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WO1993011135A1 - Procede de preparation de complexes metalliques de protection solaire absorbant les rayons ultra-violets a - Google Patents

Procede de preparation de complexes metalliques de protection solaire absorbant les rayons ultra-violets a Download PDF

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Publication number
WO1993011135A1
WO1993011135A1 PCT/US1992/009691 US9209691W WO9311135A1 WO 1993011135 A1 WO1993011135 A1 WO 1993011135A1 US 9209691 W US9209691 W US 9209691W WO 9311135 A1 WO9311135 A1 WO 9311135A1
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WIPO (PCT)
Prior art keywords
aluminum
sunscreen
mixtures
salt
complexes
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PCT/US1992/009691
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English (en)
Inventor
Craig Steven Slavtcheff
George Endel Deckner
James Neal Matheson
Rodney Dean Bush
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Richardson Vicks Inc
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Richardson Vicks Inc
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—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
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/35—Ketones, e.g. benzophenone
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/77—Preparation of chelates of aldehydes or ketones
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/92—Ketonic chelates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
    • C07F1/005—Compounds containing elements of Groups 1 or 11 of the Periodic Table without C-Metal linkages
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/02—Iron compounds
    • C07F15/025—Iron compounds without a metal-carbon linkage
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
    • C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic Table without C-Metal linkages
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/06—Aluminium compounds
    • C07F5/069—Aluminium compounds without C-aluminium linkages
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/003—Compounds containing elements of Groups 4 or 14 of the Periodic Table without C-Metal linkages
    • 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 processes for preparing sunscreen complexes, and more particularly to sunscreen metal complexes, having enhanced UVA absorption.
  • These complexes comprise a dibenzoylmethane UVA-absorbing sunscreen complexed to a cationic species, preferably a metal cation. These complexes are useful for protecting the skin from the harmful effects of ultraviolet radiation.
  • This invention also relates to methods for preparing compositions containing these complexes.
  • the damaging effects of sunlight on skin are well documented.
  • the major short term hazard of prolonged exposure to sunlight is erythema (i.e. sunburn).
  • the 290 to 320 nanometer wavelength ultraviolet radiation range designated as the "UVB” wavelength range, tends to be the primary cause of erythema.
  • the 320 to 400 nanometer wavelength ultraviolet radiation range designated as the "UVA” wavelength range, also produces erythema.
  • UVA and UVB wavelength radiation are more fully discussed in DeSimone, "Sunscreen and Suntan Products", Handbook of Nonprescription Drugs. 7th Ed., Chapter 26, pp. 499-511 (American Pharmaceutical Association, Washington, D.C.; 1982); Grove and
  • sunscreen agents and physical sunblocks are commercially available to protect the skin from UV radiation.
  • Physical sunblocks scatter, reflect, and absorb ultrabiolet radiation. See, Sayre, R.M. et al., "Physical Sunscreens", J. Soc. Cos et. Chem.. vol. 41, no. 2, pp. 103-109 (1990).
  • Examples of physical sunblocks include titanium dioxide and zinc oxide.
  • compositions containing a high level of these agents are opaque, generally unattractive in color, and are viewed as unacceptable for usage on more than just the nose or tops of the ears. Furthermore, these agents are very susceptible to rub-off or wear-off resulting in little or no protection.
  • sunscreen agents exert their effects through chemical means, i.e., they absorb ultraviolet radiation so that it cannot penetrate the skin.
  • Sunscreens present the user with several problems. For example, they must be on the surface of the skin at the time of exposure to be effective. Sunscreens are preventative 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 UVB absorbers. The number of UVA absorbers is more limited with benzophenones and dibenzoylmethanes being the most well-known.
  • UVA absorption of the dibenzoylmethane chromophore is significantly enhanced when it is complexed to certain cationic species such as metal cations.
  • sunscreen agents having enhanced UVA absorption for protecting the skin from the harmful effects of UV radiation.
  • SUBSTITUTE SHEET It is therefore an object of the present invention to provide processes for the preparation of sunscreen complexes which provide enhanced UVA absorption.
  • A is a substituent selected from H, -OR or -NR where each R is independently H, straight or branched chain alkyl having from about 1 to about 20 carbon atoms, (CH2CH2 ⁇ ) q -H, or (CH2CH(CH3)0) q -H, wherein q is an integer from 1 to about 8;
  • B is a substituent selected from H, straight or branched chain alkyl having from about 1 to about 20 carbon atoms, (CH2CH2 ⁇ ) q -H, or (CH2CH(CH3)0) q -H, wherein q is an integer from 1 to about 8;
  • said salt is selected from salts of aluminum, zinc, calcium, magnesium, copper, iron, barium, strontium,, zirconium, titanium, tin, berylium, gallium, indium, lanthanum, manganese, antimony, bismuth, cerium, thorium, niobium, tantalum
  • SUBSTITUTE SHEET providing enhanced protection to the skin of humans or lower animals from the effects of ultraviolet radiation.
  • sunscreen metal complexes useful in the present invention are those having the general structure:
  • (S)n (H)n (Dp- (S) m represents a dibenzoylmethane sunscreen moiety, where m designates the number of moieties present in the complex.
  • (M) n represents a cationic species such as a metal, or alternatively ammonium or substituted ammonium, where n designates the number of species present in the complex.
  • (L)p represents a ligand, which is optionally present in the complex, where p designates the number of ligands present in the complex.
  • the sunscreen metal complexes of the present invention preferably absorb light in the visible wavelength range (i.e. above about 400 nm) only weakly or not at all.
  • the complexes are therefore either only lightly colored (e.g., light yellow or cream colored) or are essentially white. This is desirable for cosmetic reasons.
  • the sunscreen metal complexes preferably do not have a £ of greater than about 500 for any wavelength above about 400 nm, and most preferably the 6 is essentially zero for any wavelength above about 400 nm.
  • the sunscreen moieties which comprise the sunscreen complexes of the present invention are those containing the dibenzoylmethane chromophore. This chromophore is characterized as being effective for strongly absorbing radiation in the UVA range.
  • dibenzoyl methane sunscreen moieties which comprise the complexes of the instant invention are fully disclosed in U.S. Patent Nos. 4,489,057 and 4,387,089, which have already been incorporated by reference, supra.
  • the number of sunscreen moieties present is designated by m, wherein m is an
  • SUBSTITUTE SHEET integer selected from 1 through 8 more preferably m is an integer selected from 1 through 4, even more preferably is an integer selected from 1 through 3, and most preferably is 2. Furthermore, it is realized that the complexes of the instant invention can exist as a mixture of different species in which the m value varies. Thus, it is possible to obtain a complex in which the average m value is a noninteger average of the m values for the species present.
  • A is a substituent of variable position on the aromatic ring selected from H, -OR or -NR2 where each R is independently H, straight or branched chain alkyl having from about 1 to about 20 carbon atoms, (CH CH2 ⁇ ) q -H, or (CH2CH(CH3)0) q -H, wherein q is an integer from 1 to about 8; and B is a substituent of variable position on the aromatic ring selected from H, straight or branched chain alkyl having from about 1 to about 20 carbon atoms, (CH2CH2 ⁇ ) q -H, or (CH2CH(CH3)0) q -H, wherein q is an integer from 1 to about 8.
  • A is preferably para -OCH3 and B is para t-butyl, i.e. 4,4'-methoxy-t-butyldibenzoylmethane (CTFA adopted name: butyl dibenzoylmethane, which is commercially available under the trademark Parsol R 1789 from Givaudan), or alternatively A is H and B is para isopropyl, i.e. 4-isopropyl- dibenzoylmethane (CTFA adopted name: isopropyl dibenzoylmethane, which is commercially abailable under the trademark Eusolex R 8020 from Merck) .
  • CTFA 4,4'-methoxy-t-butyldibenzoylmethane
  • the dibenzoylmethane chromophore can lose a hydrogen atom to form the corresponding anionic species. This phenonenon is more likely at higher pH values (i.e. alkaline pH values) and when the dibenzoylmethane chromophore is complexed to a cationic species such as a metal.
  • a cationic species such as a metal.
  • molar absorptivity value is a quantitative measure of the ability of a molecule to absorb ultra ⁇ violet light at a specified wavelength.
  • the molar absorptivity alue is expressed at a particular wavelength of light as the molar absorption coefficient (represented herein by “ e " which is expressed in units of liter/mole cm), which is calculated by the equation:
  • A log 10 _Jl I wherein "I 0 " is the intensity of a particular wavelength of incident radiation on an absorbing path; and "I” is the intensity of the same particular wavelength of transmitted radiation which has passed through the absorbing path.
  • absorption maximum means a wavelength of radiation at which the chro ophore-containing molecule has the greatest molar absorptivity value relative to wavelengths immediately above and below the absorption maximum wavelength.
  • absorption maximum is easily identified as a peak in the graph of the spectrum generated by the instrument measuring the UV absorption.
  • Absorption maximum (designated herein as ⁇ max) are provided for representative sunscreen compounds of the present invention in the Examples hereinafter.
  • the sunscreen complexes of the present invention comprise a cationic species, preferably a metal, or alternatively ammonium or substituted ammonium, represented by the general structure (M) n .
  • metal cations useful in the complexes of the present invention include alkali metal (e.g., sodium and potassium), alkaline earth metal (e.g., calcium and magnesium), and transition and heavy metals (e.g., aluminum and strontium).
  • alkali metal e.g., sodium and potassium
  • alkaline earth metal e.g., calcium and magnesium
  • transition and heavy metals e.g., aluminum and strontium
  • Preferred for use in the complexes of the instant invention are the metals selected from the group consisting of aluminum, zinc, calcium, magnesium, copper, iron, barium, strontium, zirconium, titanium, tin, beryllium, gallium, indium, lanthanum, manganese, antimony, bismuth, cerium, thorium, niobium, tantalum, antimony, molybdenum, tungsten, lithium, sodium, potassium and mixtures thereof.
  • These metal cations are useful in any of their possible valence states and in combinations of these states (i.e. where for example some of the metal cations are in one of the cation's allowable valence states, and some of the metal cations are in another of the metal cation's allowable valence states, etc.).
  • the sunscreen complexes of the instant invention can also comprise complexes with other cationic species such as ammonium, substituted ammonium (e.g., mono-, di-, tri- and tetra- alkyl and alkoxy substituted), and cations of diamines (e.g., tetra- alkyl and alkoxy substituted ethylene diamines).
  • other cationic species such as ammonium, substituted ammonium (e.g., mono-, di-, tri- and tetra- alkyl and alkoxy substituted), and cations of diamines (e.g., tetra- alkyl and alkoxy substituted ethylene diamines).
  • preferred cation species include metals selected from the group consisting of aluminum, titanium, copper, iron, and zinc.
  • sunscreen complexes of the present invention aluminum cations having a valence of 3+ are most preferred.
  • the number of M species present in the complex is designated by n, wherein n is an integer selected from 1 through 4, more preferably n is an integer selected from 1 through 3, even more preferably n is an integer selected from 1 and 2, and most preferably n is 1. Furthermore, it is realized that the complexes of the instant invention can exist as a mixture of different species having different n values. Thus, it is possible to obtain a complex in which the average n value is a noninteger weighted average of the n values for the species present.
  • the M species can be derived from any suitable sources.
  • the M species can be derived from any suitable sources.
  • the M when the M
  • SUBSTITUTE S! species of the complexes is a metal cation
  • the cation can be derived from a wide variety of salts.
  • salts include metal oxides, hydroxides, fluorides, chlorides, bromides, iodides, carbonates, bicarbonates, phosphates, hydrogen phosphates, dihydrogen phosphates, alkoxides (e.g., isopropxide) sulfates, hydrogensulfates, nitrates, sulfites, nitrites, borates, chlorates, bro ates, perchlorates, perbromates, diphosphates, polyphosphates, thiocyanates, carboxylates (preferably, acetates and stearates), and mixtures thereof.
  • the ammonium or substituted ammonium species can be derived from a wide variety of ammonium and substituted 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 sources of the cationic species include aluminum monoacetate, aluminum diacetate, aluminum stearate, and mixtures thereof. Expecially preferred is aluminum monoacetate. (Dp Ligand
  • the sunscreen complexes of the present invention optionally comprise an organic or inorganic ligand represented by the general structure (L) p .
  • organic or inorganic ligand represented by the general structure (L) p .
  • Both neutral and anionic ligands are useful in the complexes of the present invention.
  • Useful organic ligands include, but are not limited to, those selected from the group consisting of carboxylic acids, dicarboxylic acids, and polycarboxylic acids and their anions; amines, diamines, and polya ines; alcohols, diols, and polyols and their anions; thiols, dithiols, and polythiols and their anions; a ino acids and their anions; any other pharmaceutically-acceptable organic ligands, and mixtures thereof.
  • Useful inorganic ligands include, but are not limited to, water and hydroxide anion, halide (e.g., fluoride, chloride, bromide, and iodide), carbonate, bicarbonate, phosphate, hydrogen phosphate, dihydrogen phosphate, sulfate, hydrogen sulfate, nitrate, sulfite, nitrite, borate, chlorate, bromate, perchlorate, perbromate, diphosphate, polyphsophate, thiocyanate, any other pharmaceutically-acceptable inorganic ligands, and mixtures thereof.
  • halide e.g., fluoride, chloride, bromide, and iodide
  • carbonate bicarbonate
  • phosphate hydrogen phosphate, dihydrogen phosphate, sulfate, hydrogen sulfate, nitrate, sulfite, nitrite, borate
  • chlorate bromate, perchlorate,
  • SUBSTITUTE SHEET ligands as used herein is meant those organic and inorganic ligands which are acceptable from a toxicity viewpoint.
  • ligands selected from water, hydroxide anion, and carboxylic acids having from about 2 to about 22 carbon atoms and their anions are preferred.
  • Other preferred ligands include ethoxide and isopropoxide.
  • Especially preferred among the carboxylic acids and their anions are acetic acid and the acetate anion, octanoic acid and the octanoate anion, and stearic acid and the stearate anion.
  • the number of ligands present in the complex is designated by p, wherein p is an integer selected from 0 through 4, more preferably p is an integer selected from 0 through 3, even more preferably p is an integer selected from 0 through 2, even more preferably p is an integer selected from 0 and 1, and most preferably p is 0.
  • the complexes of the instant invention can exist as a mixture of different species having different p values.
  • the average p value is a noninteger weighted average of the p values of the species present.
  • sunscreen metal complexes of the present invention include, for example:
  • the sunscreen metal complexes of the present invention can be prepared as described in the Examples below. In further embodiments, these complexes can then be directly formulated into a desired carrier. Alternatively, these sunscreen complexes can be isolated before being formulated into the desired carrier. In yet
  • sunscreen complexes can be prepared directly in the desired carrier.
  • the sunscreen metal complex is prepared by combining a sunscreen compound and a metal salt in a suitable solvent selected from the group consisting of water, acetone, ethyl acetate, methyl t-butyl ether, C1-C5 alcohols, diols, triols, C12-15 alcohols benzoate, dimethyl isosorbide, chlorinated solvents (e.g., methylene chloride), isodecyl neopentanoate, diisopropyl adipate, and mixtures thereof.
  • a suitable solvent selected from the group consisting of water, acetone, ethyl acetate, methyl t-butyl ether, C1-C5 alcohols, diols, triols, C12-15 alcohols benzoate, dimethyl isosorbide, chlorinated solvents (e.g., methylene chloride), isodecyl neopentanoate, diisopropyl adipate, and mixture
  • Preferred metal salts include those selected from the group consisting of salts of aluminum, zinc, calcium, magnesium, copper, iron, barium, strontium, zirconium, titanium, tin, beryllium, gallium, indium, lanthanum, manganese, antimony, bismuth, cerium, thorium, niobium, tantalum, antimony, molybdenum, tungsten, lithium, sodium, potassium, and mixtures thereof. More preferred are salts of aluminum, titanium, copper, iron, zinc, and mixtures thereof.
  • salts of aluminum with those selected from the group consisting of aluminum acetate, aluminum diacetate, aluminum stearate, aluminum distearate, aluminum octanoate, aluminum ethoxide, aluminum isopropoxide, and mixtures thereof, being more preferred, and aluminum monoacetate being most preferred.
  • ammonium and substituted ammonium chlorides, bromides, and hydroxides can be employed.
  • a base can be added in order to facilitate the dissolution of the sunscreen compound.
  • the sunscreen compound and the base are prereacted in the solvent system before the metal salt is added.
  • Preferred bases include sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium bicarbonate, sodium carbonate, and mixtures thereof.
  • the solvent system can be heated to its boiling point if required. Where the sunscreen metal complex is isolated and purified, this is preferably accomplished by filtration, washing, drying, and evaporation of the filtrate. Additionally, the complex can be further purified by recrystallization from a suitable solvent. The Examples given below provide representative preparations of the sunscreen metal complexes and compositions containing them.
  • One or more of the sunscreen complexes of the present invention can be incorporated into a variety of carriers, including pharmaceutical and cosmetic carriers, paints, coatings, polymeric maxtrices, fiber matrices, and the like.
  • the complexes are incorporated into pharmaceutical and cosmetic carriers.
  • the sunscreen metal complexes of the present invention typically comprise from about 0.1% to about 30.0% by weight of the sunscreen compositions of the present invention, preferably from about 1% to about 20%, and most preferably from about 5% to about 15%.
  • the compositions of the instant invention can comprise the following components.
  • compositions of the instant invention can comprise a safe and effective amount of a topical pharmaceutically-acceptable carrier or diluent which can be of a variety of different forms.
  • safe and effective is meant an amount sufficient to act as a suitable vehicle for the sunscreen metal complexes and any other components, but not so much as to cause any side effects or skin reactions.
  • “Pharmaceutically-acceptable” means that the carrier is suitable for topical application to the skin without causing any untoward safety or toxicity concerns. In other words, these carriers are suitable for use on humans and lower animals.
  • the topical carrier can be in the form of an emulsion including, but not limited to, oil-in-water, water-in-oil, water-in-oil-in-water, and oil-in-water-in-silicone emulsions. These emulsions can cover a broad range of consistencies including thin lotions (which can also be suitable for spray or aerosol delivery), creamy lotions, light creams, heavy creams, and the like.
  • Other suitable opical carriers include anhydrous liquid solvents such as oils and alcohols; aqueous-based single phase liquid solvents (e.g. hydro-alcoholic solvent systems); anhydrous solids and semisolids (such as gels and sticks); and aqueous based gel and mousse systems. Examples of topical carrier systems useful in the present invention are described in the following four references all of which are incorporated herein by reference in their entirety: "Sun Products Formulary" Cosmetics & Toiletries, vol. 105, pp. 122-139 (December
  • the pharmaceutically-acceptable topical carriers typically comprise from about 0.1% to about 99.8% by weight of the sunscreen compositions of the present invention, preferably from about 80% to about 99%, and most preferably from about 85% to about 95%.
  • a preferred topical carrier of the compositions of the instant invention is an oil-in-water type emulsion.
  • the pH of these oil-in- water emulsion compositions herein is preferably in the range of from about 3.5 to about 9. Additionally, the mean particle size of the dispersed oil phase materials can be in the range of from about 1 to about 10 microns with greater than about 75% of the particles 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 Givaudan Corporation), p-Aminobenzoic acid, its salts and its derivatives (ethyl, isobutyl, glyceryl esters; p-dimethylamino- benzoic acid; 2-ethylhexyl N,N-dimethylaminobenzoate; p-Methoxy- cinnamic Acid Diethanolamine Salt (available as Bernel Hydro from Bernel Chemical Co.); Anthranilates (i.e., o-aminobenzoates; methyl, octyl, amyl, menthyl
  • sunscreens include the solid physical sunblocks such as titanium dioxide (micronized 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 sunscreening benefit through reflecting, scattering, and absorbing harmful UV, visible, and infrared radiation.
  • Other useful sunscreens are those having both a UVA and a UVB 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 Patent Application No. 416,837, which have already been incorporated by reference herein.
  • these additional sunscreens can comprise from zero to about 20% of the composition, preferably from about 0.5% to about 10%. Exact amounts will vary depending upon the sunscreen chosen and the desired Sun Protection Factor (SPF). SPF is a commonly used measure of photoprotection of a sunscreen against erythema. See Federal Register. Vol. 43, No. 166, pp. 38206-38269, August 25, 1978.
  • the compositions can also contain one or more artificial tanning ingredients such as dihydroxyacetone, tyrosine, a ino acids, and amino acid derivatives. Typically, artificial tanning ingredients can be incorporated into 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 instant invention is a thickener.
  • thickeners which can be employed include, but are not limited to, xanthan gum, magnesium aluminum silicate, guar gum, cationic guar gum, Rhamsan Gum (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 and bentonite, sodium magnesium silicate and mixtures thereof.
  • thickeners examples include magnesium aluminum silicate and xanthan gum and mixtures thereof.
  • compositions of the instant invention comprise from about 0.1% to about 5% thickener, preferably from about 0.25% to about 2%, and most preferably from about 0.5% to about 1%.
  • Humectants/Moisturizers The compositions of the instant invention can also optionally contain one or more humectants/moisturizers.
  • a variety of humectants/moisturizers can be employed and can be present at a level of from about 0.5% to about 30%, more preferably from about 2% to about 8% and most preferably from about 3% to about 5%.
  • These materials include urea; guanidine; glycolic acid and glycolate salts (e.g. ammonium and quaternary alkyl ammonium); lactic acid and lactate salts (e.g. ammonium and quaternary alkyl ammonium);
  • SUBSTITUTE SHEET polyhydroxy alcohols such as sorbitol, glycerin, hexanetriol, propylene glycol, hexylene glycol and the like; polyethylene glycol; sugars and starches; sugar and starch derivatives (e.g. alkoxylated glucose); panthenol ; hyaluronic acid; lactamide monoethanolamine; acetamide monoethanolamine; and mixtures thereof.
  • Preferred humectants/moisturizers for use in the compositions of the present invention are the C3-C5 diols and triols. Especially preferred is the triol, glycerin.
  • Emollients The compositions of the present invention can also optionally comprise at least one emollient.
  • suitable emollients include, but are not limited to, volatile and non-volatile silicone oils, highly branched hydrocarbons, and non-polar fatty acid and fatty alcohol esters, and mixtures thereof.
  • Emollients useful in the instant invention are further described in U.S. Patent No. 4,919,934, to Deckner et al., issued April 24 1990, which is incorporated herein by reference in its entirety.
  • the emollients can typically comprise in total from about 1% to about 50%, preferably from about 1% to about 25%, and more preferably from about 1% to about 10% by weight of the compositions of the present invention.
  • Emulsi iers are preferably comprise in total from about 1% to about 50%, preferably from about 1% to about 25%, and more preferably from about 1% to about 10% by weight of the compositions of the present invention.
  • emulsifiers can include any of a wide variety of nonionic, cationic, anionic, and zwitterionic emulsifiers disclosed in the prior patents and other references. See McCutcheon's, Detergents and Emulsifiers. North 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 December 20, 1983; and U.S. Patent No. 3,755,560, to Dickert et al., issued August 28, 1973; these four references are incorporated herein by reference in their entirety.
  • Suitable emulsifier types include esters of glycerin, esters of propylene glycol, fatty acid esters of polyethylene glycol, fatty acid esters of polypropylene glycol, esters of sorbitol, esters of sorbitan anhydrides, carboxylic acid copolymers, esters and ethers of glucose, ethoxylated ethers, ethoxylated alcohols, alkyl
  • I3STITUTE SHEET phosphates polyoxyethylene fatty ether phosphates, fatty acid 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-2 methyl glucose ether distearate, Ceteth-10, Polysorbate 80, cetyl phosphate, potassium cetyl phosphate, diethanola ine cetyl phosphate, Polysorbate 60, glyceryl stearate, PEG-100 stearate, and mixtures thereof.
  • the emulsifiers can be used individually or as a mixture of two or more and comprise from about 0.1% to about 10%, preferably from 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 the compositions of the present invention. Non-limiting examples include Vitamin A, and derivatives thereof, ascorbic acid, Vitamin B, biotin, Vitamin D, Vitamin E and derivatives thereof such as tocopheryl acetate, panthothenic acid, and mixtures thereof can also be used.
  • compositions of the instant invention is a carboxylic copolymer (acrylic acid copolymer).
  • Carbomer 1342 available as Carbopol 1342 from B.F. Goodrich. These polymers are more fully described in U.S. Patent No. 4,509,949, to Huang et al., issued April 5, 1985, and U.S. Patent No. 2,798,053, to Brown, issued July 2, 1957, these patents being incorporated herein by reference.
  • acrylate/alkyl acrylate crosspolymers such as Acrylates/C10-C30 Alkyl Acrylate Crosspolymer (available as Pemulen TR-1 and Pemulen 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 from 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 from about 0.075% to about 0.175%.
  • SUBSTITUTE SHEET examples of these additional ingredients include various polymers for aiding the film-forming properties and substantivity of the composition (such as a copolymer of eicosene and vinyl pyrrolidone, an example of which is available from GAF Chemical Corporation as Ganex V-220R); gums, resins, and thickeners; preservatives for maintaining the antimicrobial integrity of the compositions; antioxidants; chelators and sequestrants; anti-acne agents; keratolyic agents;and agents suitable for aesthetic purposes such as fragrances, pigments, and colorings.
  • Other useful materials include acidic materials such as salicylic acid, lactic acid, glycolic acid, benzoic acid, citric acid and the like. Without being limited by theory, it is believed that these acid materials are useful for maintaining the pH of the composition and enhancing product performance.
  • the present invention further relates to a method for pro ⁇ tecting the skin of humans or lower animals from the effects of UVA and UVB wavelength radiation, such as sunburn and premature aging of the skin.
  • a method comprises topically applying to the human or lower animal an effective coating of a sunscreen agent or 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 of 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. 38206-38269, August 25, 1978.
  • the sunscreen solution is then slowly added to the aluminum diacetate solution with stirring, and the mixture is refluxed for approximately 10 minutes. Next, the solvents are removed by rotary evaporation to yield the crude sunscreen aluminum complex. This crude complex is redissolved in approximately 150 L of methylene chloride with heating and is then vacuum filtered using a coarse, sintered glass funnel to remove any undissolved materials, which are washed with methylene chloride (approximately 2 X 20 L).
  • this sunscreen aluminum complex is prepared starting with 1.0 gram of aluminum dioctanoate
  • the resulting oil phase solution of the complex is suitable for incorporation into an emulsion or gel composition.
  • this sunscreen aluminum complex is prepared using 33.75 grams (0.240 moles) of aluminum monoacetate and 91.24 grams (0.343 moles) of 4-isopropyldibenzoyl- methane. A light yellow solid is obtained suitable for incorporation into a sunscreen composition.
  • Example 1 4.0 grams of the sunscreen aluminum complex prepared in Example 1 is added to 100 grams of C ⁇ 2-15 Alcohols Benzoate by heating to 90°C. The mixture is cooled to 80°C and 1 gram of dibutyllaurolyl glutamide (available as Coagulen GP-1 from Ajinomoto Co., Inc., Tokyo, Japan) is added to gel the mixture upon cooling. This gel composition is useful for topical application to the skin to provide protection from the harmful effects of ultraviolet radiation.
  • dibutyllaurolyl glutamide available as Coagulen GP-1 from Ajinomoto Co., Inc., Tokyo, Japan
  • analogous gel compositions can be prepared using the other sunscreen metal complexes of the instant invention and with other solvents such as isodecylneopentanote, diisopropyl adipate, and dimethylisosorbide.
  • An emulsion composition is prepared from the following ingredients using standard methods.
  • Phase A ingredients are combined and heated to 90°C and then cooled to 80°C.
  • Phase B ingredients are added with mixing at 80°C to form the oil phase.
  • Phase C ingredients are combined and heated to 80°C.
  • the oil phase is added to Phase C with homogenization to form the emulsion.
  • the emulsion is cooled with stirring to 40°C.
  • the Phase D ingredients are combined and added to the emulsion with mixing. The emulsion is then cooled to room temperature with stirring.
  • This emulsion composition is useful for topical application to the skin to provide protection from the harmful effects of ultraviolet radiation.
  • the above sunscreen emulsion is prepared using 0.50 grams of aluminum dioctoate in place of the aluminum distearate.
  • An emulsion composition is prepared from the following ingredients using standard methods.
  • Phase A ingredients are combined and heated with mixing to 90°C and then cooled to 80°C.
  • the Phase B ingredients are combined and heated wtih mixing to 80OC.
  • the Phase A mixture is added to the Phase B mixture with homogenization to form the emulsion.
  • the emulsion is cooled with stirring to 40°C.
  • the Phase C ingredients are combined and added to the emulsion with mixing.
  • the emulsion is then cooled to room temperature with stirring.
  • 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 to
  • Phase B 80°C to form the oil phase.
  • Phase B 80°C to form the oil phase.
  • Phase A Phase A is added to
  • Phase B with homogenization to form the emulsion which is then cooled to room temperature with stirring.
  • SUBSTITUTE SHEET 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.

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Abstract

La présente invention concerne des procédés de préparation des complexes de protection solaire, et plus particulièrement des complexes métalliques de protection solaire présentant une capacité d'absorption des rayons ultra-violets A amélioré. Ces complexes comprennent en tant qu'agent de protection solaire absorbant les rayons ultra-violets A du dibenzoylméthane complexé avec une espèce cationique, de préférence un cation métal. Ces complexes sont utilisés pour protéger la peau des effets nocifs de rayonnements ultra-violets. Cette invention concerne également des procédés de préparation de compositions contenant lesdits complexes.
PCT/US1992/009691 1991-11-27 1992-11-12 Procede de preparation de complexes metalliques de protection solaire absorbant les rayons ultra-violets a Ceased WO1993011135A1 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998038965A3 (fr) * 1997-03-07 1998-12-17 Brian Joseph Wilkins Composition d'ecran solaire et son procede de production
EP0747038A3 (fr) * 1995-06-06 1999-04-07 Unilever Plc Emulsions cosmétiques épaissis et stabilisées contenant des filtres solaires
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
AU2007287592B2 (en) * 2006-08-23 2010-07-29 Unilever Plc Sunscreen composition

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9144535B1 (en) * 2014-05-05 2015-09-29 Johnson & Johnson Consumer Inc. Particulate zinc oxide with manganese ion dopant
US9144536B1 (en) * 2014-05-05 2015-09-29 Johnson & Johnson Consumer Inc. Particulate zinc oxide with manganese, iron and copper dopant ions

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Publication number Priority date Publication date Assignee Title
FR1152191A (fr) * 1955-04-06 1958-02-12 Du Pont Composés chélatés d'aluminium
GB1387281A (en) * 1972-01-11 1975-03-12 C A Lab Inc Ultra-violet light absorber compositions

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Publication number Priority date Publication date Assignee Title
FR1152191A (fr) * 1955-04-06 1958-02-12 Du Pont Composés chélatés d'aluminium
GB1387281A (en) * 1972-01-11 1975-03-12 C A Lab Inc Ultra-violet light absorber compositions

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Title
BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN vol. 47, no. 8, 1974, pages 1901 - 1907 OHNO, T. ET AL. *
CHEMICAL ABSTRACTS, vol. 106, 1987, Columbus, Ohio, US; abstract no. 72712p, YANAGIDA, T. ET AL. page 367 ; *
CHEMICAL ABSTRACTS, vol. 116, 1992, Columbus, Ohio, US; abstract no. 91147f, MIYAMOTO, T. ET AL. page 489 ; *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0747038A3 (fr) * 1995-06-06 1999-04-07 Unilever Plc Emulsions cosmétiques épaissis et stabilisées contenant des filtres solaires
WO1998038965A3 (fr) * 1997-03-07 1998-12-17 Brian Joseph Wilkins Composition d'ecran solaire et son procede de production
US6136299A (en) * 1997-03-07 2000-10-24 Donville Holdings Limited Sunscreen composition and method of producing same
AU735323B2 (en) * 1997-03-07 2001-07-05 Donville Holdings Limited Sunscreen composition and method of producing same
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
DE19853288A1 (de) * 1998-11-19 2000-05-25 Beiersdorf Ag Aluminiumkomplexe von Dibenzoylmethanderivaten und kosmetische oder dermatologische Zubereitungen, diese enthaltend
AU2007287592B2 (en) * 2006-08-23 2010-07-29 Unilever Plc Sunscreen composition

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PT101103A (pt) 1994-02-28
AU3072192A (en) 1993-06-28
CN1073858A (zh) 1993-07-07

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