Benzophenone derivative, utraviolet absorbent and external preparation for skin

Abstract: Benzophenone derivatives expressed by the following general expression (1); A ( C-B ) n (1) wherein A in the above general expression (1) is a residual group obtained by removing one hydroxyl group from sugar or sugar alcohol, and B is a benzophenone group shown by the following general expression (2) wherein R₁ through R₁₀ each is expressed by hydrogen, hydroxyl group, an alkoxy group, or the aforesaid binder C , and at least one of them is the binder C . In the case of an alkoxy group, preferably the number of carbon atoms is 1 to 4. C is equivalent to -O-R- ( O is oxygen, R is a fatty chain, and the number of carbon atoms therein is preferably 1 to 4), or 1 mole of glycerin with one hydroxyl group therein bound to A and another hydroxyl group to B . The benzophenone derivatives according to the present invention have excellent capability to absorb ultraviolet rays as well as high compatibility with polar solvent. Also the external preparation for skin in which the benzophenone derivatives are mixed can be mixed in a polar base with wide availability for industrial purpose.

Description: This invention relates to a benzophenone derivative, an ultraviolet absorbent and an external preparation for the skin and, more particularly, to a benzophenone derivative having a high solubility in water, and an ultraviolet absorbent and an external preparation for the kin using the benzophenone derivative. Most of the ultraviolet rays normally received by a human body come from sunlight. The ultraviolet rays included in sunlight are divided into long wavelength ultraviolet rays having a wavelength from 400 nm to 320 nm (UV-A), medium wavelength ultraviolet rays having a wavelength from 320 nm to 290 nm (UV-B), and short wavelength ultraviolet rays having a wavelength of not more than 290 nm in a field of skin science. Of these, the ultraviolet rays having a wavelength of not more than 290 nm are absorbed by the ozonosphere and do not reach the surface of the earth. The ultraviolet rays reaching the surface of the earth give various influences to human skin. Of the ultraviolet rays reaching the surface of the earth, the UV-A makes the color of human skin brown, reduces the elasticity of the skin, and promotes generation of wrinkles, thus causing rapid aging of the human skin. Also the ultraviolet rays promote start of the erythema reaction, or further stimulate this reaction in certain types of patients, and furthermore sometimes may cause photo-toxicity or photo-allergy reactions. On the other hand, also UV-B forms erythema or blister on human skin, and causes aggravation of melanin formation or other changes such as deposition of pigments. For the reasons described above, in order to prevent aging of the human skin and generation or increase of wrinkles and flecks thereon, it is very important to protect human skin from ultraviolet rays, and various types of ultraviolet absorbents have been developed for that purpose. The existing ultraviolet absorbents used for practical application include a PABA derivative, a cinnamic acid derivative, a salicylic acid derivative, a benzophenone derivative, a urocanine derivative, a campher derivative, and heterocyclic derivatives. These types of ultraviolet absorbents are generally mixed in external preparations for the skin such as cosmetics, or quasidrugs, and a low molecular weight dimethyl-siloxane base has been widely used as a base for the external preparation for the skin. Namely, as anti-suntan agents are most frequently used during the summer, oily bases have been used because of their anti-sweat property as well as their high water resisting property, and as a result, most of the materials which have been used for ultraviolet absorbents are oil-soluble. Recently, however, social attention has been focused on effects of ultraviolet rays on human skin in our daily life, so that anti-suntan materials are desired for ordinary skin care. For that purpose, development of materials which are water-soluble and at the same time absorb ultraviolet rays has been strongly demanded, because such materials can be mixed in aqueous external preparations such as skin lotion in a large amount, and also because a large amount of ultraviolet absorbent is required to be mixed in the entire system to realize an external preparation having the high capability to absorb ultraviolet rays, which makes it necessary to mix an ultraviolet absorbent not only in oil phase but also in aqueous phase. The prior types of ultraviolet absorbents, however, are oil-soluble in most cases, and their solubility in water is very low, and their applications have been limited to a relatively narrow area. As a water-soluble ultraviolet absorbent, only 2-hydroxy-4-methoxy-5-sulfoxonium benzophenone sodium salt has been known, and as this is a salt, it affects the pH of the formula system. FR-A-1,481,633 refers to UV absorbing benzophenone derivatives which have been made soluble by means of an -O-alkylene-SO 3 kation. These substances lead to pH problems. FR-A-2,307,820 relates to echinatine derivatives which have been derivatised by glycosylation or acylglycosylation. These compounds are compounded into pharmaceuticals. GB-A-1,186,818 describes benzophenone compounds which are suitable for use as light stabilisers for polymers. JP-A-58110535 discloses benzophenone derivatives which are substituted with one or two glyceryl or polyglyceryl residues. The glyceryl ethers of JP '535 may be used as ultraviolet absorbers in cosmetics, however, their water-solubility is unsatisfactory low. This invention was made to solve the problem in the prior art as described above, and the object is to provide a water-soluble material having a high ultraviolet absorptivity and an external preparation for the skin in which the material is mixed. The inventors made strenuous efforts to achieve the object as described above, and found that certain benzophenone derivatives had an ultraviolet absorptivity as well as a compatibility with polar solvent, thus completing the present invention. The benzophenone derivatives described in Claim 1 of the present application are expressed by the following general expression (1). A-C-B In the general expression (1) above, A is a residual group obtained by removing a hydroxyl group from a sugar or sugar alcohol, residues derived from glycerol being excluded, while B is a benzophenone group which is expressed by the following general expression (2). wherein each of R 1 to R 10 independently represents hydrogen, a hydroxyl group, alkoxy group, or the aforesaid binder C , and one of them is said binder C . In case of an alkoxy group, the number of carbon atoms is preferably in a range from 1 to 4. C is -O-R-O ( O is oxygen, while R is a fatty chain preferably having 1 to 4 carbon atoms), or a glyceryl group. In case of glyceryl, the oxygen atom of one of the hydroxyl groups is bound to A and the oxygen atom of another hydroxyl group is bound to B . The ultraviolet absorbent described in Claim 4 is characterized in that at least one of the benzophenone derivatives expressed by the general expression (1) above is included therein. The external preparation for skin described in Claim 5 is characterized in that at least one of the benzophenone derivatives expressed by the general expression (1) above is included therein. Also, the benzophenone derivative described in the Claim 6 in the present application is expressed by the following general expression (3), A(C-B) n Herein, A is a residue derived from a sugar or sugar alcohol wherein one or more hydroxyl groups have been removed, C is a glyceryl group wherein the oxygen atom of one of the hydroxyl groups is bound to A and the oxygen atom of another hydroxyl group is bound to B . B is a benzophenone group expressed by the following general expression (4), (In the general expression (4), one of R 1 through R 9 is binder C , and the others are hydrogen or a hydroxyl group, an alkyl group, or an alkoxyl group. n is an integer of 1 to 3. The ultraviolet absorbent described in Claim 9 is characterized in that at least one of the benzophenone derivatives expressed by the general expression (3) above is included therein. The external preparation for the skin described in claim 10 is characterized in that at least one of the benzophenone derivatives expressed by the general expression (3) above is included. In the general expression (3) above, A is a residual group of a sugar or sugar alcohol, and examples of the sugar include monosaccharides such as glucose, galactose, xylose, fructose, altose, talose, mannose, arabinose, idose, lyxose, ribose, allose, gulose, erythrose, threose, tagatose, sorbose, psicose, xylulose, ribulose, erythrulose, fucose, rhamnose and a mixture thereof; disaccharides such as maltose, isomaltose, lactose, xylobiose, gentiobiose, kojiobiose, cellobiose, sohorose, nigerose, sucrose, melibiose, laminaribiose, rutinose, lactulose, palatinose, turanose, trehalose and a mixture thereof; or trisaccharides such as maltotriose, meleziose, raffinose and a mixture thereof; furthermore higher polysaccharides and a mixture thereof; and also a mixture of the monosacchride, disaccharide, and higher polysaccharide can be used for this purpose. On the other hand, examples of sugar alcohol include sugar alcohols such as maltitol, sorbitol, mannitol, galactitol, glucitol, inositol, maltitriol, threitol, arabinitol, alcritol and a mixture thereof, or higher polysaccharides and a mixture thereof, and also a mixture of these sugar alcohols can be used for this purpose. Furthermore, the same effect can be achieved by using a mixture of the monosaccharide, disaccharide, higher polysaccharide, and sugar alcohol. In the general expression (4) which expresses a benzophenone group B , one of R 1 to R 9 is binder C , and the others are hydrogen, a hydroxyl group, an alkyl group or an alkoxyl group. In case of an alkyl group or an alkoxyl group, the fatty chain may be any of a straight chain alkyl group, a branched chain alkyl group, an unsaturated alkyl group and a cycloalkyl group, and examples of the fatty chain include a methyl group, an ethyl group, an acetynyl group, a propyl group, an isopropyl group, a propenyl group, a butyl group, an isobutyl group, a t-butyl group, and a butenyl group. Wavelength of absorbed ultraviolet rays does not differ remarkably in any case, but a methyl group and an ethyl group are especially preferable because of their industrial applicability. C is a glyceryl group which is equivalent to 1 mole of glycerin, and any form of bond may be added. n indicates an integer of 1 to 3 because of the water solubility. As the benzophenone derivatives described above are in solid or syrupy state and are extremely excellent in their safety and stability, the materials can be mixed in chemical products such as dye or ink, plastics, coating agent, and chemical textile, and in addition they can be mixed in pharmaceutical products, quasidrug products, cosmetics and cleaning agents as a component. Furthermore, the materials feature the excellent capability to preserve humidity. The benzophenone derivative expressed by the general expression (3) can be produced by, for instance glycidylating hydroxy benzophenone expressed by the general expression (5) and reacting the resultant glycidyloxy benzophenone expressed by the general expression (6) with sugar or sugar alcohol according to the method described in the Japanese Patent Application No.180989/1986. For instance, the derivative can be synthesized as follows. The compound expressed by the general expression (6) can be synthesized by reacting the compound expressed by the general expression (5) according to the method developed by Sandler et. al., (S.R.Sandler, F.R.Berg, J.Appl. Polymer. Soc.9,3707(1965)), or according to the method developed by Robert et. al., (Tetrahedron, 35, 2169-2172 (1979)). Namely, the compound expressed by the general expression (6) can be synthesized by dissolving or suspending the compound expressed by the general expression (5) in a non-aqueous solvent such as dimethylsulfoxide, dimethylformamide, dioxan, dimethylacetamide, N-methylpyrrolidone, N-acetylmorpholine, N-methyl succinic acid imid, or by dissolving or suspending the compound expressed by the general expression (5) in acetone aqueous solvent, or by mixing the compound expressed by the general expression (5) with epichlorohydrin under a temperature from 90 to 130 °C in the presence of a catalyst without using any solvent. This reaction may be carried out under flow of such a gas as argon, and one or more compounds expressed by the general expression (5) may be used in this reaction. The catalysts available in this reaction include a Lewis Acidic Catalyst such as BF 3 ·Et 2 0 or aluminum trichloride; acidic catalyst such as p-toluene sulfonic acid, heteropoly phosphoric acid, chloric acid, sulfuric acid; alkali such as sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, sodium hydride, sodium alcoholate; and amine such as N-methylbenzyl amine. The compound expressed by the general expression (3) can be manufactured by reacting the compound expressed by the general expression (4) with sugar or sugar alcohol according to, for instance, the method described in Japanese Patent Application No. 180989/1986. For instance, the following method is applicable. Sugar or sugar alcohol may be dissolved or suspended in a non-aqueous solvent such as dimethylsulfoxide, dimethylformamide, dioxan, dimethylacetamide, N-methylpyrrolidone, N-acetylmorpholine, or N-methylsuccinimid, and mixed and stirred with the compound expressed by the general expression (6) under a temperature from 90 to 130 °C in the presence of a catalyst. This reaction may be carried out under a flow of gas such as N 2 or argon, and also one or more compounds expressed by the general expression (6) may be used in this reaction. The catalysts available in this reaction include an acidic catalyst such as p-toluene sulfonic acid, heteropoly phosphoric acid, chrolic acid, or sulfonic acid; alkali catalysts such as sodium hydrate, potassium hydrate, potassium carbonate, sodium carbonate, sodium alcoholate; salts such as ammonium chloride, or sodium chloride; and amines such as N-methylbenzylamine. The mole ratio of sugar or sugar alcohol vs. the compound expressed by the general expression (6) to be used in this reaction should preferably be 1:1 to 3:1 when it is necessary to obtain the monoether as a main product, and more preferably be in a range from 2:1 to 3:1. If the mole ratio of sugar or sugar alcohol and the compound expressed by the general expression (6) is out of the ranges described above, namely if sugar or sugar alcohol is too little, impurities such as tetraether would be easily generated, and if sugar or sugar alcohol is too much, a large volume of the material would remain after the reaction, which affects the purification of the product, and it is not preferable. When acid or alkali is used as a catalyst, acid such as acetic acid, chloric acid, sulfuric acid, or phosphoric acid, or alkali such as sodium hydrate or potassium hydrate should be added to neutralize the catalyst in the reaction system after all of the compound expressed by the general expression (6) is consumed. After the reaction as described above, the reactant solvent may be depressurized and removed, the product may be used as it is or may be diffused in a solvent for use, or may be purified according to the column chromatography or the recrystallizing method. In the resultant product obtained as described above, in addition to the benzophenone expressed by the general expression (3), compounds wherein n in the general expression (3) is 4 or more, salt, sugar or sugar alcohol not reacted yet may coexist. For this reason, in order to remove the sugar or sugar alcohol or salt therefrom, the product may be purified by extracting with a solvent such as methyl alcohol, ethyl alcohol, butyl alcohol, isopropyl alcohol, or by diffusing it in a mixture of water and methylethyl ketone having a large volume of salt therein and fractionating the organic solvent layer. Also in order to remove sugar or sugar alcohol and salt for separating the compound, the resultant product may be purified by dissolving or suspending the resultant product in water or a mixture of water and alcohol, passing it at first through water in a opposite phase partition column such as hyper porous polymer (such as Hi-porous® resin supplied from Mitsubishi Kasei Kogyo Kabushiki Kaisha) or octadecyl silica, and then through a mixed solution of water with alcohol such as methanol or ethanol or a polar organic solvent such as acetonitrile, and fractionating and taking out this liquid. Also the resultant product can be purified in an ordinary phase system according to the silica gel chromatography or other appropriate method. The benzophenone derivatives as described above may be used after the solvent for extraction is removed by means of distillation under reduced pressure condition or purified using a column, or may be used as it is. The benzophenone derivatives thus obtained are excellent in their chemical stability and resistance against oxidation, and are also water-soluble and can absorb ultraviolet rays in a wide range, and furthermore they are excellent in their capability to preserve humidity. As the benzophenone derivatives according to the present invention are excellent in their stability, the materials can be mixed in cosmetics or pharmaceutical drugs. In addition to the embodiments of the present invention, the materials can appropriately be mixed with other ordinary cosmetics and other components for pharmaceutical drugs. For instance, various types of hydrocarbon such as fluidized paraffin, squalane, vaseline, cetyl alcohol, isostearyl alcohol, 2-ethyl hexanoic acid cetyl, 2-octyldodecyl alcohol, triisostearic acid glycerin, Macademian nuts oil, and lanolin; fats and oils, oily components such as wax, silicone, surface active agents, thickeners, neutralizers, antiseptics, germicides, anti-oxidants, powder components, perfumes, other ultraviolet absorbents, drugs, metallic sealant, and pH modifiers can be listed as such materials. FIG.1 is a chart of an infrared absorption spectrum of 1-(4-benzoylphenyl) glycerol maltitolether according to an embodiment of the present invention; FIG.2 is a chart of 13 C-NMR spectrum of 1-(4-benzoylphenyl) glycerol maltitolether according to an embodiment of the present invention; FIG.3 is a chart of 1 H-NMR spectrum of 1-(4-benzoylphenyl) glycerol maltitolether according to an embodiment of the present invention; FIG.4 is a chart of ultraviolet absorption spectrum of 1-(4-benzoylphenyl) glycerol maltitolether according to an embodiment of the present invention; FIG.5 is a chart of an infrared absorption spectrum of 1-(4-benzoyl-3-hydroxy-phenyl) glycerol maltitolether according to an embodiment of the present invention; FIG.6 is a chart of 13 C-NMR spectrum of 1-(4-benzoyl-3-hydroxyphenyl) glycerol maltitolether according to an embodiment of the present invention; FIG.7 is a chart of 1 H-NMR spectrum of 1-(4-benzoyl-3-hydroxyphenyl) glycerol maltitolether according to an embodiment of the present invention; FIG.8 is a chart of ultraviolet absorption spectrum of 1-(4-benzoyl-3-hydroxy-phenyl) glycerol maltitolether according to an embodiment of the present invention; FIG.9 is a chart of an infrared absorption spectrum of 2-hydroxy-4-(2-maltosyloxyethoxy) benzophenone according to an embodiment of the present invention; FIG.10 is a chart of 13 C-NMR spectrum of 2-hydroxy-4-(2-maltosyloxyethoxy) benzophenone according to an embodiment of the present invention; FIG.11 is a chart of 1 H-NMR spectrum of 2-hydroxy-4-(2-maltosyloxyethoxy) benzophenone according to an embodiment of the present invention; FIG.12 is a chart of ultraviolet absorption spectrum of 2-hydroxy-4-(2-maltosyloxyethoxy) benzophenone according to an embodiment of the present invention; FIG.13 is a chart of an infrared absorption spectrum of 2-hydroxy-4-(2-glucosyloxyethoxy) benzophenone according to an embodiment of the present invention; FIG.14 is a chart of 13 C-NMR spectrum of 2-hydroxy-4-(2-glucosyloxyethoxy) benzophenone according to an embodiment of the present invention; FIG.15 is a chart of 1 H-NMR spectrum of 2-hydroxy-4-(2-glucosyloxyethoxy) benzophenone according to an embodiment of the present invention; FIG.16 is a chart of ultraviolet absorption spectrum of 2-hydroxy-4-(2-glucosyloxyethoxy) benzophenone according to an embodiment of the present invention; FIG.17 is a chart of an infrared absorption spectrum of 2-hydroxy-(3-maltosyloxypropyloxy) benzophenone according to an embodiment of the present invention; FIG.18 is a chart of 13 C-NMR spectrum of 2-hydroxy-(3-maltosyloxypropyloxy) benzophenone according to an embodiment of the present invention; FIG.19 is a chart of 1 H-NMR spectrum of 2-hydroxy-(3-maltosyloxypropyloxy) benzophenone according to an embodiment of the present invention; FIG.20 is a chart of ultraviolet absorption spectrum of 2-hydroxy-(3-maltosyloxypropyloxy) benzophenone according to an embodiment of the present invention. Description is made hereinafter for preferred embodiments of the present invention. It should be noted that the embodiments are not intended to limit the scope of the present invention. A unit for mixing rate is weight %. Embodiment 1 1-(4-benzoylphenyl) glycerol maltitolether 1 g of 4-hydroxy benzophenone and 4.668 g of epichlorohydrin (0.025 mol) were dissolved, 20.5 mg of sodium hydroxide was added, and the reaction system was heated to 100 °C and then cooled to 95 °C. Furthermore 201.4 mg of sodium hydroxide was added, and additional heating and agitation was carried out for 3 hours. The system was cooled to room temperature, and the salt was removed by filtering. The obtained filtrate was condensed under reduced pressure condition, and purified according to the silica gel chromatography to obtain 1.0 g of solid state 4-glycidyloxy benzophenone (Yield : 83 %). Then, 2.921 g of maltitol and 476.0 mg of potassium hydroxide were dissolved in 20 ml of dimethylsulfoxide, and the mixture was stirred under flow of nitrogen for 30 minutes. A solution obtained by dissolving 719 mg of the resultant 4-glycidyloxy benzophenone dissolved in 1 ml of dimethylsulfoxide was dripped to it. Furthermore, heating and agitation was continued for 1 hour under flow of nitrogen, and the reaction system was cooled to room temperature and neutralized with chloric acid. The reaction system was fractionated according to the column chromatography using the hyperporous polymer (Hiporous® resin supplied from Mitsubishi Kasei Kogyo Kabushiki Kaisha) at first as a developing solvent with purified water, and then a mixture of ethyl alcohol and purified water with the mixing ratio of 1:1, and effluent fraction in which the mixing ratio of ethyl alcohol and purified water was 1:1 was condensed to obtained 500 mg of 1-(4-benzoylphenyl) glycerol maltitolether (Yield : 30 %). (1) Infrared absorption spectroscopy Measurement was made by using the IRA-1® infrared absorption spectrometer supplied from Nihon Bunko Kabushiki Kaisha with the KBr disk method, and absorption due to stretching vibration of the hydroxyl group at 3387 cm -1 , stretching vibration of the glyceroyl group at 2928 cm -1 and stretching vibration of the carbonyl group at 1649 cm -1 were observed. The results are shown in FIG. 1. (2) 13 C-NMR spectroscopy Measurement was made by using CD 3 OD as a solvent with JEOL® GX-400 supplied from Nippon Denshi Kabushiki Kaisha at 35 °C, and signal from carbon atoms in the benzophenone part was observed at δ 197 ppm, 164 ppm, 139 ppm, 134 ppm, 133 ppm, 131 ppm, 129 ppm, and 115 ppm, and signals from the maltitol group, and the glyceryl group was observed in a range from 103 ppm to 62 ppm. The results are shown in FIG.2. (3) 1 H-NMR spectroscopy Measurement was made by using CD 3 OD as a solvent with JEOL® GX-400 supplied from Nippon Denshi Kabushiki Kaisha under room temperature, and signals from hydrogen in the benzophenone section were observed in the range of δ 7.8 -7.1 ppm and signal from hydrogen in the maltitol group and glyceryl group were observed in the range of δ 5.2 -3.3 ppm. The results are shown in FIG.3. (4) Ultraviolet ray absorption spectroscopy Measurenent was made by using the UVIDEC® 610 C ultraviolet ray absorption spectrometer from Nihon Bunko Kabushiki Kaisha with methanol as a solvent, and the peak absorption was observed at 282.7 nm. The results was shown in FIG.4. (5) Phenol indication The product was spotted on TCL, phenol indicator was sprayed with a sprayer on it. 10 % sodium carbonate solution was sprayed over it, but a color indicating presence of phenol was not observed. Embodiment 2 1-(4-benzoyl-3-hydroxyphenyl) glycerolmaltitolether 3.0 g of 2,4-dihydroxy benzophenone and 15.5 g of epichlorohydrin (0.075 mol) were dissolved, and 112.0 mg of sodium hydroxide was added. The reaction system was heated to 100 °C and then cooled to 95 °C, and 672.2 mg of sodium hydroxide was added. Additional heating and agitation was continued for 3 hours. Then, the reaction system was cooled to room temperature , and salt was removed by filtering. The resultant filtrate was condensed under reduced pressure condition, and purified according to the silica gel column chromatography. 2.8216 g of solid state 4-glycidyloxy-2-hydroxy benzophenone was obtained (Yield : 75%). Then, 1.550 g of maltitol and 84.2 mg of potassium hydroxide were dissolved in 10 ml of dimethylsulfoxide. The mixture was heated and stirred for 30 minutes under a flow of nitrogen, and a solution obtained by dissolving 406.0 mg of 4-glycidyloxy-2-hydroxy benzophenone in 6 ml of dimethylsulfoxide was dripped to it. Then, heating and agitation under flow of nitrogen was carried out for 1 hour, and then the reaction system was cooled to room temperature, and the mixture was neutralized by chloric acid. The reaction system was fractionated according to the column chromatography using the hyperporous polymer (Hiporous® resin supplied from Mitsubishi Kasei Kogyo Kabushiki Kaisha) at the first time as a solvent with purified water, and then a mixture of ethyl alcohol and purified water with the mixing ratio of 1:1. Effluent fraction in which the mixing ratio of ethyl alcohol and purified water was 1:1 was condensed to obtain 478 mg of 1-(4-benzoyl-3-phenyl)glycerol maltitolether (Yield : 52%). (1) Infrared absorption spectroscopy Measurement was made by using the IRA-1® infrared absorption spectrometer supplied from Nihon Bunko Kabushiki Kaisha with the KBr disk method, and absorption due to stretching vibration of the hydroxyl group at 3380 cm -1 , stretching vibration of the hydrocarbon group at 2928 cm -1 and stretching vibration of the carbonyl group at 1626 cm -1 were observed. The results are shown in FIG. 5. (2) 13 C-NMR spectroscopy Measurement was made by using CD 3 OD as a solvent with JEOL® GX-400 supplied from Nippon Denshi Kabushiki Kaisha at 35 °C, and signals from carbon atoms in the benzophenone part were observed at δ 201 ppm, 166 ppm, 139 ppm, 136 ppm, 133 ppm, 132 ppm, 130 ppm, 129 ppm and 114 ppm, and those from the carbons in the maltitol group and the glyceryl group were observed in a range from 109 ppm to 62 ppm. The results are shown in FIG.6. (3) 1 H-NMR spectroscopy Measurement was made by using CD 3 OD as a solvent with JEOL® GX-400 supplied from Nippon Denshi Kabushiki Kaisha, and signals from hydrogen in the benzophenone section were observed at δ 12.5 ppm and in the range of δ 7.8 -7.1 ppm, and signals from hydrogen in the maltitol group and glyceryl group were observed in the range of δ 5.2 -3.3 ppm. The results are shown in FIG.7. (4) Ultraviolet ray absorption spectroscopy Measurement was made by using the UVIDEC® 610 C ultraviolet ray absorption spectrometer from Nihon Bunko Kabushiki Kaisha with methanol as a solvent, and the peak absorption was observed at 279.8 nm. The results are shown in FIG.8. (5) Phenol indication The product was spotted on TCL, phenol indicator was sprayed with a sprayer on it. 10 % sodium carbonate solution was sprayed over it, and a color indicating presence of phenol was observed. Experiment 1 Production of Skin Lotion According to the formulation as shown in table 1, a skin lotion in which the benzophenone derivative was mixed, and a skin lotion in which 2-hydroxy-4-methoxy-5-sulfoxonium benzophenone as a control were produced. COMPONENT EXAMPLE 1 CONTROL 1 A. (ALCOHOL PHASE) Ethanol 5.0 5.0 POE oleil alcohol ether 2.0 2.0 Perfume q.s. q.s. B. (AQUEOUS PHASE) 1,3-butylene glycerol 5.0 5.0 Benzophenone derivative (Embodiment 1) 8.0 - 2-hydroxy-4-methoxy-sulfoxonium benzophenone - 8.0 Triethanol amine 0.1 0.1 Carboxy vinyl polymer 0.15 0.15 Purified water Residual Residual Alcohol phase A was added to aqueous phase B , and a perfume was made water-soluble to obtain a skin lotion. In example 1, a skin lotion which has no color and is transparent with viscosity was obtained, while in control 1 a lotion which was yellow and has no viscosity was obtained. Experiment 2 Test for Anti-suntan Material Field tests were carried out in a sea beach using 2 types of skin lotion produced in Experiment 1. In the experiment, the samples were applied to right and left halves of each member of a group consisting of 20 men and 20 women. A degree of sun burning was determined. The criteria for the determination were as follows. Criteria for evaluation of sun-burning degree Remarkable erythema recognized × Slight erythema recognized Δ Erythema not recognized ○ The results are shown in Table 2. APPLIED SECTION IN EXAMPLE 1 APPLIED SECTION IN CONTROL 1 ○ 37 6 Δ 3 12 × 0 22 NUMBER OF SKIN NONE ITCH 10 CASES TROUBLE CASES ERUPTION 2 CASES From the results as described above, the external preparation for the skin in which the benzophenone derivative is mixed is more effective for protection from ultraviolet rays than that in which the prior types of water soluble ultraviolet absorbent are mixed, and has higher safety without causing any skin trouble. Experiment 3 Capability to Preserved Humidity The change of skin conductance in a group consisting of 15 men and 15 women was measured under the environmental conditions of a room temperature of 25 °C and a relative humidity of 50 %. The skin lotion produced in Experiment 1 was applied to an arm of each member of the group, and the skin conductance of the arm skin was measured in 24 hours after the treatment. The capability to preserve humidity was determined according to the increase ratio. The results of the determination were as follows. Increase rate of conductance = Increase ratio of conductance value Conductance value before treatment Criteria for the capability to preserve humidity Increase ratio of conductance : less than 15 % ○ Increase ratio of conductance : 15 % to 30 % Δ Increase ratio of conductance : 30 % or more ○ The results are as shown in Table 3. APPLIED SECTION IN EXAMPLE 1 APPLIED SECTION IN CONTROL 1 ○ 21 6 ▵ 9 8 X 0 16 From the results as described above, it turned out that the external preparation for the skin with the benzophenone derivative according to the present invention mixed therein is more excellent in its capability to preserve humidity than the external preparation with the prior types of water soluble ultraviolet absorbent. Embodiment 3 2-Hydroxy 4-(2-maltoxyethoxy) benzophenone 1 g of 2,4-dihydroxy benzophenone was added to and dissolved in 7 g of ethylbromohydrin, 37 mg of sodium hydroxide and 0.25 g of purified water. The solution was heated to 100 °C and stirred and then cooled to 90 °C. Furthermore, 224 mg of sodium hydroxide was added to the mixture. The mixture was heated and stirred for 2 hours, and then cooled. The resultant was extracted with chloroform, washed with water, and condensed by removing the water. The product was purified using the silica gel chromatography (Toluene : Methylethyl ketone), and 1.1 g of 2-hydroxy 4-(2-hydroxyethoxy) benzophenone was obtained. Then, 100 mg of the product was dissolved in 1 ml of toluene, and 219 mg of acetylmaltose and 10 mg of molybdoric acid were added. The resultant product was heated and stirred for 30 minutes under a temperature of 100 °C. Then the reaction system was cooled by air to room temperature , extracted with toluene, and the extract was washed once with purified water and 4 times with saturated saline, and the organic layer was dried with sulfuric magnesium anhydride and condensed under reduced pressure condition. The residual materials are purified according to the silica gel chromatography (Hexan : Ethyl acetate), and 110 mg of acetylated compound of 2-hydroxy 4-(2-maltosyloxyethoxy) benzophenone was obtained. 100 mg of this acetylated 2-hydroxy 4-(2-maltosyloxy) benzophenone was dissolved in 3 ml of methanol, 0.3 ml of natrium methylate was added to the mixture. The resultant mixture was stirred for 30 minutes under room temperature, neutralized by an ion-exchange resin (such as, for instance, Amberlite® IR 120B supplied from Organo Kogyo or UBK® 530 from Mitsubishi Kasei), and the resin was removed by filtering. The reactant liquid was condensed under reduced pressure condition, and 2-hydroxy 4-(2-maltosyloxyethoxy) benzophenone was obtained. The resultant 2-hydroxy 4-(2-maltosyloxyethoxy) benzophenone was analyzed according to the methods (1) to (6). (1) Infrared absorption spectroscopy Measurement was made by using the IRA-1® infrared absorption spectrometer supplied from Nihon Bunko Kabushiki Kaisha with the KBr disk method, and absorption due to stretching vibration of the hydroxyl group at 3400 cm -1 , stretching vibration of the 2-maltosyloxyethoxy group at 2920 cm -1 and stretching vibration of the carbonyl group at 1630 cm -1 were observed. The results are shown in FIG. 9. (2) 13 C-NMR spectroscopy Measurement was made by using CD 3 OD as a solvent with JEOL® GX-400 from Nippon Denshi Kabushiki Kaisha at room temperature, and signals were observed at δ 201 ppm, 167 ppm. 167 ppm, 140 ppm, 136 ppm, 133 ppm, 130 ppm. 129 ppm, 115 ppm. 108 ppm, 105 ppm, 103 ppm, 103 ppm, 81 ppm, 78 ppm, 77 ppm, 75 ppm, 75 ppm, 75 ppm, 74 ppm, 74 ppm, 72 ppm, 69 ppm. 69 ppm, 63 ppm, and 62 ppm. The results are shown in FIG.10. (3) 1 H-NMR spectroscopy Measurement was made by using CD 3 OD as a solvent with JEOL® GX-400 supplied from Nippon Denshi Kabushiki Kaisha under room temperature, and signals were observed at δ 7.53 -7.38 ppm, 6.46 to 6.39, and 4.72 to 3.11. The results are shown in FIG.11. (4) Ultraviolet ray absorption spectroscopy Measurement was made by using an UVIDEC® 610 C ultraviolet absorption spectrometer from Nihon Bunko Kabushiki Kaisha with methanol as a solvent, and the peak absorption was observed at 287.6 nm and 324.6 nm. The results are shown in FIG.12. (5) Melting point Measuring was carried out by using the melting point measuring device based on a capillary system from Arthur H. Thoms Company, and the material was melted in the temperature range of 92 to 110 °C, but a clear melting point was not shown. (6) Water solubility 20 weight % or more was dissolved in water. Embodiment 4 2-hydroxy 4-(2-glucosyloxyethoxy) benzophenone 100 mg of the 2-hydroxy 4-(2-hydroxyethoxy) benzophenone synthesized in Embodiment 3 was dissolved in 2 ml of toluene, 136 mg of acetylglucose was added to the mixture, and the resultant mixture was heated to 100 °C, 50 mg of molybdoric acid was added to it, and the resultant mixture was heated and stirred for 30 minutes under a temperature of 100 °C. The reaction system was air cooled to room temperature, extracted with toluene, washed once with purified water and 4 times with saturated saline, and the organic layer was dried with sulfuric magnesium anhydride and was condensed under reduced pressure condition. The residual materials were purified according to the silica gel chromatography (Hexan : Ethylacetate), and 189 mg of acetylide of 2-hydroxy 4-(2-glycosyloxyethoxy) benzophenone was obtained. 189 mg of the acetylated 2-hydroxy 4-(2-maltosyloxyethoxy) benzophenone was dissolved in 6 ml of methanol, 0.6 ml of sodium methylate was added to it, and the resultant mixture was stirred for 30 minutes under room temperature, neutralized by an ion-exchange resin (such as, for instance, Amberlite® IR120B from Organo Kogyo, or UBK® 530 from Mitsubishi Kasei), the resin was removed by filtering, the reactant liquid was condensed under reduced pressure condition, and 2-hydroxy 4-(2-glucosyloxyethoxy) benzophenone was obtained. The obtained 2-hydroxy 4-(2-glucosyloxyethoxy) benzophenone was analyzed according to the method (1) to (6) described below. (1) Infrared absorption spectroscopy Measurement was made by using the IRA-1® infrared absorption spectrometer supplied from Nihon Bunko Kabushiki Kaisha with the KBr disk method, and absorption due to stretching vibration of the hydroxyl group at 3400 cm -1 , stretching vibration of the 2-glucosyloxyethoxy group at 2930 cm -1 , and stretching vibration of the carbonyl group at 1630 cm -1 were observed. The results are shown in FIG. 13. (2) 13 C-NMR spectroscopy Measurement was made by using CD 3 OD as a solvent with JEOL® GX-400 from Nippon Denshi Kabushiki Kaisha at room temperature, and signals were observed at δ 201 ppm, 167 ppm, 167 ppm, 140 ppm, 136 ppm, 133 ppm. 130 ppm, 129 ppm, 114 ppm, 109 ppm, 108 ppm, 104 ppm, 103 ppm, 78 ppm, 75 ppm, 72 ppm, 69 ppm, 69 ppm, and 62 ppm. The results are shown in FIG.14. (3) 1 H-NMR spectroscopy Measurement was made by using CD 3 OD as a solvent with JEOL® GX-400 supplied from Nippon Denshi Kabushiki Kaisha, and signals were observed at δ 7.52 -7.38 ppm, 6.45 to 6.39, and 4.28 to 3.10. The results are shown in FIG.15. (4) Ultraviolet ray absorption spectroscopy Measurement was made by using the UVIDEC® 610 C ultraviolet absorption spectrometer from Nihon Bunko Kabushiki Kaisha with methanol as a solvent, and the peak absorption was observed at 286.9 nm and 324.3 nm. The results are shown in FIG.16. (5) Melting point The compound absorbs much humidity, and measurement could not be carried out. (6) Water solubility The compound was dissolved in water by around 10 weight %. Embodiment 5 2-hydroxy 4-(3-maltosyloxypropyloxy) benzophenone 1 g of 2,4-dihydroxy benzophenone was dissolved with 7.78 g of 1-bromopropanol, 40 mg of sodium hydroxide, and 0.1 ml of purified water. The mixture was heated to 100 °C and stirred, and was cooled to 90 °C. Furthermore 220 mg of sodium hydroxide was added. The mixture was heated and stirred for 4 hours, and then air cooled, extracted with chloroform, washed with water, and then dried and condensed. The product was purified by using the silica gel column chromatography (Toluene : Methylethyl ketone), and 1.01 g of 2-hydroxy-4-(3-hydroxypropyloxy) -benzophenone was obtained (Yield : 80 %). 1.14 g of octaacetyl maltose was added to 460 mg of 2-hydroxy 4-(3-hydroxypropyloxy)-benzophenone, and the mixture was dissolved in 10 ml of toluene, and heated to 90 °C, and then a catalytic level of molybdoric acid was added to it. The mixture was heated and stirred for 30 minutes and then air cooled, extracted with 100 ml of toluene, and washed with saturated sodium bicarbonate water. After dried and condensed, the product was purified by the silica gel chromatography (Toluene : Methylethyl ketone), and 880 mg of acetylide of 2-hydroxy-4-(3-maltosyloxypropyloxy)-benzophenone was obtained (Yield : 60 %). 880 mg of the acetylide of 2-hydroxy 4-(3-maltosyloxypropyloxy)-benzophenone was dissolved in 20 ml of methanol, sodium methoxide was added. The mixture was stirred for 30 minutes and then neutralized by acidic resin, filtered and condensed and 565 mg of 2-hydroxy 4-(3-maltosyloxypropyloxy) benzophenone was obtained (Yield : 100 %). The 2-hydroxy-4-(3-maltosyloxypropyloxy)-benzophenone was confirmed according to the methods (1) to (6) described below. (1) Infrared absorption spectroscopy Measurement was made by using the IRA-1® infrared absorption spectrometer supplied from Nihon Bunko Kabushiki Kaisha with the KBr disk method, and absorption due to stretching vibration of the hydroxyl group at 3400 cm -1 , stretching vibration of the 3-maltosyloxy group at 2930 cm -1 , and stretching vibration of the carbonyl group at 1626 cm -1 were observed. The results are shown in FIG. 17. (2) 13 C-NMR spectroscopy Measurement was made by using CD 3 OD as a solvent with JEOL® GX-400 from Nippon Denshi Kabushiki Kaisha under room temperature, and signals were observed at δ 201 ppm, 167 ppm, 167 ppm, 140 ppm, 136 ppm, 133 ppm. 130 ppm, 129 ppm, 114 ppm, 109 ppm, 104 ppm, 103 ppm, 81 ppm, 78 ppm, 76 ppm, 75 ppm, 75 ppm, 74 ppm, 71 ppm, 67 ppm, 67 ppm, 63 ppm, 62 ppm, and 30 ppm. The results are shown in FIG.18. (3) 1 H-NMR spectroscopy Measurement was made by using CD 3 OD as a solvent with JEOL® GX-400 supplied from Nippon Denshi Kabushiki Kaisha under room temperature, and signals were observed at δ 7.55 ppm, 7.50 ppm, 7.43 ppm, 6.56 ppm, 6.50 ppm, 6.44 ppm, and in a range from 5.22 ppm to 1.9ppm. The results are shown in FIG.19. (4) Ultraviolet ray absorption spectroscopy Measurement was made by using the UVIDEC® 610 C ultraviolet ray absorption spectrometer from Nihon Bunko Kabushiki Kaisha with methanol as a solvent, and the peak absorption was observed at 289.4 nm and 324.1 nm. The results are shown in FIG.20. (5) Melting point Measurement was made by using the melting point measuring device based on a capillary system developed by Arthur H. Thoms Company, and the product was melted in a temperature range from 77 to 87°C, but a clear melting point was not shown. (6) Water solubility The compound was dissolved in water by around 20 weight % or more. Experiment 4 Production of Skin Lotion According to the formulation as shown in table 4, a skin lotion in which the benzophenone derivative was mixed, and a skin lotion in which 2-hydroxy-4-methoxy-5-sulfoxonium benzophenone as a control were produced. COMPONENT EXAMPLE 2 CONTROL 1 A (ALCOHOL PHASE) Ethanol 5.0 5.0 POE oleil alcohol ether 2.0 2.0 Perfume q.s. q.s. B (AQUEOUS PHASE) 1,3-butylene glycerol 5.0 5.0 Benzophenone derivative (Embodiment 3) 8.0 - 2-hydroxy-4-methoxy-sulfoxonium benzophenone - 8.0 Triethanol amine 0.1 0.1 Carboxy vinyl polymer 0.15 0.15 Purified water Residual Residual Alcohol phase A was added to aqueous phase B , and a perfume was made water soluble to obtain a skin lotion. In example 2, an excellent skin lotion which is transparent and viscosity without any specific color, while in control 2 a lotion which was yellow and had no viscosity was obtained. Experiment 5 Test for Anti-suntan Material Field tests were carried out in a sea beach using 2 types of skin lotion produced in Experiment 4. In the experiment, the samples were applied to right and left halves of each member of a group consisting of 20 men and 20 women. A degree of sun burning was determined. The criteria for the determination of a degree of burning by sunlight and other condition are the same as those in Experiment 2 above. The results are shown in Table 5. APPLIED SECTION IN EXAMPLE 2 APPLIED SECTION IN CONTROL 2 ○ 39 6 Δ 1 15 × 0 19 NUMBER OF SKIN NONE ITCH 8 CASES TROUBLE CASES ERUPTION 2 CASES From the results as described above, the external preparation for the skin in which the benzophenone derivative is mixed is more effective for protection from ultraviolet rays than that in which the prior types of water soluble ultraviolet absorbent are mixed, and has higher safety without causing any skin trouble. Experiment 6 Capability to Preserve Humidity The capability of the product to preserve humidity was tested according to the same procedure as that in experiment 3 above. The results are as shown in Table 6. APPLIED SECTION IN EXAMPLE 2 APPLIED SECTION IN CONTROL 2 ○ 26 6 Δ 4 8 × 0 16 From the results as described above, it turned out that the external preparation for the skin with the benzophenone derivative according to the present invention mixed therein is more excellent in its capability to preserve humidity than the external preparation with the prior types of water soluble ultraviolet absorbent. Description is made for examples of mixing in the external preparation for the skin according to the present invention. It should be noted that each external preparation showed an excellent effect for preventing ultraviolet rays. Formulation1 Cream A. Oily phase Stearic acid 10.0 Stearyl alcohol 4.0 Stearic acid monoglycerin 8.0 Vitamin E acetate 0.5 Perfume 0.4 Ethylparaben 0.1 Butylparaben 0.1 Propylparaben 0.1 B.Aqueous phase Propylene glycol 8.0 Glycerin 2.0 1-(4-benzoyl-3-hydroxy phenyl) glycerol maltitolether 6.0 Potassium hydroxide 0.4 Trisodium edetate 0.05 Purified water Residual <Production method> The oily fraction A and the aqueous fraction B are heated to 70 °C and completely dissolved. Then phase A is added to phase B, and the mixture is emulsified by an emulsifier. Then the emulsion is cooled by a heat exchanger and the cream is obtained. Formulation 2 Cream A. Oily phase Cetanol 4.0 Vaseline 7.0 Isopropyl myristate 8.0 Squalane 12.0 Dimethyl polysiloxane 3.0 Stearic acid monoglycerin ester 2.2 POE(20) sorbitane monostearate 0.5 Glycyrrhyzin acid stearate 0.1 BHT 0.02 Ethylparaben 0.1 Butylparaben 0.1 Propylparaben 0.1 B. Aqueous phase 1,3 butylene glycol 7.0 Disodium edetate 0.07 Phenoxyethanol 0.2 L-ascorbic acid phosphoric acid ester magnesium salt 3.0 Polyacrylic acid alkyl ester 1.0 1-(4-benzoylphenyl) glycerol maltitolether 8.0 Purified water Residual <Production method> The cream was obtained according to the procedure as in the formulation 1. Formulation 3 Milky Lotion A. Oily phase Oleylorate 3.0 Vaseline 7.0 Squalane 5.0 Sorbitane-sesqui-oleic acid ester 0.8 Polyoxyethylene oleil ether (20 E.O.) 1.2 1-(4-benzoyl-3-hydroxy phenyl) glycerol sorbitol ether 3.0 Methylparaben 0.1 Perfume 0.12 B. Aqueous phase Dipropylenglycol 6.0 Ethanol 3.0 Carboxyvinyl polymer 0.17 Sodium hyaluronate 0.01 Polyacrylic alkyl ester 1.0 1-(4-benzoyl-3-hydroxy phenyl) glycerol sugar ether 4.0 Potassium hydroxide 0.08 Hexametalic acid sodium 0.05 Purified water Residual <Production method> The milky lotion was obtained according to the same procedure as formulation 1. Formulation 4 Cream A. Oily phase Behenyl alcohol 0.5 12-hydroxy stearic acid cholestanol ester 2.0 Squalane 7.0 Jojoba oil 5.0 Self-emulsifying type monostearic acid glycerin 2.5 Polyoxyethylene sorbitane monestearic acid ester(20E0) 1.5 2-hydroxy-4-methoxy benzophenone 3.0 Ethylparaben 0.2 Butylparaben 0.1 Propylparaben 0.1 B. Aqueous phase Propylene glycol 5.0 Sodium edetate 0.08 Glycerin 5.0 Beegum (Montmorillonite) 3.0 Potassium hydroxide 3.3 1-(4-benzoyl-3-hydroxyphenyl) glycerol maltotriol ether 8.0 Purified water Residual <Production method> The cream was obtained according to the same procedure as in formulation 1. Formulation 5 Skin Lotion with powder A. Oily phase Ethanol 8.0 P0E(60) glyceryl monoisostearate 2.0 L-menthol 0.1 Campher 0.1 Methylparaben 0.2 Perfume q.s. B. Aqueous phase Glycerin 3.5 1-(4-benzoyl phenyl) glycerol maltotriolether 4.0 Zinc 1.5 Kaolin 0.5 Bentonite 0.3 Sodium hexamethalate 0.03 Purified water Residual <Production method> The skin lotion was obtained according to the same procedure as that in formulation 1. Formulation 6 Cream A. Oily phase Stearic acid 10.0 Stearyl alcohol 4.0 Stearic acid monoglycerin 3.0 Vitamin E acetate 0.5 Perfume 0.4 Ethylparaben 0.1 Butylparaben 0.1 Propylparaben 0.1 B.Aqueous phase Propylene glycol 8.0 Glycerin 2.0 2-hydroxy-4-(2-maltosyloxyethoxy)-benzophenone 8.0 Potassium hydroxide 0.4 Trisodium edetate 0.05 Purified water Residual <Production method) The cream was obtained according to the same procedure as in formulation 1. Formulation 7 Cream A. Oily phase Cetanol 4.0 Vaseline 7.0 Isopropyl myristate 8.0 Squalane 12.0 Dimethyl polysiloxane 3.0 Stearic acid monoglycerin ester 2.2 POE(20) sorbitane monostearate 0.5 Glycyrrhyzin acid stearate 0.1 BHT 0.02 Ethylparaben 0.1 Butylparaben 0.1 Propylparaben 0.1 B. Aqueous phase 1,3 butylene glycol 7.0 Disodium edetate 0.07 Phenoxyethanol 0.2 L-ascorbic acid phosphoric acid ester magnesium salt 3.0 Polyacrylic acid alkyl ester 1.0 2-hydroxy-4-(2-glyceroylethoxy) benzophenone 8.0 Purified water Residual <Production method> The cream was obtained according to the procedure as in formulation 1. Formulation 8 Milky Lotion A. Oily phase Oleylorate 3.0 Vaseline 7.0 Squalane 5.0 Sorbitane-sesqui-oleic acid ester 0.8 Polyoxyethylene oleyl ether (20 E.O.) 1.2 Di-p-methoxy cinnamic acid glycerol 3.0 Methylparaben 0.1 Perfume 0.12 B. Aqueous phase Dipropylenglycol 5.0 Ethanol 3.0 Carboxy vinyl polymer 0.17 Sodium hyaluronate 0.01 Polyacrylic alkyl ester 1.0 2,2'-dihydroxy 4-(2-maltosyloxyethoxy) benzophenone 4.0 Potassium hydroxide 0.08 Hexametalic acid sodium 0.05 Purified water Residual <Production method> The milky lotion was obtained according to the same procedure as in formulation 1. Formulation 9 Cream A. Oily phase Behenyl alcohol 0.5 12-hydroxy stearic acid cholestanol ester 2.0 Squalane 7.0 Jojoba oil 5.0 Self-emulsifying type monostearic acid glycerin 2.5 Polyoxyethylene sorbitane monestearic acid ester(20E0) 1.5 2-hydroxy-4-methoxy benzophenone 3.0 Ethylparaben 0.2 Butylparaben 0.1 Propylparaben 0.1 B. Aqueous phase Propylene glycol 5.0 Sodium edetate 0.08 Glycerin 5.0 Beegum (Montmorillonite) 3.0 Potassium hydroxide 3.3 2,2',4'-trihydroxy 4(2-maltosyloxyethoxy)-benzophenone 8.0 Purified water Residual <Production method> The cream was obtained according to the same procedure as in formulation 1. Formulation 10 Skin Lotion with powder A. Oily phase Ethanol 8.0 POE(60) glyceryl monoisostearate 2.0 L-menthol 0.1 Campher 0.1 Methylparaben 0.2 Perfume q.s. B. Aqueous phase Glycerin 3.5 2-hydroxy-4(3-maltosyloxybuthoxy) benzophenone 4.0 Zinc 1.5 Kaolin 0.5 Bentonite 0.3 Sodium hexamethalate 0.03 Purified water Residual <Production method> The skin lotion was obtained according to the same procedure as that in formulation 1. As described above, the benzophenone derivatives according to the present invention have excellent capability to absorb ultraviolet rays as well as high compatibility with polar solvents. Also, the external preparation for the skin in which the materials are mixed can be mixed in a polar base, which insures wide availability for industrial purpose.

Claims: Benzophenone derivative of general formula (1) A - C - B wherein A represents a residue derived from a sugar or a sugar alcohol wherein a hydroxyl group has been removed, residues derived from glycerol being excluded, B is benzophenone group of general formula (2) wherein each of R 1 to R 10 independently represents hydrogen, a hydroxyl group, an alkoxy group or a binder C, with the proviso that one of R 1 to R 10 is represented by said binder C, and wherein C represents a group -0-R-0-, wherein R is a fatty chain, or C is a glyceryl group. Benzophenone derivative according to claim 1, characterized in that at least one of R 1 to R 10 is an alkoxy group having 1 to 4 carbon atoms. Benzophenone derivative according to claim 1, characterized in that C is a group -O-R-O-, wherein R is a fatty chain having 1 to 4 carbon atoms. Ultraviolet absorbent, characterized in that it comprises at least one of the benzophenone derivatives according to claims 1 to 3. External preparation for the skin, characterized in that is comprises at least one of the benzophenone derivatives according to claims 1 to 3. Benzophenone derivative of general formula (3) A - (C - B) n wherein A represents a residue derived from a sugar or a sugar alcohol wherein one or more hydroxyl groups have been removed, residues derived from glycerol being excluded, B is a benzophenone group of general formula (4) wherein each of R 1 to R 9 independently represents hydrogen, a hydroxyl group, an alkyl group, an unsaturated alkyl group, a cycloalkyl group, an alkoxy group, an unsaturated alkoxy group, a cycloalkoxy group, or a binder C, with the proviso that one of R 1 to R 9 is represented by said binder C, and wherein C represents a glyceryl group, and n is an integer of 1 to 3. Benzophenone derivative according to claim 6, characterized in that at least one of R 1 to R 9 is an alkyl group having 1 to 4 carbon atoms. Benzophenone derivative according to claim 6, characterized in that at least one of R 1 to R 9 is an alkoxy group having 1 to 4 carbon atoms. Ultraviolet absorbent, characterized in that it comprises at least one of the benzophenone derivatives according to claims 6 to 8. External preparation for the skin, characterized in that it comprises at least one of the benzophenone derivatives according to claims 6 to 8.

Inventors: KATOH MIKIKO, TAKATA SADAKI, UEHARA KEIICHI, KATOH, MIKIKO, TAKATA, SADAKI, UEHARA, KEIICHI
Applicants: SHISEIDO CO LTD, SHISEIDO COMPANY LIMITED
Application year: 1992
Main classification: C07H15
IPC codes: C07C45, A61Q17, C07C49, A61K8, C07H15