US20020085981A1 - Benzoxazole derivatives for use in cosmetic compositions and for stabilizing synthetic polymers - Google Patents
Benzoxazole derivatives for use in cosmetic compositions and for stabilizing synthetic polymers Download PDFInfo
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- US20020085981A1 US20020085981A1 US09/777,684 US77768401A US2002085981A1 US 20020085981 A1 US20020085981 A1 US 20020085981A1 US 77768401 A US77768401 A US 77768401A US 2002085981 A1 US2002085981 A1 US 2002085981A1
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- 239000000203 mixture Substances 0.000 title claims abstract description 37
- 239000002537 cosmetic Substances 0.000 title claims abstract description 24
- 229920001059 synthetic polymer Polymers 0.000 title claims abstract description 9
- 230000000087 stabilizing effect Effects 0.000 title claims 2
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical class C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 title description 5
- 150000001875 compounds Chemical class 0.000 claims description 67
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- 230000000475 sunscreen effect Effects 0.000 claims description 19
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 12
- 229920000642 polymer Polymers 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 8
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 7
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- 239000003381 stabilizer Substances 0.000 claims description 7
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- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
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- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- CNHQWLUGXFIDAT-UHFFFAOYSA-N dioctyl 2-hydroxybutanedioate Chemical compound CCCCCCCCOC(=O)CC(O)C(=O)OCCCCCCCC CNHQWLUGXFIDAT-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920002549 elastin Polymers 0.000 description 1
- 239000003792 electrolyte Chemical class 0.000 description 1
- 239000003974 emollient agent Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- UVCJGUGAGLDPAA-UHFFFAOYSA-N ensulizole Chemical compound N1C2=CC(S(=O)(=O)O)=CC=C2N=C1C1=CC=CC=C1 UVCJGUGAGLDPAA-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- YQEMORVAKMFKLG-UHFFFAOYSA-N glycerine monostearate Natural products CCCCCCCCCCCCCCCCCC(=O)OC(CO)CO YQEMORVAKMFKLG-UHFFFAOYSA-N 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- SVUQHVRAGMNPLW-UHFFFAOYSA-N glycerol monostearate Natural products CCCCCCCCCCCCCCCCC(=O)OCC(O)CO SVUQHVRAGMNPLW-UHFFFAOYSA-N 0.000 description 1
- 239000000118 hair dye Substances 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000887 hydrating effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000000338 in vitro Methods 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- SJOXEWUZWQYCGL-DVOMOZLQSA-N menthyl salicylate Chemical compound CC(C)[C@@H]1CC[C@@H](C)C[C@H]1OC(=O)C1=CC=CC=C1O SJOXEWUZWQYCGL-DVOMOZLQSA-N 0.000 description 1
- 229960004665 menthyl salicylate Drugs 0.000 description 1
- LXCFILQKKLGQFO-UHFFFAOYSA-N methylparaben Chemical compound COC(=O)C1=CC=C(O)C=C1 LXCFILQKKLGQFO-UHFFFAOYSA-N 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 230000003020 moisturizing effect Effects 0.000 description 1
- 238000007040 multi-step synthesis reaction Methods 0.000 description 1
- 125000004998 naphthylethyl group Chemical group C1(=CC=CC2=CC=CC=C12)CC* 0.000 description 1
- 125000004923 naphthylmethyl group Chemical group C1(=CC=CC2=CC=CC=C12)C* 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- FMJSMJQBSVNSBF-UHFFFAOYSA-N octocrylene Chemical compound C=1C=CC=CC=1C(=C(C#N)C(=O)OCC(CC)CCCC)C1=CC=CC=C1 FMJSMJQBSVNSBF-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004344 phenylpropyl group Chemical group 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 231100000760 phototoxic Toxicity 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920005862 polyol Chemical class 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Chemical class 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- SJOXEWUZWQYCGL-UHFFFAOYSA-N salicylic acid menthyl ester Natural products CC(C)C1CCC(C)CC1OC(=O)C1=CC=CC=C1O SJOXEWUZWQYCGL-UHFFFAOYSA-N 0.000 description 1
- 239000002453 shampoo Substances 0.000 description 1
- 201000000849 skin cancer Diseases 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- CXVGEDCSTKKODG-UHFFFAOYSA-N sulisobenzone Chemical compound C1=C(S(O)(=O)=O)C(OC)=CC(O)=C1C(=O)C1=CC=CC=C1 CXVGEDCSTKKODG-UHFFFAOYSA-N 0.000 description 1
- 230000037072 sun protection Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- OULAJFUGPPVRBK-UHFFFAOYSA-N tetratriacontan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCO OULAJFUGPPVRBK-UHFFFAOYSA-N 0.000 description 1
- 238000002560 therapeutic procedure Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
- A61Q1/02—Preparations containing skin colorants, e.g. pigments
- A61Q1/04—Preparations containing skin colorants, e.g. pigments for lips
- A61Q1/06—Lipsticks
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
- A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34922—Melamine; Derivatives thereof
Definitions
- the present invention relates to benzoxazole derivatives and their use in cosmetic compositions and in the stabilization of synthetic polymers.
- sun radiations ranging from 290 to 400 nm are noxious for the organic materials, among which cutaneous tissue too.
- prolonged exposition to sun radiation is considered to be the main cause of the development of degenerative processes and of skin cancer forms.
- radiations of wavelength between 290 and 320 nm, so called UV-B radiations cause erythema and sunburns, whose severity depends on exposure length.
- UV-A the radiations ranging between 320 and 400 nm, so called UV-A, and responsible of skin tanning, can cause alterations and damages in the skin may not be disregarded, such as for example degenerative processes and even cancer forms; especially in case of sensible skins or in case of prolonged exposition to radiation.
- UV-A radiation other than causing damages to elastin and collagen, whose consequence is ageing of the skin can also be the cause of a number of phototoxic and photoallergic reactions.
- UV-B may be enhanced by the presence of UV-A (see: Willis et al.: Journal of Investigative Dermatology vol. 59, 416, 1072).
- sunscreens or UV filters capable of absorbing, at least partially, UV sunlight radiations, noxious effects on organic materials, in particular on synthetic polymers and on human skin can be prevented or at least attenuate and ageing of the same showed down.
- sunscreens or UV filters capable of absorbing, at least partially, UV sunlight radiations, noxious effects on organic materials, in particular on synthetic polymers and on human skin can be prevented or at least attenuate and ageing of the same showed down.
- protective agents a number of substances have been studied and experimented and a wide patent literature exists on this matter, wherein compounds belonging to different chemical classes capable of absorbing in the UV zone of sun radiation and particularly that between 290 and 360 nm are proposed.
- 2-Hydroxy-4-methoxybenzophenone is an often used commercial product, whose maximum absorption in the UV-A zone, at about 325 nm, is too low to give an effective protection, moreover its solubility in solvents usually used in cosmetics is very low thus making difficult its handling.
- Another compound presently used in practice is a dibenzoylmethane derivative, but not only it is incompatible with many ingredients usually employed for cosmetic compositions, but also has the severe defect of not being sufficiently photostable (Int. J. Cosm. Science 10, 53 1988), therefore the sun formulations containing these compounds may not guarantee a sufficient protection from UV-A since the sunscreens are either too weak (such as the benzophenone derivative) or are degraded too quickly by the radiation itself (such as the dibenzoylmethane derivative).
- a high solubility of UV filters in the cosmetic ingredients is, in fact, mandatory for the preparation of formulaitons having optimal sun protection factors.
- R and R1 which can be the same or different, are hydrogen, straight or branched C1-C8 alkyl, —OR3 wherein R3 is a Cl-C4 alkyl group, —COOR4 wherein R4 is a straight or branched C1-C24 alkyl, a C7-C12 aralkyl or C5-C8 cycloalkyl group or a group of formula (II) or (III):
- A is straight or branched C1-C8 alkyl, C5-C8 cycloalkyl, C6-C10 aryl optionally substituted with one or more C1-C4 alkyl, R5 and R6 are independently hydrogen or methyl, n can have values of 1 to 10,
- R2 is independently straight or branched C1-C18 alkyl, C5-12 cycloalkyl, optionally substituted with 1 to 3 straight or branched C1-C4 alkyl groups; an ammonium group optionally substituted with 1 to 4 C1-C4 alkyl groups or a group of formula (II) or (III) and the —CO-X-R2 moiety can be at the ortho or meta positions,
- X is oxygen or NH.
- a first group of preferred compounds comprises those wherein R and R1 have the meanings defined above and R2 is a straight or branched C1-C 18 alkyl group.
- a second group of preferred compounds comprises those wherein R and R1 have the meanings defined above and R2 is a group of formula (III).
- a third group of preferred compounds comprises those wherein R and R1 have the meanings defined above, R2 is a straight or branched C2-C12 alkyl residue and X is oxygen.
- alkyl groups are methyl, propyl, butyl, hexyl, heptyl, octyl, decyl, dodecyl, pentadecyl, heptadecyl, eicosanyl and the branched isomers thereof, optionally containing oxygen bridges in the form of ether groups.
- Particularly preferred are 2-octyldodecyl, 2-ethyldecyl, tert-butyl, 2-ethylhexyl, 1,1,3,3-tetramethylbutyl, isobutyl groups.
- aralkyl groups are benzyl, phenylethyl, phenylpropyl, phenylhexyl, naphthylmethyl, naphthylethyl and the isomers thereof.
- Aryl is phenyl or naphthyl, any substitutions with alkyl groups, such as methyl, ethyl, isopropyl, tert-butyl, can be at the ortho, meta and para positions and on the naphthyl fused ring.
- cycloalkyl groups are cyclopentyl, cyclohexyl, cyclooctyl.
- the compounds according to the present invention absorb UV radiations intensely and particularly in the UV-A range, therefore small amounts of these compounds are sufficient to obtain cosmetic compositions with high SPF (Sun Protecting factor).
- SPF is directly related to the specific extinction and is determined in vivo on man or according to a in vitro method as described by B. Diffey J. Robson in J. Soc. Cosmet. Chem. 40, 127-133 (1989).
- the compounds of formula (I), also depending on the R 2 -R 4 substituents show a wide absorption, which is not only confined in the UV-A range, but also extended to the UV-B range. Therefore, they can provide protection against both UV-A and UV-B radiations.
- a further object of the present invention are cosmetic compositions containing at least a compound of formula (I).
- R, R1, R2 and X have the meanings defined above, z is bromine or preferably chlorine.
- R, R1, R2, Z and X are as defined in formula (I).
- reaction between the compounds of formula (IV) and (VI) and between those of formula (V) and (VII) is carried out at a temperature ranging between 50 and 200° C., in suitable solvents, such as acetonitrile, ketones such as acetone, methylethyl ketone, ethers such as diisopropyl ether, tetrahydrofuran, dioxane, aliphatic or aromatic hydrocarbons, such as hexane, octane, cyclohexane, benzene, toluene, xylene or mixtures thereof, optionally in the presence of an acid acceptor, such as alkali or alkaline-earth hydroxide, alkali metal carbonates or bicarbonates.
- suitable solvents such as acetonitrile, ketones such as acetone, methylethyl ketone, ethers such as diisopropyl ether, tetrahydrofuran, dioxan
- the compounds of formula (I) are useful as sunscreens. Their protective activity on the skin from sun radiation is carried out by applying a suitable amount on the part of the skin which is exposed to the radiations.
- Suitable amounts for the application can be determined by those skilled in the art, depending on the specific extinction coefficient E 1 of the compound of formula (I). Said coefficient is an index of the protection efficacy.
- a further object of the present invention is represented by cosmetic compositions containing an effective amount of at least a compound of formula (I) as sunscreen in combination with conventional carriers and excipients.
- compositions can be of different types, for example in the form of solutions, lotions, water-in-oil or oil-in-water emulsions; or also in the form of gels, lipsticks, sprays.
- compositions according to the present invention can be prepared by admixing conventional ingredients, carriers and excipients such as oils, fats, emollients, hydrating agents, moisturizing agents, softening agents, preservatives, surfactants, thickening agents, antifoam agents, perfumes, pigments, dyes and the like such as alcohols, polyols, electrolytes, silicone derivatives.
- solvents are triglycerides of capric or caprylic acid, castor oil, esters of fatty acids with isopropanol, propylene glycol, glycerin, propylene glycol monomethyl or monoethyl or monobutyl ether, dioctyl malate.
- the present invention also comprises the protection of cosmetic compositions from UV radiation by using the compounds of formula (I), in case the cosmetic ingredients are liable to undergo unwanted degradation or colouring due to light, such as hair shampoos and lacquers, hairdress lotions, hair-dye compositions, make-up formulations, such as nail lacquers, foundations, lipsticks.
- Preferred cosmetic compositions are those for the protection of the skin from sun radiations.
- the cosmetic compositions of the present invention can contain one or more compounds of formula (I), in an amount comprised from 0.1 to 20%, preferably from 0.5 to 15% by weight with respect to the total weight of the composition.
- sunscreens in addition to the compounds of formula (I), also other sunscreens can be added, particularly those having a maximum absorption comprised from 290 to 320 nm.
- sunscreens according to the present invention can be carried out by means of cosmetic compositions containing one or more compounds of formula (I), optionally combined with one or more well-known sunscreens, such as those cited above.
- compositions containing the compounds of formula (I) of the invention are used for the treatment of skin, hair or for cosmetic make-up.
- the present invention also provides the use of compounds of formula (I) for the protection of synthetic polymers.
- polymeric materials which can be protected from UV radiation, include polyethylene, polypropylene, polystyrene, polybutadiene, polyisoprene and their copolymers, polyvinyl acetate and its copolymers, particularly with polyethylene, polyesters such as polyethylene terephthalate, polyamides such as Nylon 6 and Nylon 6,6, polyurethanes, polyacrylates, polymethacrylates, polyvinyl chloride.
- the compounds of formula (I) can be incorporated in polymers to be stabilized by means of any known method for mixing or blending additives to polymeric materials; for example, they can be mixed with the polymer in a suitable blender or mixer, or added in the form of solution or suspension in a suitable solvent such as methanol, ethanol, acetone, chloroform, then removing the solvent after mixing with the polymer, which can be in the form of powder, granulate or suspension or finally can be added to the polymer during the preparation of the same, for example in the last preparation step.
- a suitable solvent such as methanol, ethanol, acetone, chloroform
- the compounds of formula (I) can be also used in combination with other stabilizing agents and additives generally used for polymers, such as for example phenol-based antioxydants, phosphites, hindered amines and particularly those containing in their structure the 2,2,6,6-tetramethylpiperidine group, other types of UV-absorbers based on benzotriazoles or benzophenones, plastifiers, lubricants, flame retardants, titanium oxide.
- other stabilizing agents and additives generally used for polymers such as for example phenol-based antioxydants, phosphites, hindered amines and particularly those containing in their structure the 2,2,6,6-tetramethylpiperidine group, other types of UV-absorbers based on benzotriazoles or benzophenones, plastifiers, lubricants, flame retardants, titanium oxide.
- the amount of compounds of formula (I) necessary to an effective stabilization of the polymer depends on different factors, such as the kind and the characteristics of the polymer, the use to which it is intended, the intensity of the radiation, the duration of exposure and the presence, if any, of other stabilizing agents.
- an amount comprised from 0.01 to 5% by weight of the polymer, preferably from 0.05 to 2% will be sufficient.
- Example R m.p. ° C. 2 (CH3)3C— H 167-168 3 (CH3)3C— (CH3)3C— 168-169 4 CH3—CH2—(CH3)2—C— H 153-154
- Example 5 Operating as described in Example 5, the compounds listed in Table 2 were prepared: TABLE 2 Example R m.p. /° C. 6 151-152 7 206.5-208 8 195.5-196.5
- the fatty phase was heated to 80-90° C., the sunscreen of example 10 and 2-ethylhexyl-4-dimethylaminobenzoate were added, then the mixture was added to water, containing the hydrosoluble compounds, heated to 80-90° C. Warm-stirring was continued for 15-20 minutes. After slow cooling, perfume was added.
- Fatty acid triglycerids 20.0 g Cetystearyl alcohol 2.0 g Lanolin 4.0 g Cetyl alcohol 2.0 g Siliconic oil 0.4 g Compound of example 12 3.5 g Abiol (preservative by 3V SIGMA) 0.2 g Synthalen M (thickening agent by 3V SIGMA) 0.1 g Triethanolamine 0.15 g Perfume 0.3 g Distilled water q.s. to 100.0 g
- Synthalen M was dispersed in water, then triethanolamine, preservative, propylene glycol and ethanol mixture, in which the compound of example 14 had previously been dissolved, were added, followed by perfume.
- a base mixture was first prepared, consisting of: Beeswax 13.0 g Carnauba wax 7.5 g Lanolin 5.0 g Isopropyl myristate 8.0 g Mineral oil 3.0 g Castor oil 63.5 g
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- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Dermatology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Birds (AREA)
- Epidemiology (AREA)
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Abstract
Description
- The present invention relates to benzoxazole derivatives and their use in cosmetic compositions and in the stabilization of synthetic polymers.
- It is well known that sun radiations ranging from 290 to 400 nm are noxious for the organic materials, among which cutaneous tissue too. In fact, prolonged exposition to sun radiation is considered to be the main cause of the development of degenerative processes and of skin cancer forms. In particular, radiations of wavelength between 290 and 320 nm, so called UV-B radiations, cause erythema and sunburns, whose severity depends on exposure length.
- It was ascertained that also the radiations ranging between 320 and 400 nm, so called UV-A, and responsible of skin tanning, can cause alterations and damages in the skin may not be disregarded, such as for example degenerative processes and even cancer forms; especially in case of sensible skins or in case of prolonged exposition to radiation.
- It has also been demonstrated that the UV-A radiation other than causing damages to elastin and collagen, whose consequence is ageing of the skin, can also be the cause of a number of phototoxic and photoallergic reactions. Besides, the noxious action of UV-B may be enhanced by the presence of UV-A (see: Willis et al.: Journal of Investigative Dermatology vol. 59, 416, 1072).
- By means of the use of particular compounds or of compositions containing these particular compounds, so called sunscreens or UV filters, capable of absorbing, at least partially, UV sunlight radiations, noxious effects on organic materials, in particular on synthetic polymers and on human skin can be prevented or at least attenuate and ageing of the same showed down. As protective agents a number of substances have been studied and experimented and a wide patent literature exists on this matter, wherein compounds belonging to different chemical classes capable of absorbing in the UV zone of sun radiation and particularly that between 290 and 360 nm are proposed.
- Many compounds, such as for example derivatives of cinnamic acid, 4-aminobenzoic acid, benzylydenecamphor, benzophenone and diphenylcyanoacrylic acid are well known and widely used in cosmetic preparations for the protection from sunburns and erythema due to noxious UV-B radiation.
- Until recently the use of sunscreens for the protection from the UV-A radiation was practically unknown, other than some special cases of therapy. But recent studies show that also a continuous and intensive UV-A radiation can cause severe cutaneous damages, especially to persons having very sensible and delicate skin.
- For the protection against UV-A, really suitable products are not yet available, even if in the patent literature some compounds have been proposed, but in practice, the outcome of these compounds may not be considered sufficiently positive.
- 2-Hydroxy-4-methoxybenzophenone is an often used commercial product, whose maximum absorption in the UV-A zone, at about 325 nm, is too low to give an effective protection, moreover its solubility in solvents usually used in cosmetics is very low thus making difficult its handling.
- Another compound presently used in practice is a dibenzoylmethane derivative, but not only it is incompatible with many ingredients usually employed for cosmetic compositions, but also has the severe defect of not being sufficiently photostable (Int. J. Cosm. Science 10, 53 1988), therefore the sun formulations containing these compounds may not guarantee a sufficient protection from UV-A since the sunscreens are either too weak (such as the benzophenone derivative) or are degraded too quickly by the radiation itself (such as the dibenzoylmethane derivative).
- Better results were obtained with the benzoxazole derivatives disclosed in U.S. Pat. No. 5,744,127.
- However, the problems connected with the use of such UV sunscreens, particularly those concerning their solubility in the oily solvents conventionally used in cosmetic formulations, have not been solved.
- A high solubility of UV filters in the cosmetic ingredients is, in fact, mandatory for the preparation of formulaitons having optimal sun protection factors.
- It has now surprisingly been found that particular benzoxazole derivatives have such characteristics as to meet the present market requirements. In fact, in addition to good absorption, and therefore high protective efficiency in the zone between 320 and 360 nm, they also show good photostability, wide compatibility with the cosmetic ingredients and high solubility in the solvents usually employed in cosmetic compositions. The compounds according to the present invention have the following formula (I):
- wherein
-
- wherein A is straight or branched C1-C8 alkyl, C5-C8 cycloalkyl, C6-C10 aryl optionally substituted with one or more C1-C4 alkyl, R5 and R6 are independently hydrogen or methyl, n can have values of 1 to 10,
- R2 is independently straight or branched C1-C18 alkyl, C5-12 cycloalkyl, optionally substituted with 1 to 3 straight or branched C1-C4 alkyl groups; an ammonium group optionally substituted with 1 to 4 C1-C4 alkyl groups or a group of formula (II) or (III) and the —CO-X-R2 moiety can be at the ortho or meta positions,
- X is oxygen or NH.
- A first group of preferred compounds comprises those wherein R and R1 have the meanings defined above and R2 is a straight or branched C1-C 18 alkyl group.
- A second group of preferred compounds comprises those wherein R and R1 have the meanings defined above and R2 is a group of formula (III).
- A third group of preferred compounds comprises those wherein R and R1 have the meanings defined above, R2 is a straight or branched C2-C12 alkyl residue and X is oxygen.
- Examples of alkyl groups are methyl, propyl, butyl, hexyl, heptyl, octyl, decyl, dodecyl, pentadecyl, heptadecyl, eicosanyl and the branched isomers thereof, optionally containing oxygen bridges in the form of ether groups. Particularly preferred are 2-octyldodecyl, 2-ethyldecyl, tert-butyl, 2-ethylhexyl, 1,1,3,3-tetramethylbutyl, isobutyl groups.
- Examples of aralkyl groups are benzyl, phenylethyl, phenylpropyl, phenylhexyl, naphthylmethyl, naphthylethyl and the isomers thereof. Aryl is phenyl or naphthyl, any substitutions with alkyl groups, such as methyl, ethyl, isopropyl, tert-butyl, can be at the ortho, meta and para positions and on the naphthyl fused ring.
- Examples of cycloalkyl groups are cyclopentyl, cyclohexyl, cyclooctyl.
- The compounds according to the present invention absorb UV radiations intensely and particularly in the UV-A range, therefore small amounts of these compounds are sufficient to obtain cosmetic compositions with high SPF (Sun Protecting factor). SPF is directly related to the specific extinction and is determined in vivo on man or according to a in vitro method as described by B. Diffey J. Robson in J. Soc. Cosmet. Chem. 40, 127-133 (1989).
- Moreover, the compounds of formula (I), also depending on the R2-R4 substituents, show a wide absorption, which is not only confined in the UV-A range, but also extended to the UV-B range. Therefore, they can provide protection against both UV-A and UV-B radiations.
- It is therefore a further object of the invention the use of the compounds of formula (I) as sunscreens in cosmetic compositions and as photostabilizing agents for the protection of synthetic polymers.
- In particular, it is an object of the present invention the use of the compounds of formula (I) as sunscreens in the cosmetic treatment of the skin.
- A further object of the present invention are cosmetic compositions containing at least a compound of formula (I).
-
-
- wherein R, R1, R2 and X have the meanings defined above, z is bromine or preferably chlorine.
-
-
- wherein R, R1, R2, Z and X are as defined in formula (I).
- The intermediates of formula (IV), (V), (VI) and (VII) are prepared according to known procedures.
- The intermediates of formula (IV) and (VI), before the subsequent reaction with the compounds of formula (V) and (VII), may be isolated and purified or, more easily, they are reacted as raw materials, considering them as the first step of a multistep synthesis.
- The reaction of the trichlorotriazine to substitute the three chlorine atoms with amino groups, which can be the same or different, is well-known and thoroughly described in literature, especially that relating to some classes of dyes and optical brighteners.
- The reaction between the compounds of formula (IV) and (VI) and between those of formula (V) and (VII) is carried out at a temperature ranging between 50 and 200° C., in suitable solvents, such as acetonitrile, ketones such as acetone, methylethyl ketone, ethers such as diisopropyl ether, tetrahydrofuran, dioxane, aliphatic or aromatic hydrocarbons, such as hexane, octane, cyclohexane, benzene, toluene, xylene or mixtures thereof, optionally in the presence of an acid acceptor, such as alkali or alkaline-earth hydroxide, alkali metal carbonates or bicarbonates.
- The final compounds are isolated and purified according to usual methods.
- According to the present invention, the compounds of formula (I) are useful as sunscreens. Their protective activity on the skin from sun radiation is carried out by applying a suitable amount on the part of the skin which is exposed to the radiations.
- Suitable amounts for the application can be determined by those skilled in the art, depending on the specific extinction coefficient E1 of the compound of formula (I). Said coefficient is an index of the protection efficacy.
- A further object of the present invention is represented by cosmetic compositions containing an effective amount of at least a compound of formula (I) as sunscreen in combination with conventional carriers and excipients.
- Said compositions can be of different types, for example in the form of solutions, lotions, water-in-oil or oil-in-water emulsions; or also in the form of gels, lipsticks, sprays.
- The compositions according to the present invention can be prepared by admixing conventional ingredients, carriers and excipients such as oils, fats, emollients, hydrating agents, moisturizing agents, softening agents, preservatives, surfactants, thickening agents, antifoam agents, perfumes, pigments, dyes and the like such as alcohols, polyols, electrolytes, silicone derivatives. The most commonly used solvents are triglycerides of capric or caprylic acid, castor oil, esters of fatty acids with isopropanol, propylene glycol, glycerin, propylene glycol monomethyl or monoethyl or monobutyl ether, dioctyl malate.
- The present invention also comprises the protection of cosmetic compositions from UV radiation by using the compounds of formula (I), in case the cosmetic ingredients are liable to undergo unwanted degradation or colouring due to light, such as hair shampoos and lacquers, hairdress lotions, hair-dye compositions, make-up formulations, such as nail lacquers, foundations, lipsticks.
- Preferred cosmetic compositions are those for the protection of the skin from sun radiations.
- The cosmetic compositions of the present invention can contain one or more compounds of formula (I), in an amount comprised from 0.1 to 20%, preferably from 0.5 to 15% by weight with respect to the total weight of the composition.
- According to the invention, in addition to the compounds of formula (I), also other sunscreens can be added, particularly those having a maximum absorption comprised from 290 to 320 nm.
- In such a manner, a protection both against UV-A and UV-B radiations can be obtained. Well-known sunscreens, which can be combined with the compounds of formula (I) are for example:
- 3-(4-methylbenzylydene)-camphor; 2-ethylhexyl-(4-dimethyl-amino)benzoate; 2-ethylhexyl-4-methoxy-cinnamate menthyl salicylate; 2-hydroxy-4-methoxy-benzophenone; 2,4,6-trianilino-(p-carbo-2-ethyl-hexyloxy)-1,3,5-triazine; 4-(1,1-dimethylethyl)-4′-methoxydibenzoyl-methane; triazine derivatives disclosed in U.S. Pat. No. 5,346,691; 2-ethylhexyl-2-cyano-3,3-diphenylacrylate; 2-phenyl-benzimidazol-5-sulfonic acid, 2-hydroxy-4-methoxy-benzophenone-5-sulfonic acid or 1,4-di-(3-methylbenzylidenecamphor)-10-sulfonic salts.
- The application of the sunscreens according to the present invention can be carried out by means of cosmetic compositions containing one or more compounds of formula (I), optionally combined with one or more well-known sunscreens, such as those cited above.
- It is understood that the above list of sunscreens which may be combined with the sunscreens of formula (I) is only given by way of example, and it is not intended to be limited.
- The cosmetic compositions containing the compounds of formula (I) of the invention are used for the treatment of skin, hair or for cosmetic make-up.
- In another aspect, the present invention also provides the use of compounds of formula (I) for the protection of synthetic polymers. According to the present invention, polymeric materials, which can be protected from UV radiation, include polyethylene, polypropylene, polystyrene, polybutadiene, polyisoprene and their copolymers, polyvinyl acetate and its copolymers, particularly with polyethylene, polyesters such as polyethylene terephthalate, polyamides such as Nylon 6 and Nylon 6,6, polyurethanes, polyacrylates, polymethacrylates, polyvinyl chloride.
- The compounds of formula (I) can be incorporated in polymers to be stabilized by means of any known method for mixing or blending additives to polymeric materials; for example, they can be mixed with the polymer in a suitable blender or mixer, or added in the form of solution or suspension in a suitable solvent such as methanol, ethanol, acetone, chloroform, then removing the solvent after mixing with the polymer, which can be in the form of powder, granulate or suspension or finally can be added to the polymer during the preparation of the same, for example in the last preparation step.
- The compounds of formula (I) can be also used in combination with other stabilizing agents and additives generally used for polymers, such as for example phenol-based antioxydants, phosphites, hindered amines and particularly those containing in their structure the 2,2,6,6-tetramethylpiperidine group, other types of UV-absorbers based on benzotriazoles or benzophenones, plastifiers, lubricants, flame retardants, titanium oxide.
- The amount of compounds of formula (I) necessary to an effective stabilization of the polymer depends on different factors, such as the kind and the characteristics of the polymer, the use to which it is intended, the intensity of the radiation, the duration of exposure and the presence, if any, of other stabilizing agents.
- Generally, an amount comprised from 0.01 to 5% by weight of the polymer, preferably from 0.05 to 2% will be sufficient.
- The following examples further illustrate the invention.
- 109 g of o-aminophenol in 1000 ml of xylene were added with 185.5 g of p-nitrobenzoyl chloride. The resulting suspension was slowly heated to 130° C. The formed hydrochloric acid was neutralized by sending it to a NaOH solution.
- After HCL evolution ceased (after about 1 hour), 9.5 g of p-toluenesulfonic acid were added to the reaction mixture, stirring under reflux for about 3 hours, while azeotropically distilling off and collecting the reaction water. After cooling to 60° C., filtering and repeatedly washing with acetone and drying, 225 g of 2-(p-nitrophenyl)-benzoxazole were obtained as a cream colored substance. This was loaded, together with 1,400 ml of ethylene glycol monomethyl ether and 2 g of 5% Pt/C in autoclave, washed 2-3 times with nitrogen and then with hydrogen.
- Subsequently, hydrogen was introduced to reach a pressure of 10 atm and temperature was slowly raised to 90° C., while stirring. Stirring was continued at 80-90° C. until hydrogen absorption ceased, keeping the pressure between 10 and 15 atm.
- After cooling, overpressure was discharged, and the reaction mixture was washed with nitrogen. The catalyst was filtered off, and the resulting solution was vacuum-evaporated to dryness. The residue was crystallized from toluene with addition of decoloring earth. 170 g of 2-(p-aminophenyl)-benzoxazole with m.p. 176-179° C. were obtained. EXAMPLES 2-4
-
- A solution of 46.2 g of trichlorotriazine in 450 ml of acetone, containing 22 g of sodium bicarbonate, cooled to 0° C., was slowly added with 64.7 g of 2-ethylhexylanthranylate, keeping the temperature from 0 to 5° C. by cooling. When the addition was over, the mixture was stirred for a further ½ hour, then added with 175 ml of water and stirred for a further hour, keeping the temperature between 0 and 5° C. The formed precipitate was filtered, thoroughly washed with water, then with acetone and finally dried. 84 g of a white product were obtained, m.p. 136-138° C., with the following formula:
-
-
-
- Operating as described in Example 9, by reacting compounds of formula (IV) with those of formula (V), the compounds of formula (I) listed in Table 3 were obtained.
TABLE 3 Ex. R R1 R2 X m.p/° C. E′ nm 10 (CH3)3— H O 137.5-139 1352 337 11 (CH3)3— H O 132.5-135 1259 337 12 (CH3)3— H NH 193-194 1280 337 13 C2H5C(CH3)3— H NH 179.5-181 1276 338 14 (CH3)3— (CH3)3— O 139.5-141.5 1158 336 -
Polyglycol (Arlacel 165 ICI) 2.0 g Glycerin monostearate 4.0 g Benzoate of C12-C15 alcohol 5.0 g Cetylstearyl alcohol 3.0 g Myristic alcohol with 3 mols of propylene 29.0 g oxide (Witcamol APM-Witco) Compound of example 10 2.0 g 2-Ethylhexyl-4-dimethylaminobenzoate 2.5 g Perfume 0.3 g Distilled water q.s. to 100.0 g - The fatty phase was heated to 80-90° C., the sunscreen of example 10 and 2-ethylhexyl-4-dimethylaminobenzoate were added, then the mixture was added to water, containing the hydrosoluble compounds, heated to 80-90° C. Warm-stirring was continued for 15-20 minutes. After slow cooling, perfume was added.
-
Fatty acid triglycerids 20.0 g Cetystearyl alcohol 2.0 g Lanolin 4.0 g Cetyl alcohol 2.0 g Siliconic oil 0.4 g Compound of example 12 3.5 g Abiol (preservative by 3V SIGMA) 0.2 g Synthalen M (thickening agent by 3V SIGMA) 0.1 g Triethanolamine 0.15 g Perfume 0.3 g Distilled water q.s. to 100.0 g - The preparation was carried out as in Example A.
-
C8-C12 acid triglycerids 29.8 g Glycerol monostearate 7.0 g Stearic acid 2.0 g Lanolin 4.0 g Preservative 0.2 g Compound of example 11 2.0 g Propylene glycol 2.5 g Triethanolamine 0.5 g Perfume 0.3 g Distilled water q.s. to 100.0 g - The preparation was carried out as in Example A.
-
Propylene glycol 25.0 g Ethanol 25.0 g Synthalen M (thickening agent by 3V SIGMA) 0.6 g Compound of example 14 2.5 g Triethanolamine 0.3 g Preservative 0.3 g Perfume 0.3 g Distilled water q.s. to 100.0 g - Synthalen M was dispersed in water, then triethanolamine, preservative, propylene glycol and ethanol mixture, in which the compound of example 14 had previously been dissolved, were added, followed by perfume.
- A base mixture was first prepared, consisting of:
Beeswax 13.0 g Carnauba wax 7.5 g Lanolin 5.0 g Isopropyl myristate 8.0 g Mineral oil 3.0 g Castor oil 63.5 g - 85 g of this mixture were warmed up to melt, then the molten mass was added with 5 g of compound of example 9 and 4 g of compound of example 44 in table 3 of U.S. Pat. No. 5,346,691, as well as perfume, flavors and dyes, then it was diluted to 1000 g with castor oil and cooled to room temperature.
- 1000 g of low density polyethylene (Riblene EF 2100 R Enichem), 2 g of n-octadecyl-3-(3,5-of-terbutyl-4-hydroxyphenyl) propionate, 1 g of calcium stearate and 0.3 g of a compound of formula (I) were homogeneously mixed. The obtained mixtures were extruded at 190° C. and transformed into granules. From these, by pressing at 200° C., films of 0.2 nm were obtained.
- Samples of these films were subjected to UV radiations in a Weatheromether WOM Ci-65 at a black panel temperature of 63° C. In the irradiated samples, the increase of the carbonylic band at 5.85 nm in infrared field was measured and T-0.1, i.e. the time necessary to achieve an increase of 0.1 of the carbonylic band was determined and compared with a film which did not contain stabilizing agents of formula (I). The results are reported in the Table 4.
TABLE 4 Stabilizing agent T 0.1 (hours) Without stabilizing agent 320 Compound of example 9 1140 Compound of example 11 1030 Compound of example 12 1210
Claims (13)
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IT2000MI000226A IT1317825B1 (en) | 2000-02-11 | 2000-02-11 | BENZOSSAZOLE DERIVATIVES, THEIR USE IN COSMETIC COMPOSITIONS AND IN THE STABILIZATION OF SYNTHETIC POLYMERS. |
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Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
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US20050013782A1 (en) * | 2001-12-20 | 2005-01-20 | Beiersdorf Ag | Cosmetic or dermatological light-protective formulation comprising a bisresorcinyl triazine derivative and a benzoxazole derivative |
US20050025726A1 (en) * | 2001-12-20 | 2005-02-03 | Beiersdorf Ag | Cosmetic or dermatological light-protective formulation comprising a benzotriazole and a benzoxazole derivative |
US20050031556A1 (en) * | 2001-12-20 | 2005-02-10 | Beiersdorf Ag | Cosmetic or dermatological light-protective formulation comprising a hydroxybenzophenone and a benzoxazole derivative |
US20050048009A1 (en) * | 2001-12-20 | 2005-03-03 | Beiersdorf Ag | Cosmetic or dermatological light-protective formulation comprising a water-soluble UV filter substance and a benzoxazole derivative |
US20050142080A1 (en) * | 2001-12-20 | 2005-06-30 | Beiersdorf Ag | Cosmetic or dermatological light protection formulation with a benzoxazole derivative |
US20070071866A1 (en) * | 2005-09-23 | 2007-03-29 | Conopco Inc, D/B/A Unilever | Process for producing a frozen aerated composition |
EP3275872A1 (en) | 2016-07-29 | 2018-01-31 | 3V SIGMA S.p.A | New triazine compounds as photostabilising agents |
EP3275426A1 (en) | 2016-07-29 | 2018-01-31 | 3V SIGMA S.p.A | Cosmetic compositions of uv filters |
EP3578558A1 (en) | 2018-06-05 | 2019-12-11 | 3V SIGMA S.p.A | Highly effective photoprotective agents |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10162841A1 (en) * | 2001-12-20 | 2003-07-03 | Beiersdorf Ag | Cosmetic and dermatological light protection formulations containing benzoxazole derivatives |
US20080093981A1 (en) * | 2004-08-23 | 2008-04-24 | Semiconductor Energy Laboratory Co., Ltd. | Electron Injecting Composition, and Light Emitting Element and Light Emitting Device Using the Electron Injecting Composition |
ITMI20120644A1 (en) * | 2012-04-18 | 2013-10-19 | 3V Sigma Spa | TRIAZINE DERIVATIVES |
Family Cites Families (1)
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IT1284525B1 (en) * | 1996-09-13 | 1998-05-21 | 3V Sigma Spa | DERIVATIVES OF BENZOSSAZOLE USED AS STABILIZERS AGAINST UV RADIATION |
-
2000
- 2000-02-11 IT IT2000MI000226A patent/IT1317825B1/en active
-
2001
- 2001-02-05 EP EP01102489A patent/EP1123934A1/en not_active Withdrawn
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Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20050013782A1 (en) * | 2001-12-20 | 2005-01-20 | Beiersdorf Ag | Cosmetic or dermatological light-protective formulation comprising a bisresorcinyl triazine derivative and a benzoxazole derivative |
US20050025726A1 (en) * | 2001-12-20 | 2005-02-03 | Beiersdorf Ag | Cosmetic or dermatological light-protective formulation comprising a benzotriazole and a benzoxazole derivative |
US20050031556A1 (en) * | 2001-12-20 | 2005-02-10 | Beiersdorf Ag | Cosmetic or dermatological light-protective formulation comprising a hydroxybenzophenone and a benzoxazole derivative |
US20050048009A1 (en) * | 2001-12-20 | 2005-03-03 | Beiersdorf Ag | Cosmetic or dermatological light-protective formulation comprising a water-soluble UV filter substance and a benzoxazole derivative |
US20050142080A1 (en) * | 2001-12-20 | 2005-06-30 | Beiersdorf Ag | Cosmetic or dermatological light protection formulation with a benzoxazole derivative |
US7029660B2 (en) | 2001-12-20 | 2006-04-18 | Beiersdorf Ag | Cosmetic or dermatological light-protective formulation comprising a benzotriazole and a benzoxazole derivative |
US7060257B2 (en) | 2001-12-20 | 2006-06-13 | Beiersdorf Ag | Cosmetic or dermatological light-protective formulation comprising a water-soluble UV filter substance and a benzoxazole derivative |
US7341712B2 (en) | 2001-12-20 | 2008-03-11 | Beiersdorf Ag | Cosmetic or dermatological light-protective formulation comprising a hydroxybenzophenone and a benzoxazole derivative |
US20070071866A1 (en) * | 2005-09-23 | 2007-03-29 | Conopco Inc, D/B/A Unilever | Process for producing a frozen aerated composition |
EP3275872A1 (en) | 2016-07-29 | 2018-01-31 | 3V SIGMA S.p.A | New triazine compounds as photostabilising agents |
EP3275426A1 (en) | 2016-07-29 | 2018-01-31 | 3V SIGMA S.p.A | Cosmetic compositions of uv filters |
EP3578558A1 (en) | 2018-06-05 | 2019-12-11 | 3V SIGMA S.p.A | Highly effective photoprotective agents |
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ITMI20000226A1 (en) | 2001-08-11 |
ITMI20000226A0 (en) | 2000-02-11 |
US6399047B1 (en) | 2002-06-04 |
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IT1317825B1 (en) | 2003-07-15 |
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