WO1993010753A1 - Complexes metalliques de protection solaire absorbant les rayons ultraviolets a - Google Patents

Complexes metalliques de protection solaire absorbant les rayons ultraviolets a Download PDF

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Publication number
WO1993010753A1
WO1993010753A1 PCT/US1992/009693 US9209693W WO9310753A1 WO 1993010753 A1 WO1993010753 A1 WO 1993010753A1 US 9209693 W US9209693 W US 9209693W WO 9310753 A1 WO9310753 A1 WO 9310753A1
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Prior art keywords
sunscreen
complex
aluminum
ethylhexyl
mixtures
Prior art date
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PCT/US1992/009693
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English (en)
Inventor
Craig Steven Slavtcheff
George Endel Decker
James Neal Matheson
Original Assignee
Richardson-Vicks, Inc.
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Publication date
Application filed by Richardson-Vicks, Inc. filed Critical Richardson-Vicks, Inc.
Publication of WO1993010753A1 publication Critical patent/WO1993010753A1/fr

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    • 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
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • 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
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/26—Aluminium; Compounds thereof
    • 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
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/27—Zinc; Compounds thereof
    • 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
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/28—Zirconium; Compounds thereof
    • 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
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/29—Titanium; Compounds thereof
    • 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
    • A61K8/58—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing atoms other than carbon, hydrogen, halogen, oxygen, nitrogen, sulfur or phosphorus
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/58—Metal complex; Coordination compounds

Definitions

  • the present invention relates to sunscreen complexes, and m particularly to sunscreen metal complexes, having enhanced absorption.
  • These complexes comprise a dibenzoylmeth UVA-absorbing sunscreen complexed to a cationic species, prefera a metal cation. These complexes are useful for protecting the s from the harmful effects of ultraviolet radiation. This invent also relates to compositions containing these complexes.
  • UVB nanometer wavelen ultraviolet radiation range
  • UVA ultraviolet radiation range
  • Another long term hazard of ultraviolet radiation is premat aging of the skin. This condition is characterized by wrinkling yellowing of the skin, along with other physical changes such cracking, telangiectasis (spider vessels), solar kerato (growths), ecchymoses (subcutaneous hemorrhagic lesions), and l of elasticity (sagging).
  • telangiectasis spike vessels
  • solar kerato growths
  • ecchymoses subcutaneous hemorrhagic lesions
  • l of elasticity sagging
  • sunscreen agents and physical sunblocks are commercial available to protect the skin from UV radiation.
  • Examples of physical sunblocks include titanium dioxide and zinc oxide.
  • compositions containing high level of these agents are opaque, generally unattractive i color, and are viewed as unacceptable for usage on more than jus the nose or tops of the ears.
  • these agents are ve susceptible to rub-off or wear-off resulting in little or n protection.
  • sunscreen agents exert their effects throug chemical means, i.e., they absorb ultraviolet radiation so that i cannot penetrate the skin.
  • Sunscreens present the user with severa problems. For example, they must be on the surface of the skin a the time of exposure to be effective. Sunscreens are preventativ so one must anticipate being in the sun. To be most effective sunscreens must be on the skin as a continuous uniform film Delivering such a film to the surface of the skin is very difficult
  • Most commercially-avaible sunscreen agents are primarily UV absorbers. The number of UVA absorbers is more limited wit benzophenones and dibenzoylmethanes being the most well-known U.S. Patent No.
  • It is a still further object of the present invention provide topical sunscreen compositions containing sunscreen me complexes for providing protection for the skin from the damagi effects of UV radiation.
  • (A) S is a sunscreen moiety having the general structure
  • A is a substituent selected from H, -OR or -NR2 where each R is independently H, straight or branch chain alkyl having from about 1 to about 20 carbon atom (CH2CH2 ⁇ )q-H, or (CH2CH(CH3)0) q -H, wherein q is an integ from 1 to about 8; and B is a substituent selected from straight or branched chain alkyl having from about 1 about 20 carbon atoms, (CH2CH2 ⁇ )q-H, or (CH2CH(CH3)0)q- wherein q is an integer from 1 to about 8;
  • (B) m is an integer selected from 1, 2, 3 or 4;
  • (C) M is a metal cation, an ammonium cation, or a substitut ammonium cation
  • n is an integer selected from 1, 2, 3, or 4;
  • (E) L is a ligand comprising a neutral or negatively charg organic or inorganic moiety
  • (F) p is an integer from 0, 1, 2, 3 or 4.
  • the present invention further relates to compositions containin these complexes, and to methods for providing enhanced protection t the skin of humans or lower animals from the effects of ultraviole radiation.
  • the sunscreen metal complexes useful in the present inventio are those having the general structure: (S) m (N)n (Up.
  • (S) m represents a dibenzoylmethane sunscreen moiety, where designates the number of moieties present in the complex.
  • (M)n represents a cationic species such as a metal, o alternatively ammonium or substituted ammonium, where n designate the number of species present in the complex.
  • (L)p represents a ligand, which is optionally present in th complex, where p designates the number of ligands present in th complex.
  • the sunscreen metal complexes of the present inventio preferably absorb light in the visible wavelength range (i.e. abov about 400 nm) only weakly or not at all.
  • the complexes ar therefore either only lightly colored (e.g., light yellow or crea colored) or are essentially white. This is desirable for cosmeti reasons.
  • the sunscreen metal complexes preferably do not hav a € of greater than about 500 for any wavelength above about 400 nm, and most preferably the € is essentially zero for any wavelengt above about 400 nm.
  • the sunscreen moieties which comprise the sunscreen complex of the present invention are those containing the dibenzoylmetha chro ophore. This chromophore is characterized as being effecti for strongly absorbing radiation in the UVA range.
  • These dibenzo methane sunscreen moieties which comprise the complexes of t instant invention are fully disclosed in U.S. Patent Nos. 4,489,0 and 4,387,089, which have already been incorporated by referenc supra.
  • the numb of sunscreen moieties present is designated by , wherein is integer selected from 1 through 8, more preferably m is an integ selected from 1 through 4, even more preferably m is an integ selected from 1 through 3, and most preferably is 2.
  • UVA-absorbing dibenzoylmethane sunscre moieties useful in the sunscreen compounds of the present inventi include those of the following general structure:
  • A is a substituent of variable positi on the aromatic ring selected from H, -OR or -NR2 where each R i independently H, straight or branched chain alkyl having from abo 1 to about 20 carbon atoms, (CH2CH2 ⁇ ) q -H, or (CH2CH(CH3)0) q - wherein q is an integer from 1 to about 8; and B is a substituent variable position on the aromatic ring selected from H, straight branched chain alkyl having from about 1 to about 20 carbon atom (CH2CH2 ⁇ )q-H, or (CH2CH(CH3)0)q-H, wherein q is an integer from 1 about 8.
  • A is preferably para -OCH3 and is para t-butyl, i.e. 4,4'-methoxy-t-butyldibenzoylmethane (CT adopted name: butyl dibenzoylmethane, which is commercial available under the trademark Parsol- 1789 from Givaudan), alternatively A is H and B is para isopropyl, i.e. 4-isopropy dibenzoylmethane (CTFA adopted name: isopropyl dibenzoylmethan which is commercially abailable under the trademark Eusolex R 80 from Merck).
  • CTFA isopropyl dibenzoylmethane
  • the dibenzoylmetha chromophore is represented as a 1,3-diketone it should be understo that this representation in no way excludes other tautomeric for of the functional group such as the enol form.
  • t 1,3-diketone form it is understood that a appropriate enol tautomers are also contemplated and includ herein.
  • These tautomeric enol forms of the dibenzoylmetha chromophore can be represented by the following tautomeri structures.
  • the dibenzoylmethan chromophore can lose a hydrogen atom to form the correspondin anionic species. This phenonenon is more likely at higher pH value (i.e. alkaline pH values) and when the dibenzoylmethane chromophor is complexed to a cationic species such as a metal.
  • pH value i.e. alkaline pH values
  • al appropriate anionic forms are also contemplated and included herein
  • molar absorptivity value is quantitative measure of the ability of a molecule to absorb ultr violet light at a specified wavelength.
  • the molar absorptivi value is expressed at a particular wavelength of light as the mol absorption coefficient (represented herein by " i " which expressed in units of liter/mole cm), which is calculated by t equation:
  • a i - lc wherein "1" is the path length (in centimeters) of the absorbi media through which the light passes; "c” is the concentration the chromophore molecule (in moles per liter); and "A” is t "absorbance".
  • the absorbance is calculated from the observ difference in the intensity of the particular wavelength of lig before and after passing through the chromophore-molecule-containi absorbing media. Thus, the absorbance is calculated by t equation:
  • Absorption maximum means wavelength of radiation at which the chro ophore-containing molecu has the greatest molar absorptivity value relative to wavelengt immediately above and below the absorption maximum waveleng
  • absorption maximum is easily identified as a peak in the graph the spectrum generated by the instrument measuring the absorption.
  • Absorption maximum (designated herein as ⁇ max) provided for representative sunscreen compounds of the pres invention in the Examples hereinafter.
  • the sunscreen complexes of the present invention compris cationic species, preferably a metal, or alternatively ammonium substituted ammonium, represented by the general structure (M
  • metal cations useful in the complexes of the pres invention include alkali metal (e.g., sodium and potassiu alkaline earth metal (e.g., calcium and magnesium), and transit and heavy metals (e.g., aluminum and strontium).
  • Preferred for in the complexes of the instant invention are the metals selec from the group consisting of aluminum, zinc, calcium, magnesi copper, iron, barium, strontium, zirconium, titanium, ti beryllium, gallium, indium, lanthanum, manganese, antimony, bismut cerium, thorium, niobium, tantalum, antimony, molybdenum, tungste lithium, sodium, potassium and mixtures thereof.
  • These met cations are useful in any of their possible valence states and combinations of these states (i.e. where for example some of t metal cations are in one of the cation's allowable valence state and some of the metal cations are in another of the metal cation allowable valence states, etc.).
  • the sunscreen complexes of the instant inventi can also comprise complexes with other cationic species such ammonium, substituted ammonium (e.g., mono-, di-, tri- and tetr alkyl and alkoxy substituted), and cations of diamines (e.g., tetr alkyl and alkoxy substituted ethylene diamines).
  • other cationic species such as ammonium, substituted ammonium (e.g., mono-, di-, tri- and tetr alkyl and alkoxy substituted), and cations of diamines (e.g., tetr alkyl and alkoxy substituted ethylene diamines).
  • preferr cation species include metals selected from the group consisting aluminum, titanium, copper, iron, and zinc.
  • alumin cations having a valence of 3 + are most preferred.
  • the numb of M species present in the complex is designated by n, wherein n i an integer selected from 1 through 4, more preferably n is integer selected from 1 through 3, even more preferably n is integer selected from 1 and 2, and most preferably n is 1
  • the complexes of the insta invention can exist as a mixture of different species havi different n values.
  • the M species ca be derived from any suitable sources.
  • the cation can b derived from a wide variety of salts.
  • salts included metal oxides, hydroxides, fluorides, chlorides, bromides, iodides carbonates, bicarbonates, phosphates, hydrogen phosphates dihydrogen phosphates, alkoxides (e.g., isopropoxide), sulfates hydrogensulfates, nitrates, sulfites, nitrites, borates, chlorates bromates, perchlorates, perbromates, diphosphates, polyphosphates thiocyanates, carboxylates (preferably, acetates and stearates), an mixtures thereof.
  • the ammonium or substituted ammonium specie can be derived from a wide variety of ammonium and substitute ammonium sources such as salts (e.g., chlorides, bromides hydroxides, and the like).
  • salts e.g., chlorides, bromides hydroxides, and the like.
  • compositions of the instant invention preferred source of the cationic species include aluminum monoacetate, aluminu diacetate, aluminum stearate, and mixtures thereof.
  • Expeciall preferred is aluminum monoacetate.
  • the sunscreen complexes of the present invention optionall comprise an organic or inorganic ligand represented by the genera structure (L) p .
  • Both neutral and anionic ligands are useful in th complexes of the present invention.
  • Useful organic ligand include, but are not limited to, those selected from the grou consisting of carboxylic acids, dicarboxylic acids, an polycarboxylic acids and their anions; amines, diamines, an polyamines; alcohols, diols, and polyols and their anions; thiol dithiols, and polythiols and their anions; amino acids and the anions; any other pharmaceutically-acceptable organic ligands, a mixtures thereof.
  • Useful inorganic ligands include, but are n limited to, water and hydroxide anion, halide (e.g., fluorid chloride, bromide, and iodide), carbonate, bicarbonate, phosphat hydrogen phosphate, dihydrogen phosphate, sulfate, hydrogen sulfat nitrate, sulfite, nitrite, borate, chlorate, bromate, perchlorat perbro ate, diphosphate, polyphsophate, thiocyanate, any oth pharmaceutically-acceptable inorganic ligands, and mixtures thereo
  • pharmaceutically-acceptable organic and inorgani ligands as used herein is meant those organic and inorganic ligand which are acceptable from a toxicity viewpoint.
  • ligand selected from water, hydroxide anion, and carboxylic acids havin from about 2 to about 22 carbon atoms and their anions ar preferred.
  • Other preferred ligands include ethoxide an isopropoxide.
  • Especially preferred among the carboxylic acids an their anions are acetic acid and the acetate anion, octanoic aci and the octanoate anion, and stearic acid and the stearate anion.
  • th number of ligands present in the complex is designated by p, wherei p is an integer selected from 0 through 4, more preferably p is a integer selected from 0 through 3, even more preferably p is a integer selected from 0 through 2, even more preferably p is a integer selected from 0 and 1, and most preferably p is 0
  • the complexes of the instan invention can exist as a mixture of different species havin different p values.
  • sunscreen metal complexes of the presen invention include, for example:
  • the sunscreen metal complexes of the present invention can prepared as described in the Examples below. In furth embodiments, these complexes can then be directly formulated into desired carrier. Alternatively, these sunscreen complexes can isolated before being formulated into the desired carrier. In y another alternative, these sunscreen complexes can be prepar directly in the desired carrier.
  • the sunscreen metal complex is prepared combining a sunscreen compound and a metal salt in a suitab solvent selected from the group consisting of water, acetone, eth acetate, methyl t-butyl ether, Cj-C ⁇ alcohols, diols, triols, C12- alcohols benzoate, chlorinated solvents (e.g., ethylene chloride dimethyl isosorbide, isodecyl neopentanoate, diisopropyl adipat and mixtures thereof.
  • a suitab solvent selected from the group consisting of water, acetone, eth acetate, methyl t-butyl ether, Cj-C ⁇ alcohols, diols, triols, C12- alcohols benzoate, chlorinated solvents (e.g., ethylene chloride dimethyl isosorbide, isodecyl neopentanoate, diisopropyl adipat and mixtures thereof.
  • Preferred metal salts include tho selected from the group consisting of salts of aluminum, zin calcium, magnesium, copper, iron, barium, strontium, zirconiu titanium, tin, beryllium, gallium, indium, lanthanum, manganes antimony, bismuth, cerium, thorium, niobium, tantalum, antimon molybdenum, tungsten, lithium, sodium, potassium, and mixtur thereof. More preferred are salts of aluminum, titanium, coppe iron, zinc, and mixtures thereof.
  • salts aluminum with those selected from the group consisting of alumin acetate, aluminum diacetate, aluminum stearate, aluminum distearat aluminum octanoate, aluminum ethoxide, aluminum isopropoxide, a mixtures thereof, being more preferred, and aluminum diacetate bei most preferred.
  • ammonium and substituted ammoni chlorides, bromides, and hydroxides can be employed.
  • at least one equivalent of a base can be added i order to facilitate the dissolution of the sunscreen compoun
  • the sunscreen compound and the base are prereacted the solvent system before the metal salt is added.
  • Preferred bas include sodium hydroxide, potassium hydroxide, ammonium hydroxid sodium bicarbonate, sodium carbonate, and mixtures thereo
  • the solvent system can be heated to its boiling poi if required.
  • the sunscreen metal complex is isolated a purified, this is preferably accomplished by filtration a evaporation of the filtrate. Additionally, the complex can further purified by recrystallization from a suitable solvent. T Examples given below provide representative preparations of th sunscreen metal complexes and compositions containing them.
  • compositions Containing Sunscreen Metal Complexes One or more of the sunscreen complexes of the present inventio can be incorporated into a variety of carriers, includin pharmaceutical and cosmetic carriers, paints, coatings, polymeri maxtrices, fiber matrices, and the like. Preferably, the complexe are incorporated into pharmaceutical and cosmetic carriers.
  • the sunscreen metal complexes of the present inventio typically comprise from about 0.1% to about 30.0% by weight of th sunscreen compositions of the present invention, preferably fro about 1% to about 20%, and most preferably from about 5% to abou 15%.
  • the compositions of the instant invention can comprise th following components.
  • compositions of the instant invention can comprise a saf and effective amount of a topical pharmaceutically-acceptabl carrier or diluent which can be of a variety of different forms.
  • “safe and effective” is meant an amount sufficient to act as suitable vehicle for the sunscreen metal complexes and any othe components, but not so much as to cause any side effects or ski reactions.
  • “Pharmaceutically-acceptable” means that the carrier i suitable for topical application to the skin without causing an untoward safety or toxicity concerns. In other words, thes carriers are suitable for use on humans and lower animals.
  • Th topical carrier can be in the form of an emulsion including, but no limited to, oil-in-water, water-in-oil, water-in-oil-in-water, an oil-in-water-in-silicone emulsions.
  • emulsions can cover a broad range of consistencies including thin lotions (which can also be suitable for spray or aerosol delivery), creamy lotions, ligh creams, heavy creams, and the like.
  • suitable topical carrier include anhydrous liquid solvents such as oils and alcohols aqueous-based single phase liquid solvents (e.g. hydro-alcoholi).
  • the pharmaceutically-acceptable topical carriers in total typically comprise from about 0.1% to about 99.8% by weight of th sunscreen compositions of the present invention, preferably fro about 80% to about 99%, and most preferably from about 85% to abou 95%.
  • a preferred topical carrier of the compositions of the instan invention is an oil-in-water type emulsion.
  • the pH of these oil-in water emulsion compositions herein is preferably in the range o from about 3.5 to about 9.
  • the mean particle size o the dispersed oil phase materials can be in the range of from abou 5 ⁇ to about 10 microns with greater than about 75% of the particle being less than about 12 microns. Additional Sunscreens -
  • sunscreening agents include, but are not limited to, for example: Ethylhexyl-p-methoxycinnamate (available as Parsol MCX from Givauda Corporation), p-Aminobenzoic acid, its salts and its derivative 5 (ethyl, isobutyl, glyceryl esters; p-dimethylamino- benzoic acid 2-ethylhexyl N,N-dimethylaminobenzoate; p-Methoxy- cinnamic Aci Diethanolamine Salt (available as Bernel Hydro from Bernel Chemical Co.); Anthranilates (i.e., o-aminobenzoates; methyl, octyl , amy menth
  • sunscreens include the solid physical sunblocks suc as titanium dioxide (icronized titanium dioxide, 0.03 microns 0.035 microns, 0.050 microns, and other suitable sizes), zinc oxide silica, iron oxide and the like. Without being limited by theory it is believed that these inorganic materials provide a sunscreenin benefit through reflecting, scattering, and absorbing harmful UV visible, and infrared radiation.
  • Other useful sunscreens are those having both a UVA and a UV absorbing chromophore in the same molecule as disclosed in U.S Patent Nos. 5,041,282, 4,999,186 and 4,937,370, and European Paten Application No. 416,837, which have already been incorporated reference herein.
  • these additional sunscreens can comprise from zer to about 20% of the composition, preferably from about 0.5% to abou 10%. Exact amounts will vary depending upon the sunscreen chose and the desired Sun Protection Factor (SPF). SPF is a commonly use measure of photoprotection of a sunscreen against erythema. Se Federal Re g ister. Vol. 43, No. 166, pp. 38206-38269, August 25 1978.
  • the compositions ca also contain one or more artificial tanning ingredients such a dihydroxyacetone, tyrosine, amino acids, and amino acid derivatives Typically, artificial tanning ingredients can be incorporated int the compositions of the instant invention at levels from about 0.1 to about 10%, and preferably at levels from about 0.1% to about 5%. Thickeners
  • compositions of the instan invention is a thickener.
  • thickeners which can b employed include, but are not limited to, xanthan gum, magnesiu aluminum silicate, guar gum, cationic guar gum, Rhamsan Gu (available from Kelco Chemical Co.), kelp, algin and alginate salts starch and starch derivatives, hydroxypropylcellulose hydroxyethylcellulose, carboxymethylcellulose, methylcellulose ethylcellulose, smectite clay thickeners such as hectorite an bentonite, sodium magnesium silicate and mixtures thereof.
  • suitable thickeners are disclosed in Lochhead, R.Y.
  • compositions of th instant invention comprise from about 0.1% to about 5% thickener preferably from about 0.25% to about 2%, and most preferably fro about 0.5% to about 1%.
  • Humectants/Moisturizers include magnesium aluminum silicat and xanthan gum and mixtures thereof.
  • compositions of the instant invention can also optional contain one or more humectants/moisturizers.
  • a variety humectants/moisturizers can be employed and can be present at level of from about 0.5% to about 30%, more preferably from about to about 8% and most preferably from about 3% to about 5%.
  • the materials include urea; guanidine; glycolic acid and glycolate sal (e.g. ammonium and quaternary alkyl ammonium); lactic acid a lactate salts (e.g.
  • Preferred humectants/moisturizers for use in the compositio of the present invention are the C3-C6 diols and triols. Especial preferred is the triol, glycerin.
  • Emollients The compositions of the present invention can al optionally comprise at least one emollient.
  • suitabl emollients include, but are not limited to, volatile a non-volatile silicone oils, highly branched hydrocarbons, an non-polar fatty acid and fatty alcohol esters, and mixtures thereo Emollients useful in the instant invention are further described i U.S. Patent No. 4,919,934, to Deckner et al., issued April 24199 which is incorporated herein by reference in its entirety.
  • the emollients can typically comprise in total from about 1% t about 50%, preferably from about 1% to about 25%, and mor preferably from about 1% to about 10% by weight of the composition of the present invention.
  • emulsifiers ca include any of a wide variety of nonionic, cationic, anionic, an zwitterionic emulsifiers disclosed in the prior patents and othe references. See McCutcheon's, Detergents and Emulsifiers. Nort American Edition (1986), published by Allured Publishing Corpor ation; U.S. Patent No. 5,011,681, to Ciotti et al, issued April 30 1991; U.S. Patent No. 4,421,769, to Dixon et al., issued Decemb 20, 1983; and U.S. Patent No.
  • Suitable emulsifier types include esters of glycerin, esters propylene glycol, fatty acid esters of polyethylene glycol, fat acid esters of polypropylene glycol, esters of sorbitol, esters sorbitan anhydrides, carboxylic acid copolymers, esters and ethe of glucose, ethoxylated ethers, ethoxylated alcohols, alky phosphates, polyoxyethylene fatty ether phosphates, fatty aci amides, acyl lactylates, soaps and mixtures thereof.
  • Suitable emulsifiers can include, but are not limited to, poly ethylene glycol 20 sorbitan monolaurate (Polysorbate 20) polyethylene glycol 5 soya sterol, Steareth-20, Ceteareth-20, PPG- methyl glucose ether distearate, Ceteth-10, Polysorbate 80, cety phosphate, potassium cetyl phosphate, diethanola ine cety phosphate, Polysorbate 60, glyceryl stearate, PEG-100 stearate, an mixtures thereof.
  • Polysorbate 20 polyethylene glycol 20 sorbitan monolaurate
  • Polysorbate 20 polyethylene glycol 5 soya sterol
  • Steareth-20 Ceteareth-20
  • PPG- methyl glucose ether distearate Ceteth-10
  • Polysorbate 80 cety phosphate
  • potassium cetyl phosphate diethanola ine cety phosphate
  • Polysorbate 60 glyceryl stearate
  • the emulsifiers can be used individually or as a mixture of tw or more and comprise from about 0.1% to about 10%, preferably fro about 1% to about 7%, and most preferably from about 1% to about 5 of the compositions of the present invention.
  • Vitamins optionally, various vitamins can also be included in th compositions of the present invention. Non-limiting example include Vitamin A, and derivatives thereof, ascorbic acid, Vitami B, biotin, Vitamin D, Vitamin E and derivatives thereof such a tocopheryl acetate, panthothenic acid, and mixtures thereof can als be used.
  • compositions of the instan invention is a carboxylic copolymer (acrylic acid copolymer).
  • Mos preferred is Carbomer 1342 (available as Carbopol 1342 from B.F Goodrich).
  • Carbomer 1342 available as Carbopol 1342 from B.F Goodrich.
  • th acrylate/alkyl acrylate crosspolymers such as Acrylates/C10-C Alkyl Acrylate Crosspolymer (available as Pemulen TR-1 and Pemul TR-2 from Goodrich). Reference to Include Pemulens.
  • These polymers comprise from about 0.025% to about 0.75 preferably from about 0.05% to about 0.25% and most preferably fr about 0.075% to about 0.175%.
  • Other Optional Components are preferably from about 0.025% to about 0.75 preferably from about 0.05% to about 0.25% and most preferably fr about 0.075% to about 0.175%.
  • additional ingredients can be incorporated in the emulsion compositions of the present invention.
  • additional ingredients include various polyme for aiding the film-forming properties and substantivity of th composition (such as a copolymer of eicosene and vinyl pyrrolidone an example of which is available from GAF Chemical Corporation a Ganex V-220 R ); gums, resins, and thickeners; preservatives fo maintaining the antimicrobial integrity of the compositions antioxidants; chelators and sequestrants; anti-acne agents keratolyic agents;and agents suitable for aesthetic purposes such a fragrances, pigments, and colorings.
  • Other useful materials included acidic materials such as salicylic acid, lactic acid, glycolic acid benzoic acid, citric acid and the like. Without being limited b theory, it is believed that these acid materials are useful fo maintaining the pH of the composition and enhancing produc performance.
  • the present invention further relates to a method for pro tecting the skin of humans or lower animals from the effects of UV and UVB wavelength radiation, such as sunburn and premature aging o the skin.
  • a method for pro tecting the skin of humans or lower animals from the effects of UV and UVB wavelength radiation, such as sunburn and premature aging o the skin comprises topically applying to the huma or lower animal an effective coating of a sunscreen agent o composition of the present invention.
  • the term "effective coating”, as used herein, means a film of sunscreen agent sufficient to substantially reduce the amount of UVA and UVB wavelength light which reaches the skin's surface.
  • an effective coating of the skin is from about 0.5 mg sunscreen agent or composition o the present invention/cm 2 skin to about 5 mg sunscreen agent or composition of the present invention/cm 2 skin. See Federal Register. Vol. 43, No. 166, pp.
  • This crude complex is redissolved in approximately 150 m of methylene chloride with heating and is then vacuum filtered usin a coarse, sintered glass funnel to remove any undissolved materials which are washed with methylene chloride (approximately 2 X 20 mL) (Alternatively, other suitable solvents such as chloroform, ethy acetate or methyl t-butyl ether can be used for this redissolvin step.)
  • methylene chloride approximately 2 X 20 mL
  • other suitable solvents such as chloroform, ethy acetate or methyl t-butyl ether can be used for this redissolvin step.
  • the pooled filtrates are extracted with water (approximatel 2 X 100 mL), dried over sodium sulphate, and evaporated by rotar evaporation to yield the sunscreen aluminum complex as a ligh yellow, glassy solid. This solid is suitable for incoporation int a sunscreen composition.
  • alumin monoacetate (basic, stabilized with boric acid: Aldrich Chemic Co., Milwaukee, WI) is added to approximately 300 L of absolu ethanol and heated to boiling for approximately 10 minutes.
  • 106.33 grams (0.343 moles) of 4,4'-methox t-butyl-dibenzoylmethane acid ester with 4-hydroxydibenzoylmetha is added to approximately 200 mL of acetone and heated to boilin for approximately 10 minutes.
  • this sunscreen alumin complex is prepared starting with 1.0 gram of aluminum dioctanoa
  • this sunscreen aluminu complex is prepared using 33.75 grams (0.240 moles) of aluminu monoacetate and 91.24 grams (0.343 moles) of 4-isopropyldibenzoyl methane. A light yellow solid is obtained suitable fo incorporation into a sunscreen composition.
  • analogous gel compositions can be prepared usin the other sunscreen metal complexes of the instant invention an with other solvents such as isodecylneopentanote, diisopropy adipate, and dimethylisosorbide.
  • An emulsion composition is prepared from the followin ingredients using standard methods.
  • This emulsion composition is useful for topical application t the skin to provide protection from the harmful effects o ultraviolet radiation.
  • An emulsion composition is prepared from the followin ingredients using standard methods.
  • This emulsion composition is useful for topical application to the skin to provide protection from the harmful effects of ultraviolet radiation.
  • analogous emulsions are prepared using other isolated sunscreen metal complexes of the instant invention.
  • Phase A ingredients are combined and heated with stirring t
  • Phase B 80°C to form the oil phase.
  • Phase B ingredients ar combined and heated with stirring to 80°C.
  • Phase A is added t
  • Phase B with homogenization to form the emulsion which is the cooled to room temperature with stirring.
  • This emulsion composition is useful for topical application t the skin to provide protection from the harmful effects o ultraviolet radiation.
  • analogous emulsions are prepared using othe isolated sunscreen metal complexes of the instant invention.

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  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Birds (AREA)
  • Epidemiology (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Dermatology (AREA)
  • Cosmetics (AREA)

Abstract

La présente invention concerne des complexes métalliques de protection solaire présentant une capacité d'absorption des rayons ultraviolets A améliorée. Ces complexes comprennent, en tant qu'agent de protection solaire absorbant les rayons ultraviolets A, du dibenzoylméthane complexé avec un cation métal. Ces complexes sont utilisés pour protéger la peau des effets nocifs des rayonnements ultraviolets. Cette invention concerne également des procédés de préparation de ces complexes métalliques de protection solaire et des compositions contenant lesdits complexes.
PCT/US1992/009693 1991-11-27 1992-11-12 Complexes metalliques de protection solaire absorbant les rayons ultraviolets a WO1993010753A1 (fr)

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US80066591A 1991-11-27 1991-11-27
US800,665 1991-11-27

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AU (1) AU3132193A (fr)
MX (1) MX9206875A (fr)
PT (1) PT101102A (fr)
WO (1) WO1993010753A1 (fr)

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995005150A1 (fr) * 1993-08-13 1995-02-23 Unilever Plc Agents antisolaires
WO2000023042A1 (fr) * 1998-10-16 2000-04-27 The Procter & Gamble Company Compositions de protection uv
EP1002522A1 (fr) * 1998-11-19 2000-05-24 Beiersdorf Aktiengesellschaft Complexes d'aluminium avec des dérivés de dibenzoylméthane et compositions cosmétiques ou dermatologiques les contenant
FR2799120A1 (fr) * 1999-10-01 2001-04-06 Oreal Materiau comprenant un filtre uv-a organique et procede de deplacement de la longueur d'onde d'absorption maximale
EP2196189A1 (fr) 2001-12-07 2010-06-16 L'oreal Compositions cosmétiques antisolaires à base d'un mélange synergique de filtres et utilisations
WO2012101204A1 (fr) 2011-01-28 2012-08-02 Momentive Performance Materials Gmbh Composition cosmétique photoprotectrice contre les uv
WO2014010099A1 (fr) 2012-07-13 2014-01-16 L'oreal Pigment composite et son procédé de préparation
WO2014010100A1 (fr) 2012-07-13 2014-01-16 L'oreal Composition cosmétique comprenant des particules composites de protection solaire
WO2014009097A1 (fr) 2012-07-13 2014-01-16 L'oreal Composition cosmétique contenant des particules composites de protection
WO2014010098A1 (fr) 2012-07-13 2014-01-16 L'oreal Composition cosmétique comprenant des particules composites
WO2014111566A2 (fr) 2013-01-21 2014-07-24 L'oreal Composition cosmétique ou dermatologique comprenant une mérocyanine et un agent anti-uv organique insoluble et/ou un agent anti-uv inorganique insoluble
WO2015191004A1 (fr) * 2014-06-09 2015-12-17 Agency For Science, Technology And Research Complexes métalliques
WO2016030839A1 (fr) 2014-08-28 2016-03-03 L'oreal Composition gel/gel comprenant un filtre uv
WO2016083404A1 (fr) 2014-11-24 2016-06-02 L'oreal Composition cosmetique comprenant un phyllosilicate synthetique et un polyol et/ou un filtre uv
WO2016198581A1 (fr) 2015-06-11 2016-12-15 L'oreal Composition comprenant un agent de blocage d'ultraviolet, un polymère hydrophile réticulé anionique, un tensioactif ayant un hlb inférieur ou égal à 5, et un copolymère de silicone
WO2019096960A1 (fr) 2017-11-15 2019-05-23 L'oreal Compositions comprenant au moins un polymère acrylique et au moins un filtre uv organique insoluble
FR3083093A1 (fr) 2018-06-28 2020-01-03 L'oreal Composition photoprotectrice comprenant des particules de silice colloidale
FR3090329A1 (fr) 2018-12-21 2020-06-26 L'oreal Composition comprenant un filtre UV, un polymère hydrophile réticulé anionique, un tensioactif ayant une HLB inférieure ou égale à 5 et un alcane non volatil
FR3103704A1 (fr) 2019-11-29 2021-06-04 L'oreal Composition comprenant un filtre UV, un polymère éthylénique à groupe acide phosphonique et une huile hydrocarbonée
FR3103705A1 (fr) 2019-11-29 2021-06-04 L'oreal Composition comprenant un filtre UV, un polymère séquencé à groupe acide phosphonique et une huile hydrocarbonée
US11523976B2 (en) 2012-07-13 2022-12-13 L'oreal Composite pigment and method for preparing the same

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0242611A1 (fr) * 1986-04-02 1987-10-28 Kao Corporation Composé absorbant les rayons UV de grande longueur d'onde
EP0293579A1 (fr) * 1987-04-13 1988-12-07 L'oreal Compositions cosmétiques contenant un complexe cuivrique de l'acide 3,5-diisopropyl salicylique pour la protection contre le rayonnement UV et utilisation d'un tel composé en cosmétique
EP0303995A1 (fr) * 1987-08-17 1989-02-22 Kao Corporation Absorbeur de rayons ultraviolets de grandes longueurs d'onde, son procédé de préparation et composition cosmétique le contenant

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0242611A1 (fr) * 1986-04-02 1987-10-28 Kao Corporation Composé absorbant les rayons UV de grande longueur d'onde
EP0293579A1 (fr) * 1987-04-13 1988-12-07 L'oreal Compositions cosmétiques contenant un complexe cuivrique de l'acide 3,5-diisopropyl salicylique pour la protection contre le rayonnement UV et utilisation d'un tel composé en cosmétique
EP0303995A1 (fr) * 1987-08-17 1989-02-22 Kao Corporation Absorbeur de rayons ultraviolets de grandes longueurs d'onde, son procédé de préparation et composition cosmétique le contenant

Cited By (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995005150A1 (fr) * 1993-08-13 1995-02-23 Unilever Plc Agents antisolaires
US5573755A (en) * 1993-08-13 1996-11-12 Chesebrough-Pond's Usa Co., Division Of Conopco, Inc. Sunscreen agents
WO2000023042A1 (fr) * 1998-10-16 2000-04-27 The Procter & Gamble Company Compositions de protection uv
EP1002522A1 (fr) * 1998-11-19 2000-05-24 Beiersdorf Aktiengesellschaft Complexes d'aluminium avec des dérivés de dibenzoylméthane et compositions cosmétiques ou dermatologiques les contenant
FR2799120A1 (fr) * 1999-10-01 2001-04-06 Oreal Materiau comprenant un filtre uv-a organique et procede de deplacement de la longueur d'onde d'absorption maximale
WO2001024768A2 (fr) * 1999-10-01 2001-04-12 L'oreal Materiau comprenant un filtre uv-a organique et procede de deplacement de la longueur d'onde d'absorption maximale
WO2001024768A3 (fr) * 1999-10-01 2002-07-11 Oreal Materiau comprenant un filtre uv-a organique et procede de deplacement de la longueur d'onde d'absorption maximale
EP2196189A1 (fr) 2001-12-07 2010-06-16 L'oreal Compositions cosmétiques antisolaires à base d'un mélange synergique de filtres et utilisations
WO2012101204A1 (fr) 2011-01-28 2012-08-02 Momentive Performance Materials Gmbh Composition cosmétique photoprotectrice contre les uv
WO2014010098A1 (fr) 2012-07-13 2014-01-16 L'oreal Composition cosmétique comprenant des particules composites
WO2014009097A1 (fr) 2012-07-13 2014-01-16 L'oreal Composition cosmétique contenant des particules composites de protection
WO2014010099A1 (fr) 2012-07-13 2014-01-16 L'oreal Pigment composite et son procédé de préparation
WO2014010100A1 (fr) 2012-07-13 2014-01-16 L'oreal Composition cosmétique comprenant des particules composites de protection solaire
US11523976B2 (en) 2012-07-13 2022-12-13 L'oreal Composite pigment and method for preparing the same
US11266584B2 (en) 2012-07-13 2022-03-08 L'oreal Cosmetic composition comprising composite sunscreen particles
WO2014111566A2 (fr) 2013-01-21 2014-07-24 L'oreal Composition cosmétique ou dermatologique comprenant une mérocyanine et un agent anti-uv organique insoluble et/ou un agent anti-uv inorganique insoluble
US10934442B2 (en) 2014-06-09 2021-03-02 Agency For Science, Technology And Research Metal complexes
WO2015191004A1 (fr) * 2014-06-09 2015-12-17 Agency For Science, Technology And Research Complexes métalliques
WO2016030839A1 (fr) 2014-08-28 2016-03-03 L'oreal Composition gel/gel comprenant un filtre uv
WO2016083404A1 (fr) 2014-11-24 2016-06-02 L'oreal Composition cosmetique comprenant un phyllosilicate synthetique et un polyol et/ou un filtre uv
WO2016198581A1 (fr) 2015-06-11 2016-12-15 L'oreal Composition comprenant un agent de blocage d'ultraviolet, un polymère hydrophile réticulé anionique, un tensioactif ayant un hlb inférieur ou égal à 5, et un copolymère de silicone
WO2019096960A1 (fr) 2017-11-15 2019-05-23 L'oreal Compositions comprenant au moins un polymère acrylique et au moins un filtre uv organique insoluble
FR3083093A1 (fr) 2018-06-28 2020-01-03 L'oreal Composition photoprotectrice comprenant des particules de silice colloidale
FR3090329A1 (fr) 2018-12-21 2020-06-26 L'oreal Composition comprenant un filtre UV, un polymère hydrophile réticulé anionique, un tensioactif ayant une HLB inférieure ou égale à 5 et un alcane non volatil
FR3103704A1 (fr) 2019-11-29 2021-06-04 L'oreal Composition comprenant un filtre UV, un polymère éthylénique à groupe acide phosphonique et une huile hydrocarbonée
FR3103705A1 (fr) 2019-11-29 2021-06-04 L'oreal Composition comprenant un filtre UV, un polymère séquencé à groupe acide phosphonique et une huile hydrocarbonée

Also Published As

Publication number Publication date
AU3132193A (en) 1993-06-28
PT101102A (pt) 1994-02-28
CN1074909A (zh) 1993-08-04
MX9206875A (es) 1993-06-01

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