-phenylethyl) amine
With the 2-ethyl-1-hexylamine (4g that is dissolved among the anhydrous THF of 16ml, 0.0309mol) (concentration 50% in oil to join sodium hydride at 0 ℃ in following 15 minutes, 1.49g) in the suspension of the anhydrous THF of 10ml, mixture kept 1 hour under laboratory temperature then.Under laboratory temperature, add in 15 minutes subsequently the 2 bromoethyl benzene be dissolved among the anhydrous THF of 60ml (5.1ml, 0.037mol).Reactant mixture kept 19 hours under laboratory temperature, and kept 24 hours at 80 ℃ then.After the cooling, carefully add 100ml water, use the CH of 3 * 150ml then 2Cl 2Extraction.With saturated NaCl solution washing organic facies, through dried over sodium sulfate evaporate to dryness under reduced pressure then.(eluant: heptane/ethyl acetate 50: 50), obtain the pure fraction of N-(2-ethylhexyl)-N-(2-phenylethyl) amine of 3.4g (productive rate 47%) yellow oil form, it is used to following step to the yellow oil that obtains in the enterprising circumstances in which people get things ready for a trip spectrum of tripoli.
Second step: the preparation of embodiment 4 products
(2.2g adds 1.5ml oxalyl chloride (0.0145mol) in 0.0145mol) 0 ℃ of dihydro cinnamon acid in the mixture that is dissolved in 10ml anhydrous acetonitrile and 0.5ml dry DMF in following 10 minutes.Mixture keeps stirring 3 hours under laboratory temperature.The solvent vapourisation under reduced pressure, and the orange oil that obtains absorbs in the 20ml acetonitrile.Be cooled to-5 ℃, drip simultaneously the back product be dissolved in the 10ml acetonitrile (3.4g, 0.0145mol) and the diisopropylethylamine of 7.2ml.Reactant mixture stirred 17 hours.Its evaporate to dryness under reduced pressure then.Residue absorbs in ethyl acetate and cleans with saturated nacl aqueous solution, washes with water then twice.Isolating organic facies dried over sodium sulfate.Behind filtration and evaporating solvent, the brown oil of acquisition is at the enterprising circumstances in which people get things ready for a trip spectrum of tripoli (eluant: heptane/ethyl acetate 90: 10), obtain the pure fraction of embodiment 4 chemical compounds of 3.98g (productive rate 73%) light yellow oil form.
Embodiment 5:2-phenylethyl-3, the preparation of 4-mesitylenic acid ester:
Figure A20071013883500331
With 3, the 4-mesitylenic acid (16.53g, 0.11mol), the 2-phenylethanol (15.8ml, 0.132mol) and 98% sulphuric acid (0.6ml, 0.011mol) mixture in 170ml toluene is 80 ℃ of down heating 20 hours.Brown reactant mixture washes with water.After separating organic facies, the vapourisation under reduced pressure solvent.Residue in mixture absorbs in heptane/ethyl acetate at 97: 3, filters through the tripoli bed then.After separating pure fraction and solvent evaporated, obtain embodiment 5 chemical compounds of 20.2g (productive rate 72%) light yellow oil form.
Embodiment 6: two (2-phenylethyl) pyridine-2, the preparation of 4-dicarboxylic ester
To be dissolved in 2 in the 60ml toluene, the 4-dipicolinic acid (6g, 0.0359mol), the 2-phenylethanol (10.16ml, 0.085mol) and the mixture of 0.6ml concentrated sulphuric acid 80 ℃ of heating 15 hours down.Behind the vapourisation under reduced pressure solvent, the thickness yellow oil that obtains is dissolved in the dichloromethane, then purification on the tripoli bed.After solvent evaporated, obtain the pure fraction of embodiment 6 chemical compounds of 5.8g (productive rate 43%) white solid form.
Example of formulations 7 to 9
Compositions below the preparation is then to wherein each assesses the light stability of 4-(tert-butyl group)-4 '-methoxy dibenzoyl methane.
Form Embodiment 7 is correlated Embodiment 8 Embodiment 9
Polydimethylsiloxane ?0.5 ?0.5 ?0.5
Antiseptic ?1 ?1 ?1
Stearic acid ?1.5 ?1.5 ?1.5
Glyceryl monostearate/PEG (100 OE) stearate mixture (Arlacel P165, Uniquema) ?1 ?1 ?1
Deionized water ?73.35 ?73.35 ?73.35
Chelating agen ?0.1 ?0.1 ?0.1
Isopropyl N-Hamposyl L salt (ELDEW SL-205, Ajinomoto) (amide compound) ?10 ?9 ?9
List or alkyl diaryl amide (Compound I) ?1
List or alkyl diaryl amide (compound a) ?1
The 4-tert-butyl group-4 '-methoxy dibenzoyl methane (Parsol 1789, DSM Nutritional Pruducts) ?2 ?2 ?2
Glycerol ?5 ?5 ?5
Xanthan gum ?0.2 ?0.2 ?0.2
Cetyl acid potassium (Amphisol K, DSM Nutritional Pruducts) ?1 ?1 ?1
2-Methylpentadecane ?1 ?1 ?1
Acrylic acid/stearyl methacrylate copolymer (Pemulen TR 1, Noveon) ?0.2 ?0.2 ?0.2
Spermol ?0.5 ?0.5 ?0.5
Triethanolamine ?0.65 ?0.65 ?0.65
(Montanov 68, Seppic) for the mixture of 16/octadecyl glucoside and spermol/stearyl alcohol ?2 ?2 ?2
Measuring method
For each preparation, prepare 3 test specimens and 3 control samples.Use spatula with 2mg/cm 2Preparation be placed on poly-(methyl methacrylate) sampling plate.
Test sheet is exposed to last 38 minute of Heraeus Suntest device with xenon lamp, and it has 9.5 * 10 -3W/cm 2UV-A radiant flux and 5.43 * 10 -4W/cm 2The uv b radiation flux.The contrast sampling plate in the dark, identical temperature (38-40 ℃) places the identical time down.
After time finishes,, and extract sunscreen in order to obtain the supersound process that better extraction effect carries out 15 minutes by each sampling plate of dipping in 50g methanol.The solution that obtains is by HPLC and UV spectrophotometric analysis.
For each preparation of test, provide with the ratio of its optical density (OD) in exposed sample with unexposed optical density (OD) in the concentration of 4-(tert-butyl group)-4 '-methoxy dibenzoyl methane remaining after the exposure.The position of adopting is the absorption maximum corresponding to butyl methoxydibenzoylmethise: λ Max=358nm.
Gather in the result's table 1 below that obtains:
Compositions In UV-A, expose the remaining % of the dibenzoyl methane after 1 hour
Embodiment 7 (correlated) ?74%
Embodiment 8 ?80%
Embodiment 9 ?79%
Can see and N-Hamposyl L isopropyl ester (ELDEW SL-205, Ajinomoto) (amide compound of prior art) relatively, general formula (I) (compound a) or (II) existence of the arylalkyl amide chemical compound of (compound b) improved the light stability of dibenzoyl methane.
Example of formulations 10 to 12
Compositions below the preparation is then according to the light stability of the method shown in the previous embodiment 7 to 9 to wherein each assessment 4-(tert-butyl group)-4 '-methoxy dibenzoyl methane.
Form Embodiment 10 (contrast) Embodiment 11 Embodiment 12
Polydimethylsiloxane 0.5 ?0.5 ?0.5
Antiseptic 1 ?1 ?1
Stearic acid 1.5 ?1.5 ?1.5
Glyceryl monostearate/PEG (100 OE) stearate mixture (Arlacel P165, Uniquema) 1 ?1 ?1
Deionized water 73.35 ?73.35 ?73.35
Chelating agen 0.1 ?0.1 ?0.1
2-ethylphenyl benzoate (X-Tend 226 , ISP) 20
Alkyl aryl (chemical compound s) ?20
(chemical compound v) for alkyl aryl ?20
The 4-tert-butyl group-4 '-methoxy dibenzoyl methane (Parsol 1789 , DSM Nutritional Pruducts) 2 ?2 ?2
Glycerol 5 ?5 ?5
Xanthan gum 0.2 ?0.2 ?0.2
Potassium cetyl phosphate (Amphisol K, DSM Nutritional Pruducts) 1 ?1 ?1
2-Methylpentadecane 1 ?1 ?1
Acrylic acid/methacrylic acid octadecanol ester copolymer (Pemulen TR 1, Noveon) 0.2 ?0.2 ?0.2
Spermol 0.5 ?0.5 ?0.5
Triethanolamine 0.65 ?0.65 ?0.65
(Montanov 68, Seppic) for the mixture of 16/octadecanol glucoside and spermol/stearyl alcohol 2 ?2 ?2
Gather in the result's table below that obtains:
Compositions In UV-A, expose the remaining % of the dibenzoyl methane after 1 hour
Embodiment 10 (contrast) ?52%
Embodiment 11 ?74%
Embodiment 12 ?65%
Can see that (X-Tend 226 , ISP) relatively, (existence of chemical compound (s) and (v)) has improved the light stability of dibenzoyl methane to alkyl aryl considerably with 2-ethylphenyl benzoate.

Claims (22)

1, compositions, it contains UV-A sunscreen and at least a following general formula (I), (II) or the arylalkyl amide (III) or the ester compounds of at least a dibenzoylmethane derivative type in acceptable medium on making up:
Figure A2007101388350002C1
Wherein:
-R 1Be straight or branched C 1-C 4Alkyl group,
-a is 0-2,
-m is 0-4,
-b is 1 or 2,
-R 2Be H, straight or branched C 1-C 20Alkyl or Acetyl Groups,
-R 3Be H or methyl independently,
-p is 0-4,
-q is 0-3,
-X is O, NH or NR 5,
-Y is CH or N,
-R 4And R 5Be straight or branched C 1-C 20Alkyl group,
Condition below general formula (III) satisfies: if Y=CH, R 3=H, m=0, p=2, a is not 0 and R so 1It is not methyl.
2, compositions according to claim 1 is characterized in that, general formula (I) chemical compound is selected from following product (a) and arrives (k):
Figure A2007101388350003C1
RN=3278-14-6
Figure A2007101388350003C2
RN=73355-77-8
Figure A2007101388350003C3
RN=3271-81-6
Figure A2007101388350003C4
RN=10264-31-0
Figure A2007101388350003C5
RN=152328-83-1
Figure A2007101388350003C6
RN=1554319-75-2
RN=18859-20-6
Figure A2007101388350004C2
RN=154319-75-2。
3, compositions according to claim 1 is characterized in that, general formula (II) chemical compound is selected from following product (l) and arrives (r):
RN=1776-56-3
Figure A2007101388350004C4
RN=315711-63-8
Figure A2007101388350005C1
RN=91146-19-9
Figure A2007101388350005C2
4, compositions according to claim 1, its formula of (III) chemical compound are selected from following product (s) and arrive (x):
RN=89291-00-9
RN=726-26-1
Figure A2007101388350005C5
RN=758717-16-7
Figure A2007101388350006C1
RN=7165343-5
Figure A2007101388350006C2
5, require each compositions according to aforesaid right, there are ratio in its formula of (I), (II) or one or more arylalkyl amides (III) or ester compounds in compositions, in composition total weight, between 0.01% to 20% weight, and preferred content is between 0.1% to 10% weight.
6, require each compositions according to aforesaid right, wherein dibenzoylmethane derivative is selected from:
-2-methyldiphenyl formyl methane,
-4-methyldiphenyl formyl methane,
-4-isopropyl diphenyl formyl methane,
-4-tert-butyl group dibenzoyl methane
-2,4-dimethyl dibenzoyl methane,
-2,5-dimethyl dibenzoyl methane,
-4,4 '-diisopropyl dibenzoyl methane,
-4,4 '-dimethoxy dibenzoyl methane,
-4-the tert-butyl group-4 '-methoxy dibenzoyl methane,
-2-methyl-5-isopropyl-4 '-methoxy dibenzoyl methane,
-2-methyl 5-the tert-butyl group-4 '-methoxy dibenzoyl methane,
-2,4-diformazan-4 '-methoxy dibenzoyl methane,
-2, the 6-dimethyl-4-tert-butyl group-4 '-methoxy dibenzoyl methane.
7, according to the compositions of claim 5, wherein dibenzoylmethane derivative is the 4-isopropyl diphenyl formyl methane that meets following formula:
Figure A2007101388350007C1
8, according to the compositions of claim 5, wherein dibenzoylmethane derivative is the 4-tert-butyl group-the 4 '-methoxy dibenzoyl methane or the butyl methoxydibenzoylmethise of following formula:
Figure A2007101388350007C2
9, require each compositions according to aforesaid right, wherein the excursion of the amount of one or more dibenzoylmethane derivatives with respect to the gross weight of compositions, is 0.01 to 10% weight, preferably from 0.1 to 6% weight.
10, require each compositions according to aforesaid right, it is characterized in that, it also is included in has active other organic or inorganic UV sunscreen in UV-A and/or the UV-B zone, described sunscreen is water miscible or fat-soluble or is insoluble in the normally used beauty treatment solvent.
According to the compositions of claim 10, it is characterized in that 11, other organic uv filter is selected from: the o-aminobenzoa class; Cinnamic acid derivative; Salicyclic acid derivatives; Camphor derivatives; Methanone derivatives; β, β-diphenylacrylate; Pyrrolotriazine derivatives; Benzotriazole derivatives; The toluenyl malonic ester derivant; Benzimidizole derivatives; Imidazolidine derivatives; Two benzoxazolyl group derivants; Para-amino benzoic acid (PABA) derivant; Di-2-ethylhexylphosphine oxide (hydroxy-phenyl benzotriazole) derivant; The benzoxazol derivant; Sun-proof polymer and sun-proof silicone; Two polymer by the alpha-alkyl phenylethylene generation; 4,4-diaryl butadiene; With their mixture.
According to the compositions of claim 10, it is characterized in that 12, one or more organic uv filters are selected from following chemical compound:
Ethylhexyl methoxy cinnamate,
Heliophan,
Ethylhexyl salicylate,
Octocrylene,
Phenylbenzimidazolesulfonic acid,
Benzophenone-3,
Benzophenone-4,
Benzophenone-5,
The just own ester of 2-(4-lignocaine-2-hydroxy benzoyl) benzoic acid,
4 methyl benzylidene camphor,
The Terephthalidene Dicamphor Sulfonic Acid,
Phenyl bisbenzimidazole tetrasulfonic acid disodium,
Methylene dibenzo triazolyl tetramethyl butyl phenol,
The ethylhexyl triazinone,
It is two-ethylhexyl oxy phenol anisyl triazine,
Diethylhexyl butyrylamino triazinone,
2,4,6-three (4 '-amino benzal malonic acid two peopentyl esters)-s-triazine,
2,4,6-three (4 '-amino benzal malonic acid diisobutyl ester)-s-triazine,
2,4,6-three (xenyl-4-yl)-1,3,5-triazines,
2,4,6-three (terphenyl)-1,3,5-triazines,
The drometrizole trisiloxanes,
Polysilicone-15,
4 '-methoxyl group benzal malonic acid, two peopentyl esters,
1,1-dicarboxyl (2,2 '-dimethyl propyl)-4, the 4-diphenyl diethylene,
2, two [5-1 (dimethyl propyl) benzoxazol-2-base-(4-phenyl) imino group]-6 (2-ethylhexyl) imino group-1,3,5-triazines of 4-,
And their mixture.
According to the compositions of claim 10, it is characterized in that 13, additional inorganic UV sunscreen is the pigment of handling or untreated metal-oxide forms.
14, the compositions of foundation claim 13 is characterized in that, described pigment is selected to be handled or untreated titanium oxide, zinc oxide, ferrum oxide, zirconium oxide, cerium oxide and their mixture.
15, according to each compositions of claim 1 to 14, it is characterized in that it also contains at least a reagent that is used for the artificial tanned and/or browning of skin.
16, according to each described compositions in the claim 1 to 14, it is characterized in that, it also contains at least a adjuvant, and this adjuvant is selected from: lipoid material, organic solvent, ion or nonionic and hydrophilic or lipotropy thickening agent, softening agent, wetting agent, opacifier, stabilizing agent, emollient, silicone, defoamer, spice, antiseptic, anion, cation, nonionic, amphion or amphoteric surfactant, active component, filler, polymer, propellant or alkalization or acidulant.
17, according to each compositions in the claim 1 to 16, it is characterized in that said composition provides with the emulsion form of oil-in-water or water in oil form.
18, the purposes of each compositions in preparing the product that skin, lip, fingernail, hair, eyelashes, eyebrow and/or scalp is carried out cosmetic treatments in the claim 1 to 17.
19, the purposes of the compositions of each definition in preparation skin, lip, fingernail, hair and/or scalp care product in the claim 1 to 17.
20, the purposes of the compositions of each definition in the preparation cosmetic product in the claim 1 to 17.
21, the UV-A sunscreen of the dibenzoylmethane derivative type of at least a aforementioned arbitrary claim definition of improvement is for the method for the radiating chemical stability of UV, it is characterized in that, make general formula (I), (II) or arylalkyl amide (III) or the ester compounds combination of described dibenzoylmethane derivative and at least a aforementioned claim definition.
22, general formula (I), (II) or arylalkyl amide (III) or the purposes of ester compounds in compositions of at least a aforementioned claim definition, said composition contains the dibenzoylmethane derivative of at least a aforementioned claim definition in the beauty treatment acceptable carrier, its target is to improve the effectiveness of described compositions antagonism UV-A ray.
CNA2007101388353A 2006-06-23 2007-06-22 Dibenzoylmethane sunscreens photostabilized with arylalkyl amide or ester compounds Pending CN101095648A (en)

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FR0652621 2006-06-23
FR0652620A FR2902652A1 (en) 2006-06-23 2006-06-23 Cosmetic composition comprises a dibenzoylmethane UV-A filter and an aromatic ester

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109503528A (en) * 2018-05-15 2019-03-22 天津国际生物医药联合研究院 A kind of compound and its application in anti-arenavirus infection
CN109528535A (en) * 2012-01-31 2019-03-29 皮埃尔·法布尔皮肤化妆品公司 Stablize composition and the combination of the sun-screening agent of butylmethoxydibenzoylmethane for light

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Publication number Priority date Publication date Assignee Title
FR2947724B1 (en) 2009-07-10 2012-01-27 Oreal COMPOSITE MATERIAL COMPRISING UV FILTERS AND PLASMONIC PARTICLES AND USE IN SOLAR PROTECTION

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Publication number Priority date Publication date Assignee Title
FR2800991A1 (en) * 1999-11-17 2001-05-18 Bio Sources Ind Photo-stabilization of butyl-methoxy-dibenzoyl methane, for use in cosmetic compositions for solar protection, involves association with phenyl or preferably benzyl salicylate
IL161782A0 (en) * 2001-11-08 2005-11-20 Sol Gel Technologies Ltd Compositions containing oils havinga specific gravity higher than the specific gravity of water
FR2872413B1 (en) * 2004-07-02 2008-06-27 Oreal METHOD FOR PHOTOSTABILIZING A DIBENZOYLMETHANE DERIVATIVE WITH AN ARYLALKYL BENZOATE DERIVATIVE AND PHOTOPROTECTIVE COMPOSITIONS

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109528535A (en) * 2012-01-31 2019-03-29 皮埃尔·法布尔皮肤化妆品公司 Stablize composition and the combination of the sun-screening agent of butylmethoxydibenzoylmethane for light
CN109503528A (en) * 2018-05-15 2019-03-22 天津国际生物医药联合研究院 A kind of compound and its application in anti-arenavirus infection
CN109503528B (en) * 2018-05-15 2022-06-14 天津国际生物医药联合研究院 Compound and application thereof in resisting arenavirus infection

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