US3670074A - Sunscreen formulation containing triethanolamine neutralized 2-hydroxy-4-methoxy-benzophenone-5-sulfonic acid - Google Patents

Sunscreen formulation containing triethanolamine neutralized 2-hydroxy-4-methoxy-benzophenone-5-sulfonic acid Download PDF

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US3670074A
US3670074A US108961A US3670074DA US3670074A US 3670074 A US3670074 A US 3670074A US 108961 A US108961 A US 108961A US 3670074D A US3670074D A US 3670074DA US 3670074 A US3670074 A US 3670074A
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sulfonic acid
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Abraham J Doner
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CYRIL DONER
CYRIL DONER MILES LAB Inc
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CYRIL DONER
CYRIL DONER MILES LAB 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
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/46—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur
    • A61K8/466—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur containing sulfonic acid derivatives; Salts

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  • ABSTRACT An active sunscreen ingredient comprised of 2-hydroxy-4- methoxy-benzophenone-S-suifonic acid, neutralized with triethanoiamine, and formulated with various compatible vehicles to produce efiective sunscreens for human use.
  • the present invention relates to ultraviolet absorbers and more particularly to sunscreen formulations for protection of human skin from solar radiation.
  • agent which produce sensitivity are the sulfonamides, tranquilizers of the phenothiazine type, the sulfonylurea oral antidiabetic agents and the antihypertensive diuretic agents.
  • benzophenone derivatives are utilized as sunscreen agents in protecting natural and man-made materials, such as textile goods, dyes and coloring agents, various resins, coating and film materials, and miscellaneous chemical compositions against the action of sunlight, these benzophenones are unsuitable for human skin for a number of reasons, including that they are highly irritating and do not lend themselves to acceptable formulations for human use.
  • the invention provides a sunscreen formulation containing an active ingredient for the protection of human skin from solar radiation comprised of a triethanolamine neutralized 2- hydroxy-4-methoxy benzophenone-S-sulfonic acid, in a compatible vehicle, which may include an emulsifier, such a glycerol monostearate, a wax, such as beeswax, water, an alcoho], such as denatured or cetyl alcohol, thickening agents, preservative agents, perfumes, etc.
  • an emulsifier such as a glycerol monostearate
  • a wax such as beeswax
  • water an alcoho
  • thickening agents such as denatured or cetyl alcohol
  • preservative agents perfumes, etc.
  • the amount of active ingredient within the formulation ranges in amounts from about 0.1 percent to about 30 percent.
  • the invention provides a sunscreen agent that prevents and/or substantially minimizes the photochemical degradation and other adverse effects caused by exposure of human skin to sunlight through the absorption of ultraviolet wave lengths.
  • the sunscreen agents of the invention absorb or screen radiation wave lengths responsible for erythema on human skin, minimizes the aging effects of solar radiation on humans and inhibits freckling or irregular pigmentation from such radiation.
  • the sunscreen agents of the invention are readily incorporated into various types of vehicles for cosmetic materials, such as make-up bases, face powders, after-shave lotions, etc. for use by individuals who freckle, are afflicted with chloasma, or prefer their natural color, as well as by others.
  • the sunscreen agents of the invention also tend to decrease sunlight accelerated aging and sunlight induced carcinogenesis on exposed human skin which has been coated with a formulation of said agents.
  • the sunscreen agents of the invention comprise Z-hydroxy- 4-methoxy-benzophenone-5-sulfonic acid neutralized with a neutralization agent having properties of triethanolamine and are formulated into any desired carrier, vehicle, emulsion, cream, lotion, ointment, solution, suspension, gel, aerosol or in any other form suitable for human usage.
  • the active sunscreen agent of the invention is 2-hydroxy-4-methoxy-benzophenone-5sulfonic acid neutralized with triethanolamine.
  • the amount of active sunscreen agent of the invention in a given formulation ranges from about 0. 1 percent to about 30 percent or more as desired.
  • the emulsions, gels, vehicles, etc. utilized in preparing sunscreen formulations containing the active sunscreening agents of the invention contain any one or combinations of; cetyl alcohol, stearyl alcohol, stearic or lauric acids and all other fatty acids and alcohols generally used in cosmetic and like materials emulsions or other formulations intended for human use; various waxes such as beeswax, microcrystalline wax, spermaceti, etc., and all other waxes generally used in cosmetic and like material emulsions or other formulations intended for human use; various petroleum materials, such as petrolatum, liquid petrolatum, mineral oil, silicone oil, etc.
  • oils, fats, and the like materials generally used in cosmetic and like material emulsions or other formulations intended for human use fatty acid esters, such as isopropyl myristate and similar esters of fatty acids having a composition generally ranging from about C to about C various silicone derivatives, polyvinyl pyrrolidone methyl or propyl paraben, C to C glycols, various stearates, and other materials whether similar or otherwise that are generally used or considered suitable for use in cosmetic and like material emulsions or other formulations intended for human use.
  • the vehicle materials, emulsifiers, combination of emulsifiers, and other like material compatible with the active sunscreen ingredients or agents of the invention are also selected from various anionic surfactants, including amine soaps of fatty acids such as characterized by triethanolamine stearate; cationic surfactants, such as characterized by monoethanol ammonium fluoride; amphoteric surfactants such as characterized by N-fatty B-amino-propionate (RNI-I CH -CH COOH); and nonionic surfactants such as characterized by sorbitan derivatives of C to C fatty acids, polyoxyethylene sorbitan derivatives of C to C fatty acids, polyoxyethylene esters of C to C fatty acids, glyceryl stearates, fatty acid polyisopropylene complexes; and ethylenes oxide fatty alcohol lanolin complexes.
  • anionic surfactants including amine soaps of fatty acids such as characterized by triethanolamine stearate; cationic surfact
  • compatible materials, vehicles, carriers, gels and like materials include perfumes, clays, preservative agents, etc. and are all utilizable with the active sunscreen agents of the invention in formulating suitable gels, emulsions, either of the water-in-oil type or the oil-in-water type, aerosols, etc. or other forms suitable for application to humans.
  • a 5 percent concentration of PABA (para-amino-benzoic-acid) and a 5 percent concentration of triethanolamine neutralized 2-hydroxy-4-methoxy-benzophenone-5-sulfonic acid in a compatible vehicle each provided protection for about 20 to 25 minutes.
  • the active sunscreen agents of the invention generally comprise suitably neutralized 2-hydroxy-4-methoxybenzophenone-S-sulfonic acid, and similar benzophenone derivatives having the formula:
  • A is selected from a neutralizing agent having properties characterized by triethanolamine.
  • the active sunscreen agents of the invention are utilized in a variety of formulations and are present therein in amounts ranging from about 0.1 percent to about 30 percent by weight.
  • sunscreen agents of the invention in various formulations, bases, carriers, emulsifiers and other compatible vehicles, the following examples are set forth.
  • UVINUL MS40 A 2-hydroxy-4-methoxy benzophenone-S-sulfonic acid is available from Antara Chemical, New York, New York under the registered tradename UVINUL MS40 and U- VINUL-40-20 percent Aqueous Solution.
  • UVINUL MS-40 is a free flowing powder at 25 C., light-cream in color and has a molecular weigh of 309 and a pH 2 for a l percent aqueous solution, with a solubility of about 5 g/lOO mls of water at 25 C. after 15 minutes of agitation.
  • U- VINUL MS-40-20% Aqueous Solution is the same material in an aqueous solution at the concentration indicated.
  • the powder is first dissolved in water and then combined with a suitable neutralizing agent and a particular vehicle.
  • EXAMPLE I A typical embodiment of an oil-in-water emulsion formulation utilizing UVINUL MS-40-20% Aqueous Solution, (referred to as Benzophenone Derivative) in its neutralized form, an the active ingredient is as follows, with all parts being by weight unless otherwise noted.
  • Emulsion Vehicle ARLACEL 165 Glyceryl Monostearate
  • Cetyl Alcohol 2% Isopropyl Palmitate 2% Dimethyl Silicone Oil
  • Light Liquid Petrolatum 2% Polyvinyl Pyrrolidone 0.5%
  • ARLACEL is a tradename for a glyceryl monostearate containing emulsifier available from Atlas Chemical Industries, Inc., of Wilmington, Delaware and Sorbo 70% is a tradename for a sorbitol containing emollient having 70 percent solids also available from Atlas Chemical Industries, Inc.
  • An alternative emulsifier usable in place of "ARLACEL 165" is Prornulgen," a tradename for an emulsifier available from Robinson Wagner Company, Inc., of Mamaroneck, New York.
  • the above embodiment of a particular formulation can be varied by adjusting the amount of active ingredient so as to vary between about O.l percent to about 30 percent and by adjusting and/or omitting certain ingredients of the vehicle.
  • the amount of glycerol monostearate can vary between about 3 percent to 5 percent, the silicone oil, i.e.
  • dimethyl silicone oil, and/or the petrolatum can be replaced by mineral oil and the amount varied between about 1 percent to 15 percent, the amount of sorbitol varied between about 3 percent to 30 percent or partially replaced by a glycol, the amounts of isopropyl palmitate, and polyvinyl pyrrolidone may also be varied and/or replaced with other comparable material and even omitted as exemplified in further embodiments set forth hereinafter.
  • minor amounts perfumes and/or preservative agents are added as desired.
  • the invention is not limited to the specific proprietary items set forth in the examples but includes all emulsifiers, emollients, carriers, vehicles, preservatives, perfumes and other materials generally found in cosmetic materials, sun protective formulations, etc., suitable for use on human skin.
  • the formulation of the above embodiment of an oil-inwater emulsion is carried out by placing the appropriate amounts of ARLACEL 165, cetyl alcohol, dimethyl silicone oil and light liquid petroletum in a suitable steam-jacketed kettle or the like and subjecting the mixture to slow agitation and heating conditions to about 70 C. so as to form a first solution.
  • the remaining ingredients of the emulsion vehicle i.e. all of the remainder ingredients except the active ingredient, are placed in another suitable container and slowly agitated and heated up to about 75 C. to form a second solution.
  • the two solutions are then combined with continuous and vigorous agitation by adding the second solution to the first solution.
  • the sulfonated 2-hydroxy-4-methoxybenzophenone derivative is neutralized with a sufficient amount of an amine having properties characterized by triethanolamine and added to the combined solutions at about 35 C. with agitation sufficient to achieve a generally homogeneous or uniform mixture.
  • Perfumes or preservative agents such as methyl and/or propyl paraben or the like can readily be included in the formulation in an appropriate amount, if desired.
  • Active Ingredient Amounts Benzophenone Derivative 3% to Triethanolamine (U.S.P.) 0.5.
  • Emulsion Vehicle ARLACEL I86 (Monoand di- Glycerides of fat forming fatty acids) 3% SORBO” (70% aqueous solution of d-sorbitol) 27% Ceresin Wax 1% Beeswax 1% Mineral Oil 1 1% Water to 100% ARLACEL 186" and SORBO are tradenames of an emulsifier and an emollient respectively, available from the Atlas Chemical Industries, Inc. referred to earlier.
  • the formulation of the above embodiments is carried out by preparing an intermediate gel comprised of adding a small amount of SORBO and ARLACEL 186 and subjecting the mixture of mechanical agitation to form a relatively thick slurry. Thereafter, the remainder of SORBO ingredient is added with continuous agitation and then the benzophenone derivative, in its neutralized form, the waxes and the mineral oil are added to the intermediate gel and slowly agitated and heat up to about 70 C. The water is then heated to about 72 C. and added to the gel mixture with continuous agitation. The agitation is continued until the resultant formulation cools to room temperature. In order to provide maximum smoothness and stability, the formulation is subjected to homogenization or milling procedures.
  • EXAMPLE III A typical embodiment of a liquid solvent formulation utilizing 2-hydroxy-4-methoxy-benzophenone-S-sulfonic acid in its neutralized form as the active ingredient is as follows, with all parts being by weight.
  • the formulation of the above embodiment is carried out by combining the active ingredient with the solvent vehicle under vigorous agitation and gentle heat conditions for a period of time sufficient to produce a relatively clear solution. Perfumes or the like are also added as desired.
  • EXAMPLE IV A typical embodiment of a gel (clear or opaque) formulation utilizing 2-hydroxy-4-methoxy-benzophenone-S-sulfonic acid in its neutralized form as the active ingredient is as follows, with all parts being by weight.
  • Carbopol 940 is a tradename for an emulsifier material comprised of a vinyl polymer with active carboxyl groups available from B. F. Goodrich Company (The Merck Index, 8th Edision, 1968, Page 201
  • the formulation of the above gel embodiment is carried out by combining the gel vehicle with the benzophenone derivative under agitation and heat conditions sufficient to produce a clear gel solution. Thereafter the triethanolamine is slowly stirred into the solution until a gel forms. The formed gel is suitable for use on human skins.
  • the benzophenone derivative is carried into an appropriate vehicle by dissolving or suspending it in water, alcohol, glycerine, propylene glycol or any other suitable solvent or combination of solvents generally recognized as safe or compatible to human skin.
  • suitable suspension agents such as organic clays, pectin, synthetic resins, etc. are also utilizable in appropriate proportions in the formulations of the invention, additionally, tragacanth, agar-agar or similarly characterized thickening agents are also suitable for use in the formulations of the invention.
  • the invention provides active sunscreen agents or ingredients compatible with a wide variety of vehicles or carriers in sunscreen formulations wherein the active ingredient is present in amounts ranging from about 0.1 percent to about 30 percent.
  • the preferred active ingredient of the invention is 2-hydroxy-4-methoxy-benzophenone-5-sulfonic acid neutralized with triethanolamine, although other suitably neutralized 2-hydroxy-4-methoxy-benzophenone-5- sulfonic acid derivatives are also utilizable.
  • a sunscreen formulation in the form of an emulsified 10- tion suitable for application to human skin comprising; an active ingredient consisting essentially of 2-hydroxy-4-methoxybenzophenone-S-sulfonic acid in amounts ranging from 0.1 percent to 30 percent of said formulation, said sulfonic acid being neutralized with triethanolamine, and a compatible vehicle comprising a mixture of, by weight, 3 percent to 5 percent glycerol monostearate, 1 percent to 3 percent cetyl alcohol, 1 percent to 3 percent isopropyl palmitate, 1 percent to 15 percent dimethyl silicone oil, percent to 3 percent light liquid petrolatum, 0.1 percent to 1 percent polyvinyl pyrrolidone, 3 percent to 30 percent sorbitol and up to 100 percent water.
  • a sunscreen formulation in the form of an emulsified lotion suitable for application to human skin comprising; an active ingredient consisting essentially of 2-hydroxy-4-methoxybenzophenone-S-sulfonic acid in amounts ranging; from 0.l percent to 30 percent by weight of said formulation, said sulfonic acid being neutralized with triethanolamine, and a compatible vehicle comprising a mixture of, by weight, 3 percent to 5 percent glycerol monostearate, 2 percent cetyl alcohol, 2 percent isopropyl palrnitate, 3 percent dimethyl silicone oil, 2 percent light liquid petrolatum, 0.5 percent polyvinyl pyrrolidone, 7 percent sorbitol and up to 100 percent water.
  • a sunscreen formulation in the form of an emulsified 10- tion suitable for application to human skin comprising; an active ingredient of 2-hydroxy-4rnethoxy-benzophenone-S-sulfonic acid in an amount of 10 percent by weight of said formulation, said sulfonic acid being neutralized with triethanolamine, and a compatible vehicle comprising a mixture of, by weight, 5 percent glycerol monostearate, 2 percent cetyl alcohol, 2 percent isopropyl palmitate, 3 percent dimethyl silicone oil, 2 percent light liquid petrolatum, 0.5
  • a sunscreen formulation in the form of an emulsified lotion suitable for application to human skin comprising; an active ingredient consisting essentially of 2-hydroxy-4-methoxybenzophenone-S-sulfonic acid in amounts ranging from about 3 percent to 10 percent by weight of said formulation, said sulfonic acid being neutralized with triethanol-amine, and a compatible vehicle comprising a mixture of, by weight, 3 percent glycerol monoand di-stearate, 19 percent sorbitol, 1 percent ceresin wax, 1 percent beeswax, ll percent mineral oil and up to 100 percent water.
  • a sunscreen formulation in the form of a liquid suitable for application to human skin comprising; an active ingredient of 2-hydroxy-4-methoxy-benzophenone-S-sulfonic acid in an amount of 10 percent by weight of said formulation, said sulfonic acid being neutralized with triethanolamine, and a compatible vehicle comprising a mixture of, by weight, 20 percent denatured alcohol, 3 percent dimethyl silicone oil and up to 100 percent water.
  • a sunscreen formulation in the form of a liquid suitable for application to human skin comprising; an active ingredient of 2-hydroxy-4-methoxy-benzophenonc-5-sulfonic acid in an amount of 10 percent by weight of said formulation, said sulfonic acid being neutralized with triethanolamine, and a compatible vehicle comprising a mixture of, by weight, 30 percent denatured alcohol, 3 percent dirnethyl silicone oil, 0.5 percent glycerol monostearate and up to 100 percent water.

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Abstract

An active sunscreen ingredient comprised of 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, neutralized with triethanolamine, and formulated with various compatible vehicles to produce effective sunscreens for human use.

Description

United States Patent Doner, deceased [451 June 13, 1972 SUNSCREEN FORMULATION CONTAINING TRIETHANOLAMINE NEUTRALIZED 2-HYDROXY-4- METHOXY-BENZOPHENONE-S- SULFONIC ACID Inventor: Abraham J. Doner, deceased, late of North Miami Beach, Fla. by Cyril Doner, executor Assignee: Miles Laboratories, Inc., Eikhart, Ind.
Filed: Jan. 22, 1971 Appl. No.: 108,961
Related US. Application Data Continuation-in-part of Ser. No. 698,679, Dec. 18, 1967, abandoned.
US. Cl ..424/60, 424/47, 424/59,
424/80, 424/171, 424/184 Int. Cl. ..A61| 23/00 Field of Search ..424/59, 60, 331
Sagarin Cosmetic Science and Technology 195 7, p. 767. Lester, Handbook of Cosmetic Materials, 1954, p. 329
Primary Examiner-Albert T. Meyers Assistant ExaminerDale R. Ore Attorney-Hill, Sherman, Meroni, Gross & Simpson [57] ABSTRACT An active sunscreen ingredient comprised of 2-hydroxy-4- methoxy-benzophenone-S-suifonic acid, neutralized with triethanoiamine, and formulated with various compatible vehicles to produce efiective sunscreens for human use.
7 Claims, No Drawings SUNSCREEN FORMULATION CONTAINING TRIETHANOLAMINE NEUTRALIZED 2-HYDROXY-4- METHOXY-BENZOPHENONE-S-SULFONIC ACID CROSS-REFERENCE TO RELATED APPLICATIONS This is a continuation-in-part application of application Ser. No. 698,679 filed Dec. 18, 1967, now abandoned. Attention is also directed to prior application Ser. No. 358,616 filed Apr. 8, 1964, now abandoned.
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to ultraviolet absorbers and more particularly to sunscreen formulations for protection of human skin from solar radiation.
2. Prior Art Many sun tanning formulations for human skin are known, however, these do not effectively screen solar radiation from the skin. Chronic exposure to sunlight, even with such sun tanning formulations, has a deleterious effect on at least certain humans. For example, chronic exposure to sunlight .ap pears to significantly influence aging of human skin and/or produce skin cancer. Additionally, sunlight appears to precipitate or at least aggravate lupus erythematosus and con centrate skin lesions of pellagra and porphyria to the exposed skin areas. Also, a significant number of commonly used drugs produce photosensitivity in certain humans, which often result in polymorphic light sensitive eruptions. Among the more commonly used agent which produce sensitivity are the sulfonamides, tranquilizers of the phenothiazine type, the sulfonylurea oral antidiabetic agents and the antihypertensive diuretic agents.
The most common observation of the deleterious effect of exposure to sunlight is severe sunburn. However, a much less observed but just as common an effect of a single moderately severe sunburn is the abnormal characteristics of the blood vessels of a subject who has been exposed and which abnormalities remain present for a period of time ranging from 4 to 15 months. At present, no truly effective sunscreen agents are known that are compatible with human skin, and it will be appreciated that sun tanning agents are entirely different since they do not effectively absorb ultraviolet light. While certain benzophenone derivatives are utilized as sunscreen agents in protecting natural and man-made materials, such as textile goods, dyes and coloring agents, various resins, coating and film materials, and miscellaneous chemical compositions against the action of sunlight, these benzophenones are unsuitable for human skin for a number of reasons, including that they are highly irritating and do not lend themselves to acceptable formulations for human use.
Accordingly, it is an object of the invention to provide an effective sunscreen formulation for human skin that overcomes the aforesaid and additional disadvantages of heretofore available materials and to provide an adequate and safe protection for human skin from the effects of sunlight.
Other objects, features and advantages of the invention will become apparent to those skilled in the art from the teachings of the principles of the invention in connection with the disclosure of a preferred embodiment thereof in the specification and claims.
SUMMARY OF THE INVENTION The invention provides a sunscreen formulation containing an active ingredient for the protection of human skin from solar radiation comprised of a triethanolamine neutralized 2- hydroxy-4-methoxy benzophenone-S-sulfonic acid, in a compatible vehicle, which may include an emulsifier, such a glycerol monostearate, a wax, such as beeswax, water, an alcoho], such as denatured or cetyl alcohol, thickening agents, preservative agents, perfumes, etc. The amount of active ingredient within the formulation ranges in amounts from about 0.1 percent to about 30 percent.
DESCRIPTION OF THE PREFERRED EMBODIMENTS The invention provides a sunscreen agent that prevents and/or substantially minimizes the photochemical degradation and other adverse effects caused by exposure of human skin to sunlight through the absorption of ultraviolet wave lengths. The sunscreen agents of the invention absorb or screen radiation wave lengths responsible for erythema on human skin, minimizes the aging effects of solar radiation on humans and inhibits freckling or irregular pigmentation from such radiation. The sunscreen agents of the invention are readily incorporated into various types of vehicles for cosmetic materials, such as make-up bases, face powders, after-shave lotions, etc. for use by individuals who freckle, are afflicted with chloasma, or prefer their natural color, as well as by others. The sunscreen agents of the invention also tend to decrease sunlight accelerated aging and sunlight induced carcinogenesis on exposed human skin which has been coated with a formulation of said agents.
The sunscreen agents of the invention comprise Z-hydroxy- 4-methoxy-benzophenone-5-sulfonic acid neutralized with a neutralization agent having properties of triethanolamine and are formulated into any desired carrier, vehicle, emulsion, cream, lotion, ointment, solution, suspension, gel, aerosol or in any other form suitable for human usage. In its most preferred form, the active sunscreen agent of the invention is 2-hydroxy-4-methoxy-benzophenone-5sulfonic acid neutralized with triethanolamine. The amount of active sunscreen agent of the invention in a given formulation ranges from about 0. 1 percent to about 30 percent or more as desired.
The emulsions, gels, vehicles, etc. utilized in preparing sunscreen formulations containing the active sunscreening agents of the invention contain any one or combinations of; cetyl alcohol, stearyl alcohol, stearic or lauric acids and all other fatty acids and alcohols generally used in cosmetic and like materials emulsions or other formulations intended for human use; various waxes such as beeswax, microcrystalline wax, spermaceti, etc., and all other waxes generally used in cosmetic and like material emulsions or other formulations intended for human use; various petroleum materials, such as petrolatum, liquid petrolatum, mineral oil, silicone oil, etc. and all other oils, fats, and the like materials generally used in cosmetic and like material emulsions or other formulations intended for human use; fatty acid esters, such as isopropyl myristate and similar esters of fatty acids having a composition generally ranging from about C to about C various silicone derivatives, polyvinyl pyrrolidone methyl or propyl paraben, C to C glycols, various stearates, and other materials whether similar or otherwise that are generally used or considered suitable for use in cosmetic and like material emulsions or other formulations intended for human use.
Additionally, the vehicle materials, emulsifiers, combination of emulsifiers, and other like material compatible with the active sunscreen ingredients or agents of the invention are also selected from various anionic surfactants, including amine soaps of fatty acids such as characterized by triethanolamine stearate; cationic surfactants, such as characterized by monoethanol ammonium fluoride; amphoteric surfactants such as characterized by N-fatty B-amino-propionate (RNI-I CH -CH COOH); and nonionic surfactants such as characterized by sorbitan derivatives of C to C fatty acids, polyoxyethylene sorbitan derivatives of C to C fatty acids, polyoxyethylene esters of C to C fatty acids, glyceryl stearates, fatty acid polyisopropylene complexes; and ethylenes oxide fatty alcohol lanolin complexes. Other compatible materials, vehicles, carriers, gels and like materials include perfumes, clays, preservative agents, etc. and are all utilizable with the active sunscreen agents of the invention in formulating suitable gels, emulsions, either of the water-in-oil type or the oil-in-water type, aerosols, etc. or other forms suitable for application to humans.
In order to illustrate the invention and compare it with known sun-protective agents, comparative evaluations were made of twenty-four agents by applying such agents to the shaved abdomens of albino rabbits and determining the Minimal Erythema Dose (M.E.D.). An embodiment of the invention within this comparative group was triethanolamine neutralized 2-hydroxy-4-methoxy-benzophenone-S-sulfonic acid. The M.E.D. for an unprotected rabbit (i.e. one without having any protective agent on it) was found to be 25-30 seconds. Of the known protective agents, the longest or best protection provided was 3 to 5 minutes and only four of the preparations studied gave results that were this satisfactory. A 5 percent concentration of PABA (para-amino-benzoic-acid) and a 5 percent concentration of triethanolamine neutralized 2-hydroxy-4-methoxy-benzophenone-5-sulfonic acid in a compatible vehicle, each provided protection for about 20 to 25 minutes. By doubling the concentration of these two agents in similar formulations and applying them to rabbits, the M.E.D. was increased in both instances to approximately 100 minutes. However, PABA and its esters tended to produce epidermal sensitization and to produce cross-sensitization reaction with benzocaine, sulfonamides, and the aniline dyes.
The active sunscreen agents of the invention generally comprise suitably neutralized 2-hydroxy-4-methoxybenzophenone-S-sulfonic acid, and similar benzophenone derivatives having the formula:
i O @OCH3 wherein A is selected from a neutralizing agent having properties characterized by triethanolamine. The active sunscreen agents of the invention are utilized in a variety of formulations and are present therein in amounts ranging from about 0.1 percent to about 30 percent by weight.
In order to further illustrate, and not limit the sunscreen agents of the invention in various formulations, bases, carriers, emulsifiers and other compatible vehicles, the following examples are set forth.
A 2-hydroxy-4-methoxy benzophenone-S-sulfonic acid is available from Antara Chemical, New York, New York under the registered tradename UVINUL MS40 and U- VINUL-40-20 percent Aqueous Solution. UVINUL MS-40" is a free flowing powder at 25 C., light-cream in color and has a molecular weigh of 309 and a pH 2 for a l percent aqueous solution, with a solubility of about 5 g/lOO mls of water at 25 C. after 15 minutes of agitation. Of course U- VINUL MS-40-20% Aqueous Solution is the same material in an aqueous solution at the concentration indicated. In preparing sunscreen formulations utilizing powdered U- VINUL MS-40, the powder is first dissolved in water and then combined with a suitable neutralizing agent and a particular vehicle.
EXAMPLE I A typical embodiment of an oil-in-water emulsion formulation utilizing UVINUL MS-40-20% Aqueous Solution, (referred to as Benzophenone Derivative) in its neutralized form, an the active ingredient is as follows, with all parts being by weight unless otherwise noted.
Active Ingredient Amounts Benzophenone Derivative Triethanolamine (U.S.P.) Q.S." Emulsion Vehicle ARLACEL 165 (Glyceryl Monostearate) 5% Cetyl Alcohol 2% Isopropyl Palmitate 2% Dimethyl Silicone Oil 3% Light Liquid Petrolatum 2% Polyvinyl Pyrrolidone 0.5%
"Sorbo 70%" Distilled Water "ARLACEL is a tradename for a glyceryl monostearate containing emulsifier available from Atlas Chemical Industries, Inc., of Wilmington, Delaware and Sorbo 70% is a tradename for a sorbitol containing emollient having 70 percent solids also available from Atlas Chemical Industries, Inc. An alternative emulsifier usable in place of "ARLACEL 165" is Prornulgen," a tradename for an emulsifier available from Robinson Wagner Company, Inc., of Mamaroneck, New York.
The above embodiment of a particular formulation can be varied by adjusting the amount of active ingredient so as to vary between about O.l percent to about 30 percent and by adjusting and/or omitting certain ingredients of the vehicle. For example, the amount of glycerol monostearate can vary between about 3 percent to 5 percent, the silicone oil, i.e. dimethyl silicone oil, and/or the petrolatum can be replaced by mineral oil and the amount varied between about 1 percent to 15 percent, the amount of sorbitol varied between about 3 percent to 30 percent or partially replaced by a glycol, the amounts of isopropyl palmitate, and polyvinyl pyrrolidone may also be varied and/or replaced with other comparable material and even omitted as exemplified in further embodiments set forth hereinafter. Of course, minor amounts perfumes and/or preservative agents are added as desired.
It will be understood that the invention is not limited to the specific proprietary items set forth in the examples but includes all emulsifiers, emollients, carriers, vehicles, preservatives, perfumes and other materials generally found in cosmetic materials, sun protective formulations, etc., suitable for use on human skin.
The formulation of the above embodiment of an oil-inwater emulsion is carried out by placing the appropriate amounts of ARLACEL 165, cetyl alcohol, dimethyl silicone oil and light liquid petroletum in a suitable steam-jacketed kettle or the like and subjecting the mixture to slow agitation and heating conditions to about 70 C. so as to form a first solution. The remaining ingredients of the emulsion vehicle, i.e. all of the remainder ingredients except the active ingredient, are placed in another suitable container and slowly agitated and heated up to about 75 C. to form a second solution. The two solutions are then combined with continuous and vigorous agitation by adding the second solution to the first solution. Thereafter the sulfonated 2-hydroxy-4-methoxybenzophenone derivative is neutralized with a sufficient amount of an amine having properties characterized by triethanolamine and added to the combined solutions at about 35 C. with agitation sufficient to achieve a generally homogeneous or uniform mixture. Perfumes or preservative agents such as methyl and/or propyl paraben or the like can readily be included in the formulation in an appropriate amount, if desired.
EXAMPLE II A typical embodiment of a water-in-oil formulation utilizing 2-hydroxy-4-methoxy-benzophenone-S-sulfonic acid in its neutralized form as the active ingredient is as follows, again all parts being by weight unless otherwise noted.
Active Ingredient Amounts Benzophenone Derivative 3% to Triethanolamine (U.S.P.) 0.5.
Emulsion Vehicle ARLACEL I86" (Monoand di- Glycerides of fat forming fatty acids) 3% SORBO" (70% aqueous solution of d-sorbitol) 27% Ceresin Wax 1% Beeswax 1% Mineral Oil 1 1% Water to 100% ARLACEL 186" and SORBO are tradenames of an emulsifier and an emollient respectively, available from the Atlas Chemical Industries, Inc. referred to earlier.
The formulation of the above embodiments is carried out by preparing an intermediate gel comprised of adding a small amount of SORBO and ARLACEL 186 and subjecting the mixture of mechanical agitation to form a relatively thick slurry. Thereafter, the remainder of SORBO ingredient is added with continuous agitation and then the benzophenone derivative, in its neutralized form, the waxes and the mineral oil are added to the intermediate gel and slowly agitated and heat up to about 70 C. The water is then heated to about 72 C. and added to the gel mixture with continuous agitation. The agitation is continued until the resultant formulation cools to room temperature. In order to provide maximum smoothness and stability, the formulation is subjected to homogenization or milling procedures.
EXAMPLE III A typical embodiment of a liquid solvent formulation utilizing 2-hydroxy-4-methoxy-benzophenone-S-sulfonic acid in its neutralized form as the active ingredient is as follows, with all parts being by weight.
Active Ingredient Amounts Benzophenone Derivative Neutralizing Agent Q.S." Solvent Vehicle Specially Denatured Alcohol (SBA-40) 20% Alcohol Soluble Silicone Oil 3% Purified Water to 100% A denatured ethyl alcohol approved by the US. Government for use in various cosmetics and like formulations.
The formulation of the above embodiment is carried out by combining the active ingredient with the solvent vehicle under vigorous agitation and gentle heat conditions for a period of time sufficient to produce a relatively clear solution. Perfumes or the like are also added as desired.
EXAMPLE IV A typical embodiment of a gel (clear or opaque) formulation utilizing 2-hydroxy-4-methoxy-benzophenone-S-sulfonic acid in its neutralized form as the active ingredient is as follows, with all parts being by weight.
Active Ingredient Amounts Benzophenone Derivative 10% Triethanolamine (U.S.P.) Q.S." Gel Vehicle Specially Denatured Alcohol (SDA-40)" 30% Alcohol Soluble Silicone 3% Carbopol 940" (Synthetic I-lydrophilic Colloids in white free flowing powder form) 0.5% Water to 100% "lbid.
Carbopol 940 is a tradename for an emulsifier material comprised of a vinyl polymer with active carboxyl groups available from B. F. Goodrich Company (The Merck Index, 8th Edision, 1968, Page 201 The formulation of the above gel embodiment is carried out by combining the gel vehicle with the benzophenone derivative under agitation and heat conditions sufficient to produce a clear gel solution. Thereafter the triethanolamine is slowly stirred into the solution until a gel forms. The formed gel is suitable for use on human skins.
The benzophenone derivative is carried into an appropriate vehicle by dissolving or suspending it in water, alcohol, glycerine, propylene glycol or any other suitable solvent or combination of solvents generally recognized as safe or compatible to human skin. Further suitable suspension agents, such as organic clays, pectin, synthetic resins, etc. are also utilizable in appropriate proportions in the formulations of the invention, additionally, tragacanth, agar-agar or similarly characterized thickening agents are also suitable for use in the formulations of the invention.
In order to further illustrate the sunscreen agents and formulations of the invention and to illustrate their relative effectiveness on humans and compared them with known sun protective agents, a number of known sun protective agents and the sunscreen formulation essentially identical to that of Example I having various concentrations of active sunscreen ingredients were applied to male and female volunteers. An ultraviolet lamp, Burdick Model QA-450-N, producing ultraviolet radiation ranging from 2,400 to 3,300 angstroms, with the majority of the radiation being between 2,800 to 3,200 angstroms was used. (Sunburn to human skin is generally produced by the electromagnetic spectrum located between 2,900 and 3,170 angstroms, with maximal effects at about 2,970 angstroms.) The M.E.D. (Minimal Erythema Dose) for each volunteer was established on the abdomen and the back with the ultraviolet lamp at a distance of thirty inches. The various formulations studied were applied by hand and rubbed into a skin area in the same manner as an individual does before being exposed to the sun. No excess material was utilized and the amount varied, but was generally only sufiicient to permit the volunteers to feel comfortable. In each instance, the applied formulations were allowed to dry before exposure to the ultraviolet and the results were averaged.
Average Protection Para-amino-benzoic acid 15% in Aquaphor Red Veterinary Petrolatum 30 but less than 40 40 but less than 60 2-ethoxy-ethyl-p-methoxy-cinnamate less than 5 Yellow Vasoline (U.S.P.) 30 but less than 40 Digalloyl-trioleate less than 5 10% neutralized benzophenone derivative of the invention in a lotion base 5% neutralized benzophenone derivative of the invention in a location base 2% neutralized benzophenone derivative of the invention in a lotion base 5 10% neutralized benzophenone derivative 10 but less than 20 of the invention in an alcohol vehicle 40 The emulsion vehicle of Example I, without the active ingredient less than 5 Non-neutralized benzophenone derivative results inconelusive The non-neutralized benzophenone derivative in a lotion base was considered to be irritating and unacceptable for human use.
In summation, the invention provides active sunscreen agents or ingredients compatible with a wide variety of vehicles or carriers in sunscreen formulations wherein the active ingredient is present in amounts ranging from about 0.1 percent to about 30 percent. The preferred active ingredient of the invention is 2-hydroxy-4-methoxy-benzophenone-5-sulfonic acid neutralized with triethanolamine, although other suitably neutralized 2-hydroxy-4-methoxy-benzophenone-5- sulfonic acid derivatives are also utilizable.
It is to be understood that the foregoing relates only to the preferred embodiments of the invention and changes, modifications and variations can be effected without departing from the scope or spirit of the novel concepts of the invention.
I claim:
1. A sunscreen formulation in the form of an emulsified 10- tion suitable for application to human skin comprising; an active ingredient consisting essentially of 2-hydroxy-4-methoxybenzophenone-S-sulfonic acid in amounts ranging from 0.1 percent to 30 percent of said formulation, said sulfonic acid being neutralized with triethanolamine, and a compatible vehicle comprising a mixture of, by weight, 3 percent to 5 percent glycerol monostearate, 1 percent to 3 percent cetyl alcohol, 1 percent to 3 percent isopropyl palmitate, 1 percent to 15 percent dimethyl silicone oil, percent to 3 percent light liquid petrolatum, 0.1 percent to 1 percent polyvinyl pyrrolidone, 3 percent to 30 percent sorbitol and up to 100 percent water.
2. A sunscreen formulation as defined in claim 11 wherein the compatible vehicle includes a preservative amount of preservative material selected from the group consisting of methyl paraben, propyl paraben and mixtures thereof.
3. A sunscreen formulation in the form of an emulsified lotion suitable for application to human skin comprising; an active ingredient consisting essentially of 2-hydroxy-4-methoxybenzophenone-S-sulfonic acid in amounts ranging; from 0.l percent to 30 percent by weight of said formulation, said sulfonic acid being neutralized with triethanolamine, and a compatible vehicle comprising a mixture of, by weight, 3 percent to 5 percent glycerol monostearate, 2 percent cetyl alcohol, 2 percent isopropyl palrnitate, 3 percent dimethyl silicone oil, 2 percent light liquid petrolatum, 0.5 percent polyvinyl pyrrolidone, 7 percent sorbitol and up to 100 percent water.
4. A sunscreen formulation in the form of an emulsified 10- tion suitable for application to human skin comprising; an active ingredient of 2-hydroxy-4rnethoxy-benzophenone-S-sulfonic acid in an amount of 10 percent by weight of said formulation, said sulfonic acid being neutralized with triethanolamine, and a compatible vehicle comprising a mixture of, by weight, 5 percent glycerol monostearate, 2 percent cetyl alcohol, 2 percent isopropyl palmitate, 3 percent dimethyl silicone oil, 2 percent light liquid petrolatum, 0.5
percent polyvinyl pyrrolidone, 7 percent sorbitol and up to percent water.
5. A sunscreen formulation in the form of an emulsified lotion suitable for application to human skin comprising; an active ingredient consisting essentially of 2-hydroxy-4-methoxybenzophenone-S-sulfonic acid in amounts ranging from about 3 percent to 10 percent by weight of said formulation, said sulfonic acid being neutralized with triethanol-amine, and a compatible vehicle comprising a mixture of, by weight, 3 percent glycerol monoand di-stearate, 19 percent sorbitol, 1 percent ceresin wax, 1 percent beeswax, ll percent mineral oil and up to 100 percent water.
6. A sunscreen formulation in the form of a liquid suitable for application to human skin comprising; an active ingredient of 2-hydroxy-4-methoxy-benzophenone-S-sulfonic acid in an amount of 10 percent by weight of said formulation, said sulfonic acid being neutralized with triethanolamine, and a compatible vehicle comprising a mixture of, by weight, 20 percent denatured alcohol, 3 percent dimethyl silicone oil and up to 100 percent water.
7. A sunscreen formulation in the form of a liquid suitable for application to human skin comprising; an active ingredient of 2-hydroxy-4-methoxy-benzophenonc-5-sulfonic acid in an amount of 10 percent by weight of said formulation, said sulfonic acid being neutralized with triethanolamine, and a compatible vehicle comprising a mixture of, by weight, 30 percent denatured alcohol, 3 percent dirnethyl silicone oil, 0.5 percent glycerol monostearate and up to 100 percent water.
I! 4 I I III UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTIQN 3, 670, 074 Dated June 13, 1972 Patent No.
lnvvnrorhz) Aln'uhzun J. Holler It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:
Column 6, line 42, change "location" to --1otion-,
Column 7, line 6, change "11" to --l--.
Signed and sealed this 17th day of September 1974 (SEAL) Attest:
MCCOY M. GIBSON JR. C. MARSHALL DANN Attesting Officer Commissioner of Patents ORM PO-1OSO (10-69) USCOMM-DC 60376-P69 u.s, eovsnmaam PRINTlNG orncs; I969 o-ass-aaa.

Claims (6)

  1. 2. A sunscreen formulation as defined in claim 11 wherein the compatible vehicle includes a preservative amount of preservative material selected from the group consisting of methyl paraben, propyl paraben and mixtures thereof.
  2. 3. A sunscreen formulation in the form of an emulsified lotion suitable for application to human skin comprising; an active ingredient consisting essentially of 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid in amounts ranging from 0.1 percent to 30 percent by weight of said formulation, said sulfonic acid being neutralized with triethanolamine, and a compatible vehicle comprising a mixture of, by weight, 3 percent to 5 percent glycerol monostearate, 2 percent cetyl alcohol, 2 percent isopropyl palmitate, 3 percent dimethyl silicone oil, 2 percent light liquid petrolatum, 0.5 percent polyvinyl pyrrolidone, 7 percent sorbitol and up to 100 percent water.
  3. 4. A sunscreen formulation in the form of an emulsified lotion suitable for application to human skin comprising; an active ingredient of 2-hydroxy-4methoxy-benzophenone-5-sulfonic acid in an amount of 10 percent by weight of said formulation, said sulfonic acid being neutralized with triethanolamine, and a compatible vehicle comprising a mixture of, by weight, 5 percent glycerol monostearate, 2 percent cetyl alcohol, 2 percent isopropyl palmitate, 3 percent dimethyl silicone oil, 2 percent light liquid petrolatum, 0.5 percent polyvinyl pyrrolidone, 7 percent sorbitol and up to 100 percent water.
  4. 5. A sunscreen formulation in the form of an emulsified lotion suitable for application to human skin comprising; an active ingredient consisting essentially of 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid in amounts ranging from about 3 percent to 10 percent by weight of said formulation, said sulfonic acid being neutralized with triethanol-amine, and a compatible vehicle comprising a mixture of, by weight, 3 percent glycerol mono- and di-stearate, 19 percent sorbitol, 1 percent ceresin wax, 1 percent beeswax, 11 percent mineral oil and up to 100 percent water.
  5. 6. A sunscreen formulation in the form of a liquid suitable for application to human skin comprising; an active ingredient of 2-hydroxy-4-methoxy-benzophenone-5-sulfonic acid in an amount of 10 percent by weight of said formulation, said sulfonic acid being neutralized with triethanolamine, and a compatible vehicle comprising a mixture of, by weight, 20 percent denatured alcohol, 3 percent dimethyl silicone oil and up to 100 percent water.
  6. 7. A sunscreen formulation in the form of a liquid suitable for application to human skin comprising; an active ingredient of 2-hydroxy-4-methoxy-benzophenone-5-sulfonic acid in an amount of 10 percent by weight of said formulation, said sulfonic acid being neutralized with triethanolamine, and a compatible vehicle comprising a mixture of, by weight, 30 percent denatured alcohol, 3 percent dimethyl silicone oil, 0.5 percent glycerol monostearate and up to 100 percent water.
US108961A 1971-01-22 1971-01-22 Sunscreen formulation containing triethanolamine neutralized 2-hydroxy-4-methoxy-benzophenone-5-sulfonic acid Expired - Lifetime US3670074A (en)

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US4250108A (en) * 1973-02-19 1981-02-10 L'oreal Process for preparing (2-oxo-3-bornylidene/methyl)-benzene sulfonic acids
FR2493838A1 (en) * 1980-11-12 1982-05-14 Riedel De Haen Ag Neutralising aq. 2-hydroxy-4-methoxy- benzophenone-5-sulphonic acid - with amine forming no ppte., soln. used as impregnant for UV light-sensitive substrate
US4331651A (en) * 1979-01-23 1982-05-25 Hoechst Aktiengesellschaft Depot body on the basis of silicone rubber and process for the preparation thereof
US4457911A (en) * 1981-01-28 1984-07-03 Van Dyk & Company Inc. Dialkyl malonates as organic sunscreen adjuvants
US4699779A (en) * 1986-02-18 1987-10-13 Victor Palinczar Waterproof sunscreen compositions
US4710371A (en) * 1986-02-19 1987-12-01 Victor Palinczar Waterproof sunscreen compositions
EP0275719A3 (en) * 1986-12-30 1988-08-10 Richardson-Vicks, Inc. Ultraviolet absorbing compounds and formulations including same
US4810489A (en) * 1986-12-04 1989-03-07 Bristol-Myers Company High oil phase pharmaceutical vehicles and sunscreen compositions having waterproof sun protection factors
US4840788A (en) * 1986-07-15 1989-06-20 Ici Americas Inc. Nonalcoholic sunscreen gel
FR2627085A1 (en) * 1988-02-11 1989-08-18 Oreal USE OF 2-HYDROXY-4-METHOXYBENZOPHENONE-5-SULFONIC ACID OR ITS SALTS FOR HAIR PROTECTION AGAINST ATMOSPHERIC AGGRESSIONS, ESPECIALLY AGAINST LIGHT, AND HAIR PROTECTION METHOD USING THE SAME
US4897259A (en) * 1986-12-04 1990-01-30 Bristol-Myers Company High oil phase pharmaceutical vehicles and sunscreen compositions having waterproof sun protection factors
US5004598A (en) * 1986-11-10 1991-04-02 The B. F. Goodrich Company Stable and quick-breaking topical skin compositions
FR2680685A1 (en) * 1991-08-30 1993-03-05 Oreal SOLAR COSMETIC GEL CONTAINING SUSPENSION HYDRATED SPHEROUIDS OF A HYDROPHILIC LIPID SUBSTANCE AND, IN SOLUTION IN THE AQUEOUS PHASE, A SULPHONIC UV FILTER.
US5240695A (en) * 1988-02-11 1993-08-31 L'oreal Use of 2-hydroxy-4-methoxybenzophenone-5-sulphonic acid or its salts for protecting the hair against environmental attacking agents, and especially against light and process for protecting the hair using the compound
DE4322759C1 (en) * 1993-07-08 1994-09-01 Kao Corp Gmbh Hair-treatment composition
FR2706766A1 (en) * 1993-06-21 1994-12-30 Oreal
EP0821940A1 (en) * 1996-07-31 1998-02-04 3V SIGMA S.p.A Sun screening preparations comprising triazine derivatives
WO2019032059A1 (en) 2017-08-11 2019-02-14 Dokuz Eylül Üni̇versi̇tesi̇ Rektörlüğü A phosphorus based sunscreen converting ultraviolet radiation to red wavelengths

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Cited By (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4250108A (en) * 1973-02-19 1981-02-10 L'oreal Process for preparing (2-oxo-3-bornylidene/methyl)-benzene sulfonic acids
US4331651A (en) * 1979-01-23 1982-05-25 Hoechst Aktiengesellschaft Depot body on the basis of silicone rubber and process for the preparation thereof
FR2493838A1 (en) * 1980-11-12 1982-05-14 Riedel De Haen Ag Neutralising aq. 2-hydroxy-4-methoxy- benzophenone-5-sulphonic acid - with amine forming no ppte., soln. used as impregnant for UV light-sensitive substrate
DE3042541A1 (en) * 1980-11-12 1982-05-19 Riedel-De Haen Ag, 3016 Seelze AQUEOUS SOLUTION OF 2-HYDROXY-4-METHOXYBENZOPHENONE-5-SULFONIC ACID, METHOD FOR THE PRODUCTION AND USE THEREOF
US4457911A (en) * 1981-01-28 1984-07-03 Van Dyk & Company Inc. Dialkyl malonates as organic sunscreen adjuvants
US4699779A (en) * 1986-02-18 1987-10-13 Victor Palinczar Waterproof sunscreen compositions
US4710371A (en) * 1986-02-19 1987-12-01 Victor Palinczar Waterproof sunscreen compositions
US4840788A (en) * 1986-07-15 1989-06-20 Ici Americas Inc. Nonalcoholic sunscreen gel
US5004598A (en) * 1986-11-10 1991-04-02 The B. F. Goodrich Company Stable and quick-breaking topical skin compositions
US4897259A (en) * 1986-12-04 1990-01-30 Bristol-Myers Company High oil phase pharmaceutical vehicles and sunscreen compositions having waterproof sun protection factors
US4810489A (en) * 1986-12-04 1989-03-07 Bristol-Myers Company High oil phase pharmaceutical vehicles and sunscreen compositions having waterproof sun protection factors
EP0275719A3 (en) * 1986-12-30 1988-08-10 Richardson-Vicks, Inc. Ultraviolet absorbing compounds and formulations including same
US5240695A (en) * 1988-02-11 1993-08-31 L'oreal Use of 2-hydroxy-4-methoxybenzophenone-5-sulphonic acid or its salts for protecting the hair against environmental attacking agents, and especially against light and process for protecting the hair using the compound
GB2215602A (en) * 1988-02-11 1989-09-27 Oreal A process for protecting the hair using 2-hydroxy-4-methoxybenzophenone-5-sulphonic acid or a salt thereof
GB2215602B (en) * 1988-02-11 1991-10-02 Oreal A process for protecting the hair using 2-hydroxy-4-methoxybenzophenone-5- sulphonic acid or a salt thereof
BE1003099A5 (en) * 1988-02-11 1991-11-26 Oreal USE OF 2-HYDROXY-4-METHOXYBENZOPHENONE-5-SULFONIC ACID OR ITS SALTS FOR THE PROTECTION OF HAIR AGAINST ATMOSPHERIC AGGRESSIONS, AND PARTICULARLY AGAINST LIGHT, AND METHOD FOR PROTECTING HAIR USING THIS COMPOUND.
FR2627085A1 (en) * 1988-02-11 1989-08-18 Oreal USE OF 2-HYDROXY-4-METHOXYBENZOPHENONE-5-SULFONIC ACID OR ITS SALTS FOR HAIR PROTECTION AGAINST ATMOSPHERIC AGGRESSIONS, ESPECIALLY AGAINST LIGHT, AND HAIR PROTECTION METHOD USING THE SAME
FR2680685A1 (en) * 1991-08-30 1993-03-05 Oreal SOLAR COSMETIC GEL CONTAINING SUSPENSION HYDRATED SPHEROUIDS OF A HYDROPHILIC LIPID SUBSTANCE AND, IN SOLUTION IN THE AQUEOUS PHASE, A SULPHONIC UV FILTER.
EP0531192A1 (en) * 1991-08-30 1993-03-10 L'oreal Cosmetic sunblock gels containing in suspension hydrated spheroids of hydrophilic lipidic substance and in solution in this aqueous gel an UV-filter of the sulfonic type
US5635163A (en) * 1993-06-21 1997-06-03 L'oreal Screening cosmetic compositions containing a hydrophilic agent comprising at least one sulphonic acid radical
FR2706766A1 (en) * 1993-06-21 1994-12-30 Oreal
WO1995000111A1 (en) * 1993-06-21 1995-01-05 L'oreal Cosmetic filtering compositions containing a hydrophilic agent with at least one sulphonic acid radical
JP2865425B2 (en) 1993-06-21 1999-03-08 ロレアル Shielding cosmetic composition containing hydrophilic agent having at least one sulfonic acid group
DE4322759C1 (en) * 1993-07-08 1994-09-01 Kao Corp Gmbh Hair-treatment composition
EP0821940A1 (en) * 1996-07-31 1998-02-04 3V SIGMA S.p.A Sun screening preparations comprising triazine derivatives
WO2019032059A1 (en) 2017-08-11 2019-02-14 Dokuz Eylül Üni̇versi̇tesi̇ Rektörlüğü A phosphorus based sunscreen converting ultraviolet radiation to red wavelengths

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