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    • 专利摘要:
    The present invention relates to a novel cosmetic or skin composition for topical use, in particular for photoprotection of skin and / or hair, characterized in that it contains the following in a cosmetically acceptable carrier: (i) at least one silicone derivative having a benzotriazole functional group as a first blocking agent; (ii) as a second blocking agent, at least one dibenzoylmethane derivative; (iii) at least one amino substituted 2-hydroxybenzophenone derivative as third blocking agent. The combination of the three blockers results in a synergistic effect obtained for the provided block index UV-A PPD . The invention also relates to their application in protecting skin and hair against the effects of ultraviolet radiation.
    公开号:KR20030047812A
    申请号:KR1020020077385
    申请日:2002-12-06
    公开日:2003-06-18
    发明作者:깡도디디에
    申请人:로레알；
    IPC主号:
    专利说明:

    Sunscreen cosmetic compositions based on synergistic mixtures of blockers, and use thereof {ANTISUN COSMETIC COMPOSITIONS BASED ON A SYNERGISTIC MIXTURE OF SCREENING AGENTS, AND USES}
    [1] The present invention relates to a novel cosmetic or skin composition for topical use, in particular for photoprotection of skin and / or hair, characterized in that it contains the following in a cosmetically acceptable carrier:
    [2] (i) at least one silicone derivative having a benzotriazole functional group as a first blocking agent;
    [3] (ii) as a second blocking agent, at least one dibenzoylmethane derivative;
    [4] (iii) at least one specific amino substituted 2-hydroxybenzophenone derivative as third blocking agent. The combination of the three blockers results in a synergistic effect obtained for the provided block index UV-A PPD .
    [5] The invention also relates to their application in the protection of skin and hair against the effects of ultraviolet radiation.
    [6] Light radiation with a wavelength of 280 nm to 400 nm can brown the human epidermis, and light rays with a wavelength of 280 nm to 320 nm, known under the name UV-B, can be detrimental to the occurrence of natural tanning. It is known that this UV-B radiation should be blocked, as it causes erythema and skin burns.
    [7] It is also known that UV-A rays of wavelength 320 nm to 400 nm, which cause browning of the skin, can cause harmful changes in the latter, especially in case of sensitive skin or in the case of continuous exposure to sunlight. It is. UV-A rays cause loss of elasticity and wrinkled appearance of the skin resulting in premature ejaculation. They promote the triggering of the lupus erythematosus reaction, or in some subjects, make the reaction prominent and even cause phototoxic or photoallergic reactions. Therefore, it is also desirable to block UV-A radiation.
    [8] Numerous cosmetic compositions intended to photoprotect (UV-A and / or UV-B) skin have been provided to date.
    [9] The efficacy of a sunscreen composition is commonly expressed in terms of the sunscreen index (SPF), which is mathematically needed to reach the erythema threshold with a UV blocker, against the UV radiation dose required to reach the erythema threshold without a UV blocker. Expressed as the ratio of UV radiation dose. The index thus relates to the blocking effect on erythema whose spectrum of biological action is centered in the UV-B region and consequently describes the blocking on the UV-B radiation.
    [10] Specific methods for evaluating the blocking of UV-A radiation in terms of the effects of UV-A radiation on the skin and the production of numerous compositions comprising a combination of blocking agents capable of absorbing UV-B and / or UV-A radiation. This was developed.
    [11] For the identification of blocking against UV-A radiation, the PPD (persistent immediate blackening) method of measuring the color of the skin observed 2-4 hours after exposure of the skin to UV-A radiation is particularly preferably used. The method was adopted in 1996 as the official test procedure for the UV-A labeling of products by the Japan Cosmetic Industry Association (JCIA) and is often used in laboratories in Europe and the United States (Japan Cosmetic Industry Association Technical Bulletin, Measurement Standards for UVA). protection efficacy.published November 21, 1995, useful for 1996.1.1).
    [12] The sun protection index UV-A PPD (PF-A PPD PF) mathematically measures the UV-A radiation dose (MPPPD np ) pigmentation threshold without the UV-A radiation dose required to reach the (MPPPD p ) pigmentation threshold with UV blocker. It is expressed as the ratio of UV-A radiation dose required to reach.
    [13]
    [14] The sunscreen composition is often present in an oil-in-water emulsion form (ie, a cosmetically acceptable carrier consisting of a continuous aqueous disperse phase and a discontinuous oily disperse phase), which are in various concentrations, one or more conventional lipophilic and / or It contains organic blockers that can selectively absorb hydrophilic, harmful UV radiation, which blockers (and their amounts) are selected according to the desired sunscreen index.
    [15] Cosmetic UV blockers formed from lipophilic silicone derivatives with benzotriazole functionalities, which exhibit good blocking in both the UV-A and UV-B radiation regions, are known in the art. These are disclosed in the applications EP-A-0 392 883, EP-A-0 660 701, EP-A-0 708 108, EP-A-0 711 778 and EP-A-711 779.
    [16] For the purpose of obtaining synergistic activity against the sun block index, the silicone blocker and benzotriazole functional group, specific water soluble blocker and sulfone groups, ie, benzene-1,4-di (3-methylidene-10-camphorsulfonic acid ) Or the combination of 2-phenylbenzimidazole-5-sulfonic acid and salts thereof has already been provided in applications EP-A-0 742 003 and EP-A-0 860 165. The synergistic next step requires the use of at least one aqueous phase to dissolve the water soluble blocker and a fatty phase to dissolve the silicone blocker, which substantially reduces the formulation potential.
    [17] Sunscreen compositions based on amino substituted 2-hydroxybenzophenone derivatives which may contain other additional blocking agents such as silicone derivatives with benzotriazole functional groups or dibenzoylmethane derivatives are described in patent applications EP-A-1 046 391 and DE. 10 012 408 is known.
    [18] Following many studies conducted in the field of photoprotection, the present applicant company surprisingly and unexpectedly has three specific groups of blocker compounds already known in the art, namely (1) dibenzoylmethane derivatives, The combination of (2) benzotriazole silicone derivatives and (3) specific amino-substituted 2-hydroxybenzophenone derivatives makes it possible to obtain sunscreen compositions exhibiting significantly improved sunscreen index UV-A PPD due to synergistic effects. I found that. With such a combination it is possible to obtain sunscreen compositions which are markedly improved and, in any case, have a higher sunscreen index UV-A PPD than can be obtained with any blocker used alone.
    [19] Moreover, the specific combination of blocking agents according to the invention can be readily incorporated in a wide variety of cosmetic carriers.
    [20] The finding forms the basis of the present invention.
    [21] Thus, according to one subject of the invention there is now provided a novel cosmetic composition, in particular a sunscreen cosmetic composition, characterized in that it contains the following in a cosmetically acceptable carrier:
    [22] (i) at least one silicone derivative having a benzotriazole functional group as a first blocking agent;
    [23] (ii) as a second blocking agent, at least one dibenzoylmethane derivative;
    [24] (iii) at least one amino substituted 2-hydroxybenzophenone derivative of formula (III) as defined below as a third blocking agent.
    [25] Another subject of the invention is the use of said composition in the preparation of a cosmetic composition for protection of skin and / or hair against ultraviolet radiation, in particular solar radiation.
    [26] Generally, the first, second and third blockers are present in the compositions of the present invention at a rate that produces a synergistic effect on the provided sunscreen index UV-A PPD .
    [27] Other features, aspects, and advantages of the invention will be apparent from the following detailed description.
    [28] Silicone derivatives having benzotriazole functional groups used in the present invention are preferably silanes or siloxanes having benzotriazole functional groups comprising one or more units of the formula (1):
    [29] O (3-a) / 2 Si (R 7 ) a -G
    [30] [In the meal,
    [31] R 7 represents an optionally halogenated C 1 -C 10 alkyl radical or phenyl radical or trimethylsilyloxy radical,
    [32] a is an integer from 0 to 3,
    [33] The symbol G represents a monovalent radical bonded directly to the silicon atom corresponding to formula (2):
    [34]
    [35] (In the meal,
    [36] -Y is the same or different and is selected from a C 1 -C 8 alkyl radical, a halogen and a C 1 -C 4 alkoxy radical, in the latter case two adjacent Y radicals on the same aromatic nucleus have an alkylidene group having from 1 to It is understood that an alkylidenedioxy group including 2 can be formed,
    [37] -X represents O or NH,
    [38] Z represents hydrogen or a C 1 -C 4 alkyl radical,
    [39] n is an integer from 0 to 3,
    [40] m is 0 or 1,
    [41] -p is an integer from 1 to 10 or less).
    [42] Such compounds are disclosed in particular in patent applications EP-A-0 392 883, EP-A-0 660 701, EP-A-0 708 108, EP-A-0 711 778 and EP-A-711 779.
    [43] Silicone derivatives used in the context of the present invention preferably belong to the general group of benzotriazole silicones disclosed in particular in EP-A-0 660 701.
    [44] Particularly suitable groups of benzotriazole silicones for the practice of the present invention are those comprising compounds corresponding to formula (5) or (6):
    [45]
    [46] or
    [47]
    [48] [In the meal,
    [49] R 7 is the same or different and is selected from C 1 -C 10 alkyl, phenyl, 3,3,3-trifluoropropyl and trimethylsilyloxy radicals and at least 80% of the number of R 7 radicals are methyl,
    [50] D is the same or different and is selected from a R 7 radical and a G radical,
    [51] -r is an integer from 0 to 50 or less, s is an integer from 0 to 20 or less, and if s = 0, at least one of the two symbols D represents G,
    [52] -u is an integer of 1 to 6 or less, t is an integer of 0 to 10 or less, t + u is understood to be 3 or more,
    [53] The symbol G corresponds to the above formula (2).
    [54] -(X) m- (CH 2 ) p -CH (Z) to the benzotriazole unit, confirming that the benzotriazole unit is linked to the silicon atom of the silicon chain, as shown above in formula (2) The attachment of —CH 2 —links takes place at all possible positions provided by the two aromatic nuclei of benzotriazole, according to the invention:
    [55]
    [56] Preferably, the attachment takes place at the 3, 4 or 5 position (aromatic nucleus with hydroxyl functionality) or 4 'position (benzene nucleus adjacent to the triazole ring), more preferably still at the 3, 4 or 5 position Happens. In a preferred embodiment of the invention, the attachment takes place in three positions.
    [57] Likewise, attachment of the Y substituent unit (s) can occur at all other possible positions in the benzotriazole. However, the attachment preferably takes place at the 3, 4, 4 ', 5 and / or 6 positions. In a preferred embodiment of the invention, the attachment of Y units takes place at the 5 position.
    [58] In the above formulas (5) and (6), the alkyl radicals can be linear or branched, in particular methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-amyl, isoamyl And neopentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl and tert-octyl radicals. Preferred R 7 alkyl radicals according to the invention are the methyl, ethyl, propyl, n-butyl, n-octyl and 2-ethylhexyl radicals. More preferably, all R 7 radicals are methyl radicals.
    [59] Among the compounds of the formula (5) or (6), it is preferable to use the one corresponding to the formula (5), that is, diorganosiloxane having a short straight chain.
    [60] Among the compounds of the formula (5), it is preferred to use those in which the D radicals are both R 7 radicals.
    [61] Among the linear diorganosiloxanes that are combined within the scope of the present invention, more particularly preferably, statistical derivatives or alternatively block defined derivatives exhibiting one or more, more preferably all of the following properties:
    [62] D is a R 7 radical,
    [63] R 7 is alkyl, more preferably methyl,
    [64] r is 0 to 15 or less; s is 1 to 10 or less,
    [65] n is not 0, preferably 1, Y is selected from methyl, tert-butyl or C 1 -C 4 alkoxy,
    [66] Z is hydrogen or methyl,
    [67] m = 0 or [m = 1 and X = 0]
    [68] -p is 1
    [69] Particularly suitable benzotriazole silicone groups for the present invention are those defined by the following general formula (7):
    [70]
    [71] [In the meal,
    [72] r is 0 to 10, s is 1 to 10,
    [73] E is a divalent radical ].
    [74] In a particularly preferred embodiment of the invention, the benzotriazole silicone is a compound drometrizol trisiloxane (CTFA name) corresponding to the formula:
    [75]
    [76] Suitable methods for the preparation of the products of the above formulas (1), (5), (6) and (7) are in particular US patents US 3 220 972, US 3 697 473, US 4 340 709, US 4 316 033, and US 4 328 346 and patent applications EP-A-0 392 883 and EP-A-0 742 003.
    [77] Silicone derivatives having benzotriazole functional groups are always present in the composition according to the invention in an amount of from 0.5 to 20% by weight, preferably from 1 to 10% by weight and more preferably from 2 to 8% by weight relative to the total weight of the composition. exist.
    [78] The dibenzoylmethane derivatives aimed at by the invention, indicated above, are already known per se and are in particular the products disclosed in publications FR-A-2 326 405, FR-A-2 440 933 and EP-A-0 114 607. The teachings of this publication are incorporated herein by reference in their entirety, as long as they affect the practical definition of these products.
    [79] Among the dibenzoylmethane derivatives in which the invention is more particularly desired, there is no limitation, in particular the following may be mentioned:
    [80] 2-methyldibenzoylmethane,
    [81] 4-methyldibenzoylmethane,
    [82] 4-isopropyldibenzoylmethane,
    [83] 4-tert-butyldibenzoylmethane,
    [84] 2,4-dimethyldibenzoylmethane,
    [85] 2,5-dimethyldibenzoylmethane,
    [86] 4,4'-diisopropyldibenzoylmethane,
    [87] 4-tert-butyl-4'-methoxydibenzoylmethane,
    [88] 2-methyl-5-isopropyl-4'-methoxydibenzoylmethane,
    [89] 2-methyl-5-tert-butyl-4'-methoxydibenzoylmethane,
    [90] 2,4-dimethyl-4'-methoxydibenzoylmethane,
    [91] 2,6-dimethyl-4-tert-butyl-4'-methoxydibenzoylmethane.
    [92] According to the invention, among the aforementioned dibenzoylmethane derivatives, 4-tert-butyl-4 ', which is provided for sale for the purpose of selling under the trade name "Parsol 1789", in particular by Hoffmann-LaRoche, and which corresponds to the following extended formula (I) More particularly preferably the use of -methoxydibenzoylmethane is provided:
    [93] [Formula I]
    [94]
    [95] Another preferred dibenzoylmethane derivative according to the present invention is 4-isopropyldibenzoylmethane, sold under Merck trade name "Eusolex 8020", which is a blocking agent corresponding to the following extended formula (II):
    [96] [Formula II]
    [97]
    [98] The dibenzoylmethane derivative (s) is preferably from 0.5 to 20% by weight, more preferably from 1 to 10% by weight and more preferably from 2 to 8% by weight relative to the total weight of the composition in the composition according to the invention. Present in quantities.
    [99] The amino substituted 2-hydroxybenzophenone derivatives according to the invention correspond to the general formula (III)
    [100] [Formula III]
    [101]
    [102] (In the meal,
    [103] R 1 and R 2 are the same or different and represent a hydrogen atom, a C 1 -C 20 alkyl radical, a C 2 -C 10 alkenyl radical, a C 3 -C 10 cycloalkyl radical or a C 3 -C 10 cycloalkenyl radical Represent;
    [104] R 1 and R 2 may also form a 5- or 6-membered ring with the nitrogen atom bonded thereto;
    [105] R 3 and R 4 are the same or different and are C 1 -C 20 alkyl radicals, C 2 -C 10 alkenyl radicals, C 3 -C 10 cycloalkyl radicals, C 3 -C 10 cycloalkenyl radicals, C 1- C 12 alkoxy radical, (C 1 -C 20 ) alkoxycarbonyl radical, C 1 -C 12 alkylamino radical, di (C 1 -C 12 ) alkylamino radical, optionally substituted aryl radical or heteroaryl, or carboxyl A water-soluble substituent selected from a late group, a sulfonate group or an ammonium residue;
    [106] X 'represents a hydrogen atom or a COOR 5 or CONR 6 R 7 group;
    [107] R 5 , R 6 and R 7 are the same or different and represent a hydrogen atom, a C 1 -C 20 alkyl radical, a C 2 -C 10 alkenyl radical, a C 3 -C 10 cycloalkyl radical, a C 3 -C 10 cycloal A kenyl radical, a-(Y'O) o- Z 'group or an aryl group;
    [108] Y 'represents-(CH 2 ) 2 -,-(CH 2 ) 3 -,-(CH 2 ) 4 -or -CH- (CH 3 ) -CH 2- ;
    [109] Z 'represents -CH 2 -CH 3 , -CH 2 CH 2 CH 3 , -CH 2 CH 2 CH 2 CH 3 , or -CH (CH 3 ) -CH 3 ;
    [110] m 'is an integer from 0 to 3;
    [111] n 'is an integer from 0 to 3;
    [112] o is an integer from 1 to 2).
    [113] As C 1 -C 20 alkyl radicals, for example, mention may be made of: methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl, 1,1- Dimethylethyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1,1-dimethylpropyl, 1,2-dimethyl Propyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl , n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-hepta Decyl, n-octadecyl, n-nonadecyl or n-icosyl.
    [114] As the C 2 -C 10 alkenyl group, for example, mention may be made of: vinyl, n-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 1-pentenyl, 2-pentenyl, 2-methyl-1-butenyl, 2-methyl-2-butenyl, 3-methyl-1-butenyl, 1-hexenyl, 2-hexenyl, 1-heptenyl, 2-heptenyl, 1-jade Tenyl or 2-octenyl.
    [115] As the C 1 -C 12 alkoxy radical, mention may be made of: methoxy, ethoxy, n-propoxy, n-butoxy, n-pentoxy, 1-methylpropoxy, 3-methylbutoxy, 2 , 2-dimethylpropoxy, 1-methyl-1-ethylpropoxy, octoxy, 2-methylpropoxy, 1,1-dimethylpropoxy, hexoxy, heptoxy or 2-ethylhexoxy.
    [116] As the C 3 -C 10 cycloalkyl radical, for example, the following may be mentioned: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, 1-methylcyclopropyl, 2-ethylcyclopropyl, 1-propyl Cyclopropyl, 1-butylcyclopropyl, 1-pentylcyclopropyl, 1-methyl-1-butylcyclopropyl, 1,2-dimethylcyclopropyl, 1-methyl-2-ethylcyclopropyl, cyclooctyl, cyclononyl or cyclo Decyl.
    [117] As C 3 -C 10 cycloalkenyl radicals having one or more double bonds, the following may be mentioned: cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, 1,3-cyclo Hexadienyl, 1,4-cyclohexadienyl, cycloheptenyl, cycloheptatrienyl, cyclooctenyl, 1,5-cyclooctadienyl, cyclooctatetraenyl, cyclononenyl or cyclodecenyl.
    [118] Cycloalkyl or cycloalkenyl radicals may include, for example, one or more (preferably 1 to 3) substituents selected from: halogen, for example chlorine, fluorine or bromine; Cyano; Nitro; Amino; C 1 -C 4 alkylamino; Di (C 1 -C 4 ) alkylamino; C 1 -C 4 alkyl; C 1 -C 4 alkoxy; Or hydroxyl. They may also include from 1 to 3 heteroatoms, for example sulfur, oxygen or nitrogen, whose free valences may be filled by hydrogen or C 1 -C 4 alkyl radicals.
    [119] The aryl group is preferably selected from phenyl or naphthyl rings which may contain, for example, one or more substituents (preferably 1 to 3) selected from: halogen, eg chlorine, fluorine or bromine ; Cyano; Nitro; Amino; C 1 -C 4 alkylamino; Di (C 1 -C 4 ) alkylamino; C 1 -C 4 alkyl; C 1 -C 4 alkoxy; Or hydroxyl, more particularly phenyl, methoxyphenyl and naphthyl.
    [120] Heteroaryl groups typically include one or more hetero atoms selected from sulfur, oxygen or nitrogen.
    [121] Water-soluble groups are, for example, salts with carboxylate or sulfonate groups, more particularly with physiologically acceptable cations such as alkali metal salts or trialkylammonium salts such as tri (hydroxy Alkyl) ammonium or 2-methylpropan-1-ol-2-ammonium salt. Mention may also be made of ammonium groups such as alkylammonium, and physiologically acceptable anions and their chlorinated forms.
    [122] As examples of 5- or 6-membered rings formed by R 1 and R 2 radicals and nitrogen atoms, mention may in particular be made of pyrrolidine or piperidine.
    [123] The amino group may be attached to the benzene ring in the ortho, meta or para position, more preferably in the para position relative to the carbonyl radical.
    [124] Preferred groups of compounds of formula (III) include those selected from those of formula (IIIa):
    [125] [Formula IIIa]
    [126]
    [127] (In the meal,
    [128] R 1 and R 2 are the same or different and represent a hydrogen atom or a C 1 -C 12 alkyl radical or form a 5- or 6-membered ring with the nitrogen atom bonded thereto;
    [129] X 'represents COOR 5 or CONR 6 R 7 ;
    [130] R 5 represents a hydrogen atom, a C 1 -C 12 alkyl radical or a C 3 -C 6 cycloalkyl radical;
    [131] R 6 and R 7 are the same or different and represent a hydrogen atom, a C 1 -C 12 alkyl radical or a C 5 -C 6 cycloalkyl radical).
    [132] More particularly preferred compounds of formula (IIIa) are the following compounds:
    [133] R 1 and R 2 are the same or different and represent a C 1-4 alkyl radical, more particularly ethyl;
    [134] R 5 represents a C 3 -C 8 alkyl radical;
    [135] R 6 and R 7 are the same or different and represent a C 1 -C 8 alkyl radical.
    [136] Another group of preferred compounds of formula (III) include those selected from those of formula (IIIb):
    [137] [Formula IIIb]
    [138]
    [139] [In the meal,
    [140] R 1 and R 2 are the same or different and represent a C 1 -C 12 alkyl radical or form a 5- or 6-membered ring with the nitrogen atom to which they are attached.
    [141] Among the compounds of the formula (IIIb), the following may be more particularly mentioned:
    [142] 4-diethylamino-2-hydroxyphenyl phenyl ketone,
    [143] 4-pyrrolidino-2-hydroxyphenyl phenyl ketone.
    [144] More particularly preferred groups of compounds of formula (III) include those selected from those represented by the following formula (IIIc).
    [145] [Formula IIIc]
    [146]
    [147] [In the meal,
    [148] R 1 and R 2 are the same or different and represent a hydrogen atom or a C 1 -C 8 alkyl radical or together with the nitrogen atom to which they are attached form a 5- or 6-membered ring;
    [149] R 5 represents a hydrogen atom, a C 1 -C 12 alkyl radical or a C 3 -C 6 cycloalkyl radical.
    [150] Among the compounds of the formula (IIIc), the following may be mentioned:
    [151] 2- (4-pyrrolidino-2-hydroxybenzoyl) benzoate
    [152] Methyl 2- (4-diethylamino-2-hydroxybenzoyl) benzoate
    [153] 2-ethylhexyl 2- (4-diethylamino-2-hydroxybenzoyl) benzoate
    [154] Cyclohexyl 2- (4-diethylamino-2-hydroxybenzoyl) benzoate
    [155] n-hexyl 2- (4-diethylamino-2-hydroxybenzoyl) benzoate
    [156] [lacuna] 2- (4-dibutylamino-2-hydroxybenzoyl) benzoate
    [157] Methyl 2- (4-dibutylamino-2-hydroxybenzoyl) benzoate
    [158] Isobutyl 2- (4-dibutylamino-2-hydroxybenzoyl) benzoate.
    [159] Very particularly preferred compound of formula (IIIc) is n-hexyl 2- (4-diethylamino-2-hydroxybenzoyl) benzoate.
    [160] The compounds of formula (I) as defined above are known per se and their structures and their synthesis are disclosed in patent applications EP 1 046 391 and DE 100 12 408 (which form an integral part of the description). It is.
    [161] The amino substituted 2-hydroxybenzophenone derivatives according to the invention are preferably 0.1 to 20% by weight, more preferably 0.1 to 15% by weight, more particularly 0.5 to 10, based on the total weight of the composition in the composition of the invention. It is present in ratios in the range by weight.
    [162] In addition, the compositions according to the invention may contain other additional organic UV blockers (absorbers) which are active in the UV-A and / or UV-B regions, which are water soluble, fat soluble or commonly used cosmetics. Insoluble in solvents.
    [163] Additional organic UV blockers include in particular anthranilates; Cinnamic acid derivatives; Salicylic acid derivatives; Camphor derivatives; Triazine derivatives such as those disclosed in patent applications US 4 367 390, EP 863 145, EP 517 104, EP 570 838, EP 796 851, EP 775 698, EP 878 469 and EP 933 376; Benzophenone derivatives other than those of formula (III) as defined above; β, β-diphenylacrylate derivatives; Benzotriazole derivatives; Benzalmalonate derivatives; Benzimidazole derivatives; Imidazoline; Bisbenzoazolyl derivatives disclosed in patents EP 669 323 and US 2 463 264; p-aminobenzoic acid (PABA) derivatives; Methylenebis (hydroxyphenylbenzotriazole) derivatives disclosed in the applications US 5 237 071, US 5 166 355, GB 2 303 549, DE 197 26 184 and EP 893 119; Blocking polymers and blocking silicones other than those of the invention, for example those disclosed in the application WO 93/04665; And alkylstyrene derivatives, for example those disclosed in patent application DE 198 55 649, 4,4-diarylbutadiene derivatives disclosed in patent applications EP0967200, DE19755649, EP1333981 and mixtures thereof.
    [164] As examples of additional organic blockers active in the UV-A and / or UV-B region, those indicated by the INCI name may be mentioned below:
    [165] Para-aminobenzoic acid derivatives:
    [166] -PABA,
    [167] Ethyl PABA,
    [168] Ethyl dihydroxypropyl PABA,
    [169] Ethylhexyl dimethyl PABA, in particular sold under the trade name "Escalol 507" by the ISP,
    [170] Glyceryl PABA,
    [171] PEG-25 PABA sold under the trade name "Uvinul P25" by BASF,
    [172] Salicylic Acid Derivatives:
    [173] Homoslate sold under the trade name "Eusolex HMS" by Rona / EM Industries,
    [174] Ethylhexyl salicylate, sold under the trade name "Neo Heliopan OS" by Haarmann and Reimer,
    [175] Dipropylene glycol salicylate, sold under the trade name "Dipsal" by Scher,
    [176] TEA salicylate, sold under the name "Neo Heliopan TS" by Haarmann and Reimer.
    [177] Cinnamic acid derivatives:
    [178] Ethylhexyl methoxycinnamate, especially those sold under the trade name "Parsol MCX" by Hoffman-LaRoche,
    [179] Isopropyl methoxy cinnamate,
    [180] Isoamyl methoxy cinnamate sold by Haarmann and Reimer under the trade name "Neo Heliopan E 1000",
    [181] -Synoxate,
    [182] DEA methoxycinnamate,
    [183] Diisopropyl methylcinnamate,
    [184] Glyceryl ethylhexanoate dimethoxycinnamate,
    [185] β, β-diphenylacrylate derivatives:
    [186] Octocrylene, in particular sold under the trade name "Uvinul N539" by BASF,
    [187] Etocrylene, especially those sold under the trade name "Uvinul N35" by BASF,
    [188] Benzophenone Derivatives:
    [189] Benzophenone-1 sold under the trade name "Uvinul 400" by BASF,
    [190] Benzophenone-2 sold by BASF under the trade name "Uvinul D50",
    [191] Benzophenone-3 or oxybenzone, sold under the trade name "Uvinul M40" by BASF,
    [192] Benzophenone-4 sold by BASF under the trade name "Uvinul MS4O",
    [193] Benzophenone-5,
    [194] Benzophenone-6 sold under the trade name "Helisorb 11" by Norquay,
    [195] Benzophenone-8 sold under the trade name "Spectra-Sorb UV-24" by American Cyanamid,
    [196] Benzophenone-9 sold by BASF under the trade name "Uvinul DS-49",
    [197] Benzophenone-12,
    [198] Benzylidene camphor derivatives:
    [199] 3-benzylidene camphor made by Chimex under the trade name "Mexoryl SD",
    [200] Benzylidene camphor sulfonic acid made by Chimex under the trade name "Mexoryl SL",
    [201] Camphor benzalkonium methosulfate manufactured by Chimex under the trade name "Mexoryl SO",
    [202] Terephthalidene dicamphor sulfonic acid made by Chimex under the trade name "Mexoryl SX",
    [203] Polyacrylamidomethyl benzylidene camphor made by Chimex under the trade name "Mexoryl SW",
    [204] Benzimidazole Derivatives:
    [205] Phenylbenzimidazole sulfonic acid, especially those sold under the trade name "Eusolex 232" by Merck,
    [206] Disodium phenyl dibenzimidazole tetrasulfonate sold by Haarmann and Reimer under the trade name "Neo Heliopan AP",
    [207] Triazine Derivatives:
    [208] Anisotriazine sold under the trade name "Tinosorb S" by Ciba Specialty Chemicals,
    [209] Ethylhexyl triazone, in particular sold under the trade name "Uvinul T150" by BASF,
    [210] Diethylhexyl butamido triazone sold by Sigma 3V under the trade name "Uvasorb HEB",
    [211] 2,4,6-tris (diisobutyl 4'-aminobenzalmalonate) -s-triazine,
    [212] Phenylbenzotriazole Derivatives:
    [213] -Drometrizol trisiloxane sold under the trade name "Silatrizole" by Rhodia Chimie,
    [214] Methylenebis (benzotriazolyltetramethylbutylphenol) sold as a solid form by trade name "Mixxim BB / 100" by Fairmount Chemical or as a micronized form in an aqueous dispersion by trade name "Tinosorb M" by Ciba Specialty Chemicals,
    [215] Anthranilic acid derivatives:
    [216] Menthyl anthranilate sold by Haarmann and Reimer under the trade name "Neo Heliopan MA",
    [217] Imidazoline Derivatives:
    [218] Ethylhexyl dimethoxybenzylidene dioxoimidazoline propionate,
    [219] Benzalmalonate Derivatives:
    [220] Polyorganosiloxanes having benzalmalonate functionality, marketed under the trade name "Parsol SLX" by Hoffmann-LaRoche,
    [221] 4,4-diarylbutadiene derivatives:
    [222] 1,1-dicarboxy (2,2'-dimethyl-propyl) -4,4-diphenylbutadiene,
    [223] And mixtures thereof.
    [224] More particularly preferred soluble organic UV blockers are selected from the following compounds:
    [225] Ethylhexyl salicylate,
    [226] Ethylhexyl methoxycinnamate,
    [227] -Octocrylene,
    [228] Phenylbenzimidazole sulfonic acid,
    [229] Benzophenone-3,
    [230] Benzophenone-4,
    [231] Benzophenone-5,
    [232] 4-methylbenzylidene camphor,
    [233] Disodium phenyl dibenzimidazole tetrasulfonate,
    [234] -Anisotriazine,
    [235] Ethylhexyl triazone,
    [236] Diethylhexyl butamido triazone,
    [237] 2,4,6-tris (diisobutyl 4'-aminobenzalmalonate) -s-triazine,
    [238] Methylenebis (benzotriazolyltetramethylbutylphenol),
    [239] And mixtures thereof.
    [240] The cosmetic composition according to the invention also comprises a pigment, or alternatively a nanopigment formed from a coated or uncoated metal oxide (average size of primary particles: generally 5 nm to 100 nm, preferably 10 nm to 50 nm). And may contain, for example, nanopigments formed from titanium oxide, iron oxide, zinc oxide, zirconium oxide or cerium oxide (crystalline or rutile and / or anatase), all of which are known so far. It is a photoprotectant. Conventional coating agents are also alumina and / or aluminum stearate. Such coated and uncoated metal oxide nanopigments are described in particular in patent applications EP-A-0 518 772 and EP-A-0 518 773.
    [241] The composition according to the invention may also comprise artificial tanning agents and / or browning agents (self-tanning agents) of the skin, for example dihydroxyacetone (DHA).
    [242] The compositions of the present invention may further contain conventional cosmetic auxiliaries, in particular selected from: fatty substances, organic solvents, ionic or nonionic thickeners, softeners, antioxidants, free radical breakers, brighteners, stabilizers, emollients (emollient), silicones, α-hydroxy acids, antifoams, wetting agents, vitamins, insect repellents, flavorings, preservatives, surfactants, anti-inflammatory agents, P substance antagonists, fillers, polymers, propellants, basic or acidic agents, colorants or cosmetics, Any other component commonly used in the manufacture of sunscreen compositions, especially in the form of emulsions.
    [243] Fatty substances may consist of oils or waxes or mixtures thereof. The term "oil" is understood to mean a compound that is liquid at ambient temperature. The term "wax" is understood to mean a compound that is solid or substantially solid at ambient temperature and whose melting point is generally above 35 ° C. They also include linear or cyclic fatty acids, fatty alcohols and fatty acid esters, for example derivatives of benzoic acid, trimellitic acid and hydroxybenzoic acid.
    [244] As oils, mention may be made of: mineral oils (liquid paraffin); Vegetable oils (sweet almonds, macadamia, currant or jojoba oil); Synthetic oils such as perhydrosqualene, fatty alcohols, acids or esters (eg C 12 -C 15 sold under the trade name “Finsolv TN” by Finetex, including those of capric acid / caprylic acid) Alkyl benzoate, octyl palmitate, isopropyl ranolate or triglycerides), or oxyethylene or oxypropylene based esters and ethers; Silicone oils (cyclomethicone, polydimethylsiloxane or PDMS); Fluorinated oils; Or polyalkylene.
    [245] As the waxy compound, mention may be made of paraffin wax, carnauba wax, beeswax or hydrogenated castor oil.
    [246] Of course, those skilled in the art will appreciate that the beneficial properties inherently added to the composition according to the invention, in particular the synergistic effect of the blocking index, are not damaged or substantially damaged by the expected addition (s). Additional compounds and / or amounts thereof will be carefully selected.
    [247] The compositions of the present invention can be prepared according to techniques known to those skilled in the art, in particular for the purpose of preparing emulsions of oil-in-water or water-in-oil type.
    [248] The compositions are particularly useful in the form of simple or complex emulsions (O / W, W / O, O / W / O or W / O / W), for example creams, milks, gels or cream gels, powders or solid tubes. It may be provided in the form, optionally packaged as an aerosol, and may be provided in the form of a foam or a spray.
    [249] If the emulsion is suspected, the latter aqueous phase may comprise a nonionic foam dispersion prepared according to known methods (Bangham, Standish and Watkins, J. Mol. Biol., 13, 238 (1965), FR). 2 315 991 and FR 2 416 008).
    [250] The cosmetic composition of the present invention can be used as a composition, sunscreen composition or makeup product that protects the epidermis or hair against ultraviolet rays.
    [251] When the cosmetic composition according to the invention is used for the protection of the human epidermis against ultraviolet light or as a sunscreen composition, it is in the form of a suspension or dispersion in the solvent or fatty substance, in the form of a nonionic foam dispersion or in the form of an emulsion, preferably Oil-in-water, for example, cream or milk, ointment, gel, cream gel, solid tube, powder, stick, aerosol foam or spray form.
    [252] When the cosmetic composition according to the invention is used for protection of hair against ultraviolet rays, it can be provided in the form of shampoos, lotions, gels, emulsions or nonionic foam dispersions, for example before and after shampooing, dyeing or bleaching. Rinse-out compositions, styling or treating lotions or styling or treating gels, blow drying or hair setting lotions or gels, perm or straight, hair applied before, during or after perm or hair straightening The composition for dyeing or bleaching can be configured.
    [253] Anhydrous or aqueous, paste or solid when the composition is used as an eyelash, eyebrow or skin cosmetic product, such as epidermal treatment cream, foundation, lipstick tube, eyeshadow, face powder, mascara or eyeliner In the form of oil-in-water or water-in-oil emulsions, nonionic foam dispersions, or suspensions.
    [254] For sunscreen formulations according to the invention which represent a carrier in oil-in-water emulsion, the aqueous phase (in particular comprising a hydrophilic blocker), by indication, is generally from 50 to 95% by weight, preferably to the total formulation. 70 to 90% by weight, the oil phase (particularly including lipophilic blockers) represents 5 to 50% by weight, preferably 10 to 30% by weight, relative to the total formulation, and (co) emulsifier (s) Represents 0.5 to 20% by weight, preferably 2 to 10% by weight relative to the total formulation.
    [255] The subject matter of the present invention, shown at the beginning of the specification, is the use of a composition as defined above in the preparation of a make-up or skin composition for the purpose of protecting the skin and / or hair against ultraviolet radiation, in particular solar radiation.
    [256] Specific but non-limiting examples illustrating the invention will now be provided.
    [257] Example
    [258] Example 1
    [259] 80/20 mixture of cetearyl alcohol and oxyethylene-based (33 EO) cetearyl alcohol (Sinnowax AO, Henkel)7 g Glycerol Mono- and Distearate Mixtures (Cerasynt SD-V, ISP)2 g Cetyl alcohol1.5 g Polydimethylsiloxane (Dow Corning 200 Fluid, Dow Corning)1 g C 12 -C 15 alkyl benzoate (Witconol TN, Witco)20 g n-hexyl 2- (4-diethylamino-2-hydroxybenzoyl) benzoate2 g Glycerol10 g Butyl Methoxydibenzoylmethane (Parsol 1789, Hoffmann-LaRoche)2 g Drometrizole Trisiloxane (Silatrizole, Rhodia Chimie)2 g PreservativeQuantity Demineralized water100 g
    [260] Example 2
    [261] Glycerol Mono / Distearate / Polyethylene Glycol (100 EO) Stearate Mixture (Arlacel 165 FL, ICI)2 g Stearyl Alcohol (Lanette 18, Henkel)1 g Palm oil stearic acid (Stearine TP, Stearinerie Dubois)2.5 g Polydimethylsiloxane (Dow Corning 200 Fluid, Dow Corning)0.5 g C 12 / C 15 alkyl benzoate (Witconol TN, Witco)18 g Triethanolamine0.5 g n-hexyl 2- (4-diethylamino-2-hydroxybenzoyl) benzoate2.5 g Drometrisol trisiloxane (Silatrizole, Rhodia Chimie)2 g Butyl Methoxydibenzoylmethane (Parsol 1789, Hoffmann-LaRoche)1.5 g Glycerol5 g Hexadecyl phosphate, potassium salt (Amphisol K, Hoffmann-LaRoche)1 g Polyacrylic Acid (Synthalen K, 3V)0.3 g Hydroxypropyl methyl cellulose (Methocel F4M, Dow Chemical)0.1 g TriethanolamineSuitable pH 7 PreservativeQuantity Demineralized water100 g
    [262] Significantly improved due to synergistic effects with a combination of three specific groups of blocker compounds, namely (1) dibenzoylmethane derivatives, (2) benzotriazole silicone derivatives and (3) specific amino substituted 2-hydroxybenzophenone derivatives It is possible to obtain a sunscreen composition exhibiting a sunscreen index UV-A PPD , which is significantly improved with such a combination, and in any case even higher than can be obtained with any blocker used alone. It is possible to obtain sunscreen compositions having a blocking index UV-A PPD .
    权利要求:
    Claims (36)
    [1" claim-type="Currently amended] A cosmetic composition, such as a sunscreen cosmetic composition, comprising: a cosmetically acceptable carrier;
    (i) at least one silicone derivative having a benzotriazole functional group as a first blocking agent;
    (ii) as a second blocking agent, at least one dibenzoylmethane derivative; And
    (iii) as a third blocker, at least one amino substituted 2-hydroxybenzophenone derivative of formula (III)
    [Formula III]
    (In the meal,
    R 1 and R 2 are the same or different and represent a hydrogen atom, a C 1 -C 20 alkyl radical, a C 2 -C 10 alkenyl radical, a C 3 -C 10 cycloalkyl radical or a C 3 -C 10 cycloalkenyl radical Represent;
    R 1 and R 2 may also form a 5- or 6-membered ring with the nitrogen atom bonded thereto;
    R 3 and R 4 are the same or different and are C 1 -C 20 alkyl radicals, C 2 -C 10 alkenyl radicals, C 3 -C 10 cycloalkyl radicals, C 3 -C 10 cycloalkenyl radicals, C 1- C 12 alkoxy radical, (C 1 -C 20 ) alkoxycarbonyl radical, C 1 -C 12 alkylamino radical, di (C 1 -C 12 ) alkylamino radical, aryl radical which may be substituted or heteroaryl, or car A water soluble substituent selected from a carboxylate group, a sulfonate group or an ammonium moiety;
    X 'represents a hydrogen atom or a COOR 5 or CONR 6 R 7 group;
    R 5 , R 6 and R 7 are the same or different and represent a hydrogen atom, a C 1 -C 20 alkyl radical, a C 2 -C 10 alkenyl radical, a C 3 -C 10 cycloalkyl radical, a C 3 -C 10 cycloal A kenyl radical, a-(Y'O) o- Z 'group or an aryl group;
    Y 'represents-(CH 2 ) 2 -,-(CH 2 ) 3 -,-(CH 2 ) 4 -or -CH- (CH 3 ) -CH 2- ;
    Z 'represents -CH 2 -CH 3 , -CH 2 CH 2 CH 3 , -CH 2 CH 2 CH 2 CH 3 , or -CH (CH 3 ) -CH 3 ;
    m 'is an integer from 0 to 3;
    n 'is an integer from 0 to 3;
    o is an integer from 1 to 2).
    [2" claim-type="Currently amended] The composition of claim 1, wherein the first, second and third blockers are present in the composition at a rate that produces synergistic activity against the provided sun block index UV-A PPD .
    [3" claim-type="Currently amended] 3. The silane, polyorganosiloxane or silane and polyorganosiloxane according to claim 1, wherein the silicone derivative having a benzotriazole functional group has a benzotriazole functional group comprising at least one unit of formula (1) Compositions selected from:
    [Formula 1] O (3-a) / 2 Si (R 7 ) a -G
    [In the meal,
    R 7 represents halogenated or non-halogenated C 1 -C 10 alkyl radical or phenyl radical or trimethylsilyloxy radical,
    a is an integer from 0 to 3,
    The symbol G represents a monovalent radical bonded directly to the silicon atom corresponding to formula (2):
    [Formula 2]
    (In the meal,
    -Y is the same or different and is selected from a C 1 -C 8 alkyl radical, a halogen and a C 1 -C 4 alkoxy radical, in the latter case two adjacent Y radicals on the same aromatic nucleus have an alkylidene group having from 1 to It is understood that an alkylidenedioxy group including 2 can be formed,
    -X represents O or NH,
    Z represents hydrogen or a C 1 -C 4 alkyl radical,
    n is an integer from 0 to 3,
    m is 0 or 1,
    -p is an integer from 1 to 10 or less).
    [4" claim-type="Currently amended] The composition according to claim 1 or 2, wherein the silicone derivative having a benzotriazole functional group corresponds to the formula (5) or (6):
    [Formula 5]
    or
    [Formula 6]
    [In the meal,
    R 7 is the same or different and is selected from C 1 -C 10 alkyl, phenyl, 3,3,3-trifluoropropyl and trimethylsilyloxy radicals and at least 80% of the number of R 7 radicals are methyl,
    D is the same or different and is selected from a R 7 radical and a G radical,
    -r is an integer from 0 to 50 or less, s is an integer from 0 to 20 or less, and if s = 0, at least one of the two symbols D represents G,
    -u is an integer of 1 to 6 or less, t is an integer of 0 to 10 or less, t + u is understood to be 3 or more,
    The symbol G corresponds to formula (2) as defined in claim 3].
    [5" claim-type="Currently amended] The composition according to claim 4, wherein the silicone derivative having a benzotriazole functional group corresponds to formula (7):
    [Formula 7]
    [In the meal,
    r is 0 to 10, s is 1 to 10,
    E is a divalent radical ].
    [6" claim-type="Currently amended] 6. A composition according to claim 5, wherein the silicone derivative having a benzotriazole functional group is dromethazole trisiloxane of the formula:

    [7" claim-type="Currently amended] 3. A composition according to claim 1 or 2, wherein the silicone derivative having benzotriazole functional groups is present in an amount of from 0.5 to 15% by weight, relative to the total weight of the composition.
    [8" claim-type="Currently amended] The composition of claim 1 or 2, wherein the dibenzoylmethane derivative is selected from:
    2-methyldibenzoylmethane,
    4-methyldibenzoylmethane,
    4-isopropyldibenzoylmethane,
    4-tert-butyldibenzoylmethane,
    2,4-dimethyldibenzoylmethane,
    2,5-dimethyldibenzoylmethane,
    4,4'-diisopropyldibenzoylmethane,
    4,4'-dimethoxydibenzoylmethane,
    4-tert-butyl-4'-methoxydibenzoylmethane,
    2-methyl-5-isopropyl-4'-methoxydibenzoylmethane,
    2-methyl-5-tert-butyl-4'-methoxydibenzoylmethane,
    2,4-dimethyl-4'-methoxydibenzoylmethane,
    2,6-dimethyl-4-tert-butyl-4'-methoxydibenzoylmethane.
    [9" claim-type="Currently amended] 9. The composition of claim 8, wherein the dibenzoylmethane derivative is 4-tert-butyl-4'-methoxydibenzoylmethane.
    [10" claim-type="Currently amended] 9. The composition of claim 8 wherein the dibenzoylmethane derivative is 4-isopropyldibenzoylmethane.
    [11" claim-type="Currently amended] The composition according to claim 1 or 2, wherein the dibenzoylmethane derivative is present in an amount of 0.5 to 15% by weight, relative to the total weight of the composition.
    [12" claim-type="Currently amended] A composition according to claim 1 or 2, wherein the amino substituted 2-hydroxybenzophenone derivative (s) of formula (III) is selected from those of formula (IIIa):
    [Formula IIIa]
    (In the meal,
    R 1 and R 2 are the same or different and represent a hydrogen atom or a C 1 -C 12 alkyl radical or form a 5- or 6-membered ring with the nitrogen atom bonded thereto;
    X 'represents COOR 5 or CONR 6 R 7 ;
    R 5 represents a hydrogen atom, a C 1 -C 12 alkyl radical or a C 3 -C 6 cycloalkyl radical;
    R 6 and R 7 are the same or different and represent a hydrogen atom, a C 1 -C 12 alkyl radical or a C 5 -C 6 cycloalkyl radical).
    [13" claim-type="Currently amended] 13. The composition of claim 12, wherein the compound of formula (IIIa) is a compound as follows:
    R 1 and R 2 are the same or different and represent a C 1-4 alkyl radical such as ethyl;
    R 5 represents a C 3 -C 8 alkyl radical;
    R 6 and R 7 are the same or different and represent a C 1 -C 8 alkyl radical.
    [14" claim-type="Currently amended] The composition of claim 1 or 2, wherein the amino substituted 2-hydroxybenzophenone derivative (s) of formula (III) is selected from those of formula (IIIb):
    [Formula IIIb]
    [In the meal,
    R 1 and R 2 are the same or different and represent a C 1 -C 12 alkyl radical or form a 5- or 6-membered ring with the nitrogen atom to which they are attached.
    [15" claim-type="Currently amended] The composition of claim 14 wherein the compound of formula (IIIb) is
    4-diethylamino-2-hydroxyphenyl phenyl ketone,
    4-pyrrolidino-2-hydroxyphenyl phenyl ketone.
    [16" claim-type="Currently amended] A composition according to claim 1 or 2, wherein the amino substituted 2-hydroxybenzophenone derivative (s) of formula (III) is selected from those of formula (IIIc):
    [Formula IIIc]
    [In the meal,
    R 1 and R 2 are the same or different and represent a hydrogen atom or a C 1 -C 8 alkyl radical or together with the nitrogen atom to which they are attached form a 5- or 6-membered ring;
    R 5 represents a hydrogen atom, a C 1 -C 12 alkyl radical or a C 3 -C 6 cycloalkyl radical.
    [17" claim-type="Currently amended] The composition of claim 16, wherein the compound of formula (IIIc) is selected from:
    2- (4-pyrrolidino-2-hydroxybenzoyl) benzoate
    Methyl 2- (4-diethylamino-2-hydroxybenzoyl) benzoate
    2-ethylhexyl 2- (4-diethylamino-2-hydroxybenzoyl) benzoate
    Cyclohexyl 2- (4-diethylamino-2-hydroxybenzoyl) benzoate
    n-hexyl 2- (4-diethylamino-2-hydroxybenzoyl) benzoate
    [lacuna] 2- (4-dibutylamino-2-hydroxybenzoyl) benzoate
    Methyl 2- (4-dibutylamino-2-hydroxybenzoyl) benzoate
    Isobutyl 2- (4-dibutylamino-2-hydroxybenzoyl) benzoate.
    [18" claim-type="Currently amended] 18. The composition of claim 17, wherein the compound of formula (IIIc) is n-hexyl 2- (4-diethylamino-2-hydroxybenzoyl) benzoate.
    [19" claim-type="Currently amended] 3. The amino substituted 2-hydroxybenzophenone derivative (s) of formula (III) are present in a ratio of preferably 0.1 to 20% by weight relative to the total weight of the composition. Composition.
    [20" claim-type="Currently amended] 20. The composition of claim 19, wherein the amino substituted 2-hydroxybenzophenone derivative (s) of formula (III) are present in a ratio preferably in the range of 0.1 to 20% by weight relative to the total weight of the composition.
    [21" claim-type="Currently amended] 21. The composition of claim 20, wherein the amino substituted 2-hydroxybenzophenone derivative (s) of formula (III) are present in a ratio ranging from 0.5 to 10% by weight relative to the total weight of the composition.
    [22" claim-type="Currently amended] The composition of claim 1 or 2, further comprising UV-A, UV-B or other organic blocker active in the UV-A and UV-B regions.
    [23" claim-type="Currently amended] The composition of claim 22, wherein the additional organic UV blocker (s) are selected from:
    Anthranilates; Cinnamic acid derivatives; Salicylic acid derivatives; Camphor derivatives; Triazine derivatives; Benzophenone derivatives other than those of the formula (III); β, β-diphenylacrylate derivatives; Benzotriazole derivatives; Benzalmalonate derivatives; Benzimidazole derivatives; Imidazoline; Bisbenzoazolyl derivatives; p-aminobenzoic acid (PABA) derivatives; Methylenebis (hydroxyphenylbenzotriazole) derivatives; Barrier polymers and barrier silicones other than benzotriazole silicone derivatives; And dimers derived from α-alkylstyrene; 4,4-diarylbutadiene derivatives and mixtures thereof.
    [24" claim-type="Currently amended] The composition of claim 23, wherein the organic UV blocker (s) are selected from the following compounds:
    Ethylhexyl salicylate,
    Butyl methoxydibenzoylmethane,
    Ethylhexyl methoxycinnamate,
    -Octocrylene,
    Phenylbenzimidazole sulfonic acid,
    Terephthalylidene dicamphor sulfoic acid,
    Benzophenone-3,
    Benzophenone-4,
    Benzophenone-5,
    4-methylbenzylidene camphor,
    Disodium phenyl dibenzimidazole tetrasulfonate,
    -Anisotriazine,
    Ethylhexyl triazone,
    Diethylhexyl butamido triazone,
    2,4,6-tris (diisobutyl 4'-aminobenzalmalonate) -s-triazine,
    Methylenebis (benzotriazolyltetramethylbutylphenol),
    1,1-dicarboxy (2,2'-dimethyl-propyl) -4-4-diphenylbutadiene
    And mixtures thereof.
    [25" claim-type="Currently amended] The composition of claim 1 or 2, further comprising a coated or uncoated metal oxide pigment or nanopigment.
    [26" claim-type="Currently amended] 26. The composition of claim 25, wherein the pigment or nanopigment is selected from coated or uncoated titanium oxide, zinc oxide, iron oxide, zirconium oxide or cerium oxide, and mixtures thereof.
    [27" claim-type="Currently amended] The composition of claim 1 or 2, further comprising at least one artificial tanning agent, browning agent or tanning agent and browning agent of the skin.
    [28" claim-type="Currently amended] The composition of claim 1 or 2, further comprising one or more adjuvants selected from:
    Fatty substances, organic solvents, ionic or nonionic thickeners, softeners, antioxidants, free radical destroyers, varnishes, stabilizers, emollients, silicones, α-hydroxy acids, antifoams, wetting agents, vitamins, insect repellents, flavorings , Preservatives, surfactants, anti-inflammatory agents, P substance antagonists, fillers, polymers, propellants, basic or acidic agents, or colorants.
    [29" claim-type="Currently amended] The method according to claim 1 or 2, which is provided in the form of a nonionic foam dispersion, an emulsion such as an oil-in-water emulsion, cream, milk, gel, cream gel, suspension, dispersion, powder, solid tube, foam or spray, A composition for protection of the epidermis or a sunscreen composition.
    [30" claim-type="Currently amended] The composition according to claim 1 or 2, which is provided in anhydrous or aqueous, paste or solid form, in the form of an emulsion, suspension or dispersion and is for eyelashes, eyebrows or skin cosmetics.
    [31" claim-type="Currently amended] The composition according to claim 1 or 2, which is provided in the form of a shampoo, lotion, gel, emulsion or nonionic foam dispersion, aimed at protecting the hair against ultraviolet rays.
    [32" claim-type="Currently amended] The composition according to claim 1 or 2, which is used for the preparation of cosmetics or skin compositions for the purpose of protecting the skin, hair or skin and hair against ultraviolet radiation such as solar radiation.
    [33" claim-type="Currently amended] For the purpose of obtaining a synergistic effect on the provided sunscreen index UV-A PPD, it contains at least one benzotriazole silicone derivative blocker and at least one dibenzoylmethane derivative blocker, and contains skin, against ultraviolet radiation such as solar radiation, A method of using an amino substituted 2-hydroxybenzophenone derivative as defined in claim 1, in the preparation of a cosmetic or skin composition for the purpose of protecting hair or skin and hair.
    [34" claim-type="Currently amended] 8. A composition according to claim 7, wherein the silicone derivative having benzotriazole functional groups is present in an amount of from 1 to 10% by weight, relative to the total weight of the composition.
    [35" claim-type="Currently amended] 12. The composition of claim 11, wherein the dibenzoylmethane derivative is present in an amount of from 1 to 10% by weight, relative to the total weight of the composition.
    [36" claim-type="Currently amended] 36. The composition of claim 35, wherein the dibenzoylmethane derivative is present in an amount of from 2 to 8 weight percent, relative to the total weight of the composition.
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    同族专利:
    公开号 | 公开日
    FR2833167A1|2003-06-13|
    BR0207143A|2003-09-30|
    AU2002302149A1|2003-06-19|
    CA2412803A1|2003-06-07|
    AU2002302149B2|2004-05-06|
    EP1323411A1|2003-07-02|
    CN1425366A|2003-06-25|
    US6627179B2|2003-09-30|
    JP2003171251A|2003-06-17|
    FR2833167B1|2004-05-21|
    US20030157038A1|2003-08-21|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    2001-12-07|Priority to FR0115857A
    2001-12-07|Priority to FR0115857
    2002-12-06|Application filed by 로레알
    2003-06-18|Publication of KR20030047812A
    优先权:
    申请号 | 申请日 | 专利标题
    FR0115857A|FR2833167B1|2001-12-07|2001-12-07|Antisolar cosmetic compositions based on a synergistic mixture of filters and uses|
    FR0115857|2001-12-07|
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