Cosmetics having photoprotection properties

Abstract: The present invention provides a useful cosmetic having high ultraviolet-screening effects (sunburn preventing effects), and excellent safety, and giving a natural makeup finish. This composition comprises a metal oxide flake having an average thickness of from 0.01 to 3 µm, and an average size of from 1 to 100 µm and a high polymer resin powder containing polymerization of a high polymer resin monomer uniformly mixed with an ultraviolet absorbent.

Description: Technical Field This invention relates to sunburn preventive cosmetics, and more particularly to cosmetics comprising a combination of a metal oxide flake and an ultraviolet absorbent-containing high polymer resin so as to exhibit high sunburn preventing effects. Background of the Invention Ultraviolet rays reaching the grounds are known to include middle ultraviolet rays (290-320 µm; called UV-B) which induce rash of the skin, followed by inflammation leading to skin darkening and are regarded as one of causes of cutaneous cancer, and near ultraviolet rays (320-400 nm; called UV-A) which are less causative of rash but oxidize reduced melanin in the skin to cause deposition of melanin pigment leading to skin darkening or which are regarded to accelerate aging of the skin through long-term exposure. With elucidation of the influences of ultraviolet rays on the skin, there has been an increasing demand for sunburn preventive cosmetics. A sun protection factor (SPF) value has been proposed as an index for protection of the skin from ultraviolet rays, and a higher SPF value is deemed to indicate a higher sunburn preventing effect. Reference can be made, for example, to Fukuda Minoru, KOSHOKAISHI , "Sun-Screen and SPF," Vol. 8, No. 4, pp. 315-323 (1984). In general, sunburn preventive cosmetics contain ultraviolet absorbents or ultraviolet scattering agents for obtaining high SPF values. Known ultraviolet absorbents include benzophenone compounds, cinnamic acid compounds, and benzoic acid compounds. Achievement of effective sunburn prevention requires incorporating a relatively large quantity of the ultraviolet absorbent into cosmetic compositions. However, incorporating a large quantity of the ultraviolet absorbent causes various problems, such as reduction in compatibility with cosmetics bases, adverse influences on cosmetic bases (e.g., denaturation), decomposition of the ultraviolet absorbent which leads to reduction in ultraviolet absorptivity, coloring, etc., and impairment of safety (e.g., increased irritation to the skin). Therefore, use of ultraviolet absorbents as cosmetic material involves many disadvantages, and cosmetics containing such materials in large quantities lose their values as cosmetics. On the other hand, ultraviolet scattering agents include zinc oxide, titanium oxide, and kaolin. These inorganic pigments show an effect of scattering a broad range of ultraviolet rays, are less liable to denaturation on exposure to ultraviolet rays, and are less irritating to the skin because they do not penetrate into the skin. However, when they are applied to the skin, unsightly white matter remains on the skin due to their high covering power. In order to overcome these disadvantages, zinc oxide, titanium oxide, zirconium oxide, etc. in the form of fine particles have been proposed. However, such particles undergo secondary agglomeration when incorpaorated into cosmetics, not only failing to exhibit sufficient sunburn preventive effects as expected from sunburn preventive cosmetics, but also resulting in poor spreadability on the skin. In the light of the above-described circumstances, plate-like metal oxides have been proposed for use as cosmetic materials. These materials are said to have high safety, provide a satisfactory makeup finish, and exhibit high ultraviolet scattering ability, as diclosed in Japanese Patent Application Laid-Open Nos. Sho-61-161212, Sho-62-4212, Sho-63-166819, and Hei-1-175921. Although these materials are safe and give a natural makeup finish, the sunburn preventing effects attained are still insufficient irrespective of whether they are used alone or in combination with ordinary ultraviolet absorbents in amounts that cause no safety problem. Accordingly, there still has been a demand in the art to develop cosmetics that are safe to use and yet have high sunburn preventing effects. An object of the present invention, therefore, is to solve the above- mentioned problems. That is, an object of the present invention is to provide a cosmetic which exhibits high ultraviolet-screening effects (sunburn preventing effects), which is excellent in safety, which stably maintains an ultraviolet absorbent in the base thereof, and which gives a natural makeup finish. Summary of the Invention The present invention relates to cosmetics compositions for application to the skin to inhibit sunburn effects, comprising: (a) an effective amount (preferably from about 1% to about 70%) of metal oxide flakes (preferably zinc oxide, titanium oxide, zirconium oxide and mixtures thereof) having a thickness of from about 0.01 to about 3 mm and an average size of from abuot 1 to about 100 µm, and (b) an effective amount (preferably from about 0.1% to about 70%) of a high polymer resin powder obtained by polymerizing a monomer of the high polymer resin uniformly mixed with the UV absorbent. In preferred polymer resin powders, the high polymer resin wall covers a core comprising the ultraviolet absorbent. Preferred high polymer resin materials include vinyl polymers, olefin-vinyl polymers, olefin-alkyl polymers, polyamides, acrylic resins, polystyrene, polyesters, and mixtures thereof; while preferred ultraviolet absorbents include aminobenzoic acid and its derivatives, salicyclic acid and its derivatives, cinnamic acid and its derivatives, benzophenone derivatives, urocanic acid and its derivatives, and mixtures thereof. Brief Description of the Drawings Fig. 1 shows ultraviolet absorption characteristic curves of the ultraviolet absorbent-containing high polymer resin powders (UV-Powders) used in the present invention. Fig. 2 shows infrared-screening effects of the multi-layer cosmetics described in Case 2. Detailed Description of the Invention The inventors have conducted extensive investigations to solve the above-described problems and, as a result, found that a cosmetic containing a metal oxide flake having an average thickness of from 0.01 to 3 µm and an average size of from 1 to 100 µm and a high polymer resin powder containing therein an ultraviolet absorbent which is obtained by polymerization of a monomer for a high polymer resin uniformly mixed with an ultraviolet absorbent exhibits high ultraviolet-screening effects (sunburn preventing effects), has excellent safety, stably maintains an ultraviolet absorbent in the base thereof, and gives a natural makeup finish, thus having completed the present invention. That is, when a metal oxide flake and an ultraviolet absorbent-containing high polymer resin are combined, a significantly high SPF value can be obtained even if the total amount of these two components in cosmetics is relatively small. From the standpoint of safety, there is no need to consider the safety problem since the above-mentioned synergistic effect of two components allows the requisite amount of the ultraviolet absorbent to be relatively reduced and, in addition, the ultraviolet absorbent, being covered with the high polymer resin, is not brought into direct contact with the skin. Moreover, from the standpoint of utility, the cosmetics using these two components exhibit excellent performance, for example, in terms of makeup finish and spreadability on the skin. The plate-like metal oxide which can be used in the present invention has an average thickness of from 0.01 to 3 µm and an average size of from 1 to 100 µm. The term "average thickness" as used herein means the average of thickness values measured on 100 flakes, and the term "average size" as used herein means the average value of (maximum diameter + minimum diameter)/2 as measured on 100 flakes. The metal oxide is not limited in kind as long as it is acceptable as a cosmetic material and has a shape or size within the above-specified range. Usable oxides include, for example, inorganic pigments, e.g., zinc oxide, titanium oxide, and zirconium oxide. The metal oxide flakes which can be used in the present invention may be prepared, for example, as follows. First of all, a plate-like metal oxide of a desired thickness is prepared, for example, using a method in which an organic solvent solution of a metal oxide is coated on a smooth surface action and the resulting film is cracked the action of steam to obtain thin plates as described in U.S. Patent 2,941,895; a method in which a metal oxide solution is coated on a gelatin film, and the gelatin film is then dissolved as described in Japanese Patent Publication No. Sho-30-473; a method of using vacuum evaporation as described in Japanese Patent Publication No. Sho-39-25280; or a method in which metal oxide fibers are treated with an acid and then with heat as described in Japanese Patent Application Laid-Open No. Sho-58-88121. Subsequently, the resulting plate-like metal oxide is ground in a dry ball mill, a wet ball mill, a vibration mill, a jet mill, ertc. or subjected to one or more of classification means, such as vibrating sieves (e.g., a gyroshifter, a hammer screen), wet classifiers (e.g., a spiral classifier, a hydraulic classifier), dry classifiers (e.g., dynamic or centrifugal air classifier), or flotation, to obtain a specific size. Flaky titanium oxide falling within the scope of the present invention is available from Sumitomo Chemical Co., Ltd., under the trade name of Luxelen (registered trademark). The high polymer resin containing therein an ultraviolet absorbent has such a structure that a high polymer resin wall covers a core comprising an ultraviolet absorbent. The ultraviolet absorbent-containing high polymer resin having such a structure is different from a resin powder containing an ultraviolet absorbent which is obtained merely by uniformly mixing an ultraviolet absorbent and a high polymer resin powder as diclosed in Japanese Patent Appplication Laid-Open No. Sho-62-22710. Namely, the resin material in the latter resin powder has a slow release property so that the ultraviolet absorbent is released into the cosmetic base over time causing the problem of poor stability of resin, whereas the ultraviolet absorbent-containing high polymer resin used in the present invention is free from such a disadvantage owing to the above-described structure. The high polymer resin materials capable of containing ultraviolet absorbents include, while not being limited to, vinyl polymers, olefin-vinyl polymers, olefin-allyl polymers, polyamides, acrylic resins, polystyrene, and polyesters. The ultraviolet absorbents which can be incorporated into the high polymer resin materials include, while not being limited to, aminobenzoic acid and/or derivatives thereof, salicyclic acid and/or derivatives thereof, cinnamic acid and/or derivatives thereof, benzophenone derivatives, and urocanic acid and/or derivatives thereof. Specific examples of these ultraviolet absorbents are 2-hydroxy-4-methoxybezophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2,2′-dihydroxy-4-methoxybenzophenone, diethanolamine p-methoxyhydrocinnamate, ethyl-dihydroxypropyl p-aminobenzoate, glyceryl p-aminobenzoate, homomethyl salicylate, methyl o-amino-benzoate, 2-ethylhexyl-2-cyano-3,3-diphenylacrylate, octyldimethyl p-aminobenzoate, 2-ethylhexyl-p-methoxycinnamic acid, 2-ethylhexylsalicylic acid, p-amino-benzoic acid, 2-phenylbenzimidazoyl-5-sulfonic acid, triethanolamine salicylate, 3-(4-methylbenzylidene)-camphor, 2,4-dihydroxybenzophenone, 2,2′,4,4′-tetrahydroxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, octabenzone, 4-isopropyldibenzoylmethane, 4-t-butyl-4′-methoxybenzoyl-methane, 2-ethyl-2-cyano-3,3′-diphenylacrylate, urocanic acid, and ethyl urocanate. These ultraviolet absorbents may be used either individually or as a mixture of two or more thereof. They may be used in combination with conventional additives which can be used in cosmetics, such as fats and oils, esters, hydrocarbons, and liquid higher alcohols. The ultraviolet absorbent-containing high polymer resin used in the present invention can be prepared by, for example, an in situ polymerization process in which an ultraviolet absorbent and, if desired, other arbitrary additives such as fats and oils are mixed a monomer of a high polymer resin in a dissolved state, and the mixture is emulsified by using an inorganic dispersion stabilizer to form an O/W emulsion, followed by polymerization to obtain a powder. The amount of the ultraviolet absorbent to be incorporated into the high polymer resin is usually not less than about 0.01% by weight, and preferably of from about 1.0 to about 50% by weight, per 100% by weight of the resin, though dependent on the amount in which the resulting ultraviolet absorbent-containing high polymer resin is incorporated into cosmetics, the kind of the ultraviolet absorbent used, the desired sunburn preventing effects, and the like. If the amount of the ultraviolet absorbent in the resin is so small as less than about 0.01% by weight, the ultraviolet absorbent-containing resin tends to fail to produce sufficient sunburn preventing effects even incorporated into cosmetics in a relatively large proportion. Besides, such an ultraviolet absorbent-containing resin is unsuitable as a cosmetic material, in such aspects as adhesion, spreadability and durability on the skin. On the other hand, if it exceeds about 50% by weight, the high polymer resin wall covering the ultraviolet absorbent becomes thin and instable with time so that the wall is apt to break when incorporated into cosmetics. One sometimes fails to obtain high polymer resins containing such a large amount of an ultraviolet absorbent depending on the kind of the ultraviolet absorbent used. The ultraviolet absorbent-containing high polymer resin usually has a size of from about 5 to about 20µm. The amount of the metal oxide flake to be incorporated into cosmetics usually ranges from about 1 to about 70% by weight based on the total weight of a cosmetics though varying depending on the desired degree of sunburn preventing effects, the amount of the ultraviolet absorbent-containing high polymer resin powder to be used, and the like. If it is less than about 1% by weight, sufficient sunburn preventing effects will not be exhibited. If it exceeds about 70% by weight, the resulting cosmetics cannot be uniformly applied to the skin or they show poor utility (spreadability, durability, color formation, etc.) and are thus unsatisfactory as sunburn preventive cosmetics. The amount of the ultraviolet absorbent-containing high polymer resin powder to be incorporated into a cosmetic usually ranges from about 0.1 to about 70% by weight based on the total weight of the cosmetic, though varying depending on the desired degree of sunburn preventing effects, the amount of the metal oxide flake used in combination, and the like. If it is less than about 0.1% by weight, sufficient sunburn preventing effects cannot be obtained. If it exceeds about 70% by weight, the resulting cosmetics cannot be uniformly applied to the skin or they show poor utility (spreadability, durability, color formation, etc.) and are thus unsatisfactory as sunburn preventive cosmetics. In addition to the metal oxide flake and the ultraviolet absorbent-containing high polymer resin powder, the cosmetics according to the present invention may further contain, a cosmetically acceptable topical carrier which may include conventional levels of additives commonly employed in cosmetics, such as surface active agents, oily components, moisture retaining agents, pigments, antiseptics, etc. See, for example, U.S. Patent 5,041,282, Sabatelli et al, August 20, 1991, incorporated hereby by reference. Of course, the nature and level of these components will vary based upon the form which the final cosmetic composition will have (e.g. a lotion, a foundation, a face powder, a lipstick, a cream or mousse, to name a few). This cosmetically acceptable carrier comprises the balance of the composition and would generally be present at up to about 98.9%, preferably from about 20% to about 98.9%, of the composition. Without being bound by theory, it is believed that the unexpectedly enhanced ultraviolet-screening effects provided by the present invention result from the fact that the ultraviolet absorbent-containing high polymer resin powder is uniformly dispersed among layers of metal oxide flakes to absorb ultraviolet rays which remain unabsorbed by the metal oxide flakes alone. Examples The present invention is now illustrated in greater detail by way of Examples, but it should be understood that the present invention is not deemed to be limited thereto. Material: (1) Metal Oxide Flakes: "Luxelen" (registered trademark) produced by Sumitomo Chemical Co., Ltd. was used as titanium oxide. Luxelen has an average thickness of 0.2 µm, an average size of 3 to 20 µm, a refractive index of 2.7, and a reflectance of 7 to 15%. Zinc oxide and zirconium oxide used in Examples had an average thickness and average size falling within the ranges as specified in the present invention. (2) Ultraviolet Absorbent-Containing High Polymer Resin Powder: Polymethyl methacrylate resin (PMMA) particles containing octyldimethyl p-aminobenzoate [UV-(1)] and/or 4-t-butyl-4′-methoxybenzoylmethane [UV-(2)] as an ultraviolet absorbent in the proportions shown in Table 1 below were used. In liquid paraffin used as a dispersion medium, 2% of each of the PMMA resin powders containing the ultraviolet absorbent as shown in Table 1 was uniformly dispersed to prepare a paste. Ultraviolet absorption characteristics of each paste (thickness: 7 µm) are shown in Fig. 1. UV-Powder 0000 showed no ultraviolet absorption characteristics, revealing its absorption spectrum as a base line. Measurement of SPF Value: Ten or more Hartley female guinea pigs (b.w.: 250-350 g) were used us test animals. The back of the animal was shaved with an electric shaver, and any remaining hair was removed with a depilatory cream prior to exposure to sunlight. The animal being fixed, the shaved back was divided into a right purt and a left part along the back bone. One of the parts (right of left) was uniformly coated with a sample to give a spread of 2 mg/cm, with the other part (left or right) remaining uncoated. Then, a 2 x 10 cm sun-screening tape having seven vertically aligned 1 x 1 cm square openings was adhered to each of the coated part and the uncoated part. Sunlight irradiation was started 15 minutes after the coating. While monitoring the UV-irradiation dose by means of a UV integrating meter, Radiometer, manufactured by Suga Test Instruments Co., Ltd., the openings were successively shut against sunlight with sun-screening tape at a point when a respective predetermined UV-irradiation dose, varying stepwise, was reached. On shutting all the openings, UV-irradiation was ceased, the tape was stripped off, and the animal was allowed to stand for 24 hours before evaluation. The skin reaction in the area corresponding to each opening was observed with eyes. The integrated irradiation dose on the area which showed the weakest erythema (rash) was taken as a minimum erythema dose (MED). An SPF value for each sample under test was calculated from equation: Test on Utility: Organoleptic tests were conducted with respect to a makeup finish and spreadability on the skin. Fifteen to twenty female panel members were asked to make up with each sample in the usual manner and to evaluate the finish and spreadability according to a 5-rank system: 5 ... excellent; 4 ... good; 3 ... moderate; 2 ... slightly bad; 1 ... bad. The sum of scores each sample gained was divided by the number of panel members, and the quotient was judged as follows. Case 1: Formulations of cosmetics under test (compressed face powder), SPF values obtained, and the results of utility test are shown in Table 2. As can be seen from Table 2, the cosmetics according to the present invention in which titanium oxide flakes and the ultraviolet absorbent-containing high polymer resin are used in combination (Examples Nos. 1 to 7) are excellent in both SPF value and utility, especially showing high SPF values, as compared with those containing titanium oxide alone (Comparative Examples 1-5 and Comparative Example 7 in which a high polymer resin powder containing no ultraviolet absorbent was used in combination), those containing titanium oxide flakes alone (Comparative Example Nos. 6 and 11), those containing the ultraviolet absorbent-containing high polymer alone (Comparative Example Nos. 8-10), those containing titanium oxide in combination with the ultraviolet absorbent (octyldimethyl p-aminobenzoate) (Comparative Example No. 12), and those containing titanium oxide in combination with titanium oxide flakes. Case 2: Table 3 below shows formulations of multi-layer cosmetics (comprising 2 or 3 separate layers in a stationary state but which are to be used after shaking to provide a homogeneous phase), their SPF values and utility thereof. As shown in Table 3, the cosmetic of Example 8 according to the present invention is significantly superior to that of Comparative Example 15 in SFP value and also excellent in utility, proving to have high sunburn preventing effects. Further, the cosmetic of Example 8 also proved excellent in infrared-screening effect as shown in Fig. 2. Case 3: Various cosmetics falling within the scope of the present invention were prepared as follows and evaluated for SPF value and utility. The compositions shown below are given by percent by weight. EXAMPLE 9 The sunburn preventive cream having the above formulation had an SPF value of 17.2 and exhibited satisfactory spreadability on the skin to give a natural makeup finish. EXAMPLE 10 The sunburn preventive milky lotion having the above formulation had an SPF value of 16.7 and exhibited satisfactory spreadability on the skin to give a natural makeup finish. EXAMPLE 11 The creamy foundation having the above formulation had an SPF value of 16.2 and exhibited satisfactory spreadability on the skin to give a natural makeup finish. EXAMPLE 12 The creamy foundation having the above formulation had an SPF value of 18.7 and exhibited satisfactory spreadability on the skin to give a natural makeup finish and was excellent in durability after makeup. EXAMPLE 13 The composition having the above formulation had an SPF value of 14.7, showing sunburn preventing effects, and exhibited satisfactory spreadability on the skin to give a natural makeup finish. EXAMPLE 14 The sunburn preventive oil having the above formulation had an SPF value of 17.5 showing sunburn preventing effects and exhibited a natural makeup finish and satisfactory spreadability on the skin. EXAMPLE 15 The lip-glow having the above formulation had an SPF value of 15.6, showing sunburn preventing effects, and exhibited a natural makeup finish and satisfactory spreadability on the skin. The cosmetics according to the present invention not only produce excellent effects of protecting the skin from harmful ultraviolet rays as can be seen from the SPF values obtained in the foregoing Examples but also safety, satisfactory utility, and satisfactory makeup finishes. They are valuable cosmetics which give a natural finish when used for facing.

Claims: A photoprotective cosmetic composition for application to skin comprising: (a) an effective amount of metal oxide flakes having a thickness of from about 0.01 to about 3 µm and an average size of from about 1 to about 100 µm; and (b) an effective amount of a high polymer resin powder obtained by polymerizing a monomer of a high polymer resin uniformly mixed with an ultraviolet absorbent. The cosmetic composition according to Claim 1, the balance of which comprises a cosmetically acceptable topical carrier. The cosmetic composition according to Claim 2 wherein the high polymer resin powder has a structure wherein a high polymer resin well covers a core comprising the ultraviolet absorbent. The cosmetic composition according to Claim 3 wherein the metal oxide flakes comprise from about 1% to about 70% of said composition. The cosmetic composition according to Claim 4 wherein the high polymer resin powder comprises from about 0.1% to about 70% of said composition. The cosmetic composition according to Claim 5 wherein the high resin powder contains from about 1% to about 50% (by weight of the powder) of the ultraviolet absorbent. The cosmetic composition according to Claim 6 wherein the high polymer resin is selected from the group consisting of vinyl polymers, olefin-vinyl polymers, olefin-alkyl polymers, polyamides, acrylic rsins, polystyrene, polyesters, and the mixtures thereof. The cosmetic composition according to Claim 7 wherein the ultraviolet absorbent is selected from the group consisting of aminobenzoic acid and derivatives thereof, salicyclic acid and deerivatives thereof, cinnamic acid and derivatives thereof, benzophenone derivatives, urocanic acid and derivatives thereof, and mixtures thereof. The cosmetic composition according to Claim 8 wherein the ultraviolet absorbent is selected from the group consisting of 2-hydroxy-4-methoxybezo-phenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2,2′-dihydroxy-4-methoxybenzophenone, diethanolamine p-methoxyhydrocinnamate, ethyl-dihydroxypropyl p-amino-benzoate, glyceryl p-aminobenzoate, homomethyl salicylate, methyl o-amino-benzoate, 2-ethylhexyl-2-cyano-3,3-diphenylacrylate, octyldimethyl p-aminobenzoate, 2-ethylhexyl-p-methoxycinnamic acid, 2-ethylhexylsalicyclic acid, p-amino-benzoic acid, 2-phenylbenzimidazoyl-5-sulfonic acid, triethanolamine salicylate, 3-(4-methylbenzylidene)-camphor, 2,4-dihydroxybenzophenone, 2,2′,4,4′-tetrahydroxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzopheneone, octabenzone, 4-isopropyldibenzoylmethane, 4-t-butyl-4′-methoxybenzoyl-methane, 2-ethyl-2-cyano-3,3′-diphenylacrylate, urocanic acid, ethyl urocanate, and mixtures thereof. The cosmetic composition according to Claim 8 wherein the metal oxide flakes are selected from the group consisting of zinc oxide, titanium oxide, zirconium oxide, and mixtures thereof. The cosmetic composition according to Claim 10 wherein the high polymer resin powder has a size of from about 5 µm to about 20 µm. The cosmetic composition according to Claim 10 wherein, in the high polymer resin powder, the high polymer resin is polymethyl methacrylate and the ultraviolet absorbent is selected from the group consisting of octyldimethyl 4-t-butyl-4′-methoxybenzoyl-methane, and mixtures thereof. A method of providing cosmetic and photoprotection benefits to the skin by applying to the skin an effective amount of the cosmetic composition according to Claim 5 provided that therapeutical methods are excluded. A method of providing cosmetic and photoprotection benefits to the skin by applying to the skin an effective amount of the cosmetic composition according to Claim 10 provided that therapeutical methods are excluded.

Inventors: MASUDA HISATOSHI, TANAKA HIDEKAZU, YOSHIOKA TAKATSUGU, MASUDA, HISATOSHI, TANAKA, HIDEKAZU, YOSHIOKA, TAKATSUGU
Applicants: MAX FACTOR KK, MAX FACTOR K.K.
Application year: 1992
Main classification: A61K7
IPC codes: A61Q1, A61K8, A61Q17