Patent Application
20100221199
The present invention relates to a sunscreen cosmetic. More specifically, it relates to a sunscreen cosmetic that prevents staining due to secondary adhesion to clothing.
Important ultraviolet wavelength regions absorbed by sunscreen cosmetics are the UV-A region (320-400 nm) and UV-B region (290-320 nm). It was believed that the ultraviolet light in the UV-A region darkened the skin but it would not cause sunburn and accelerate aging of the skin as the ultraviolet light in the UV-B region would.
However, in recent years, it has been made clear that, whereas the ultraviolet light in the UV-B region only reaches the surface part of the skin, the ultraviolet light in the UV-A region reaches the deeper part of the skin and induces not only skin aging but also skin cancer. Therefore, there is an increasing demand for sunscreen cosmetics to have ultraviolet absorption in the UV-A region.
There are many kinds of ultraviolet absorbents that are added to sunscreen cosmetics. 4-(1,1-dimethylethyl)-4′-methoxydibenzoylmethane is used as an ultraviolet absorbent in the UV-A region. Hexyl diethylaminohydroxybenzoylbenzoate is also used.
An endermic liniment that has superior ultraviolet absorption in the UV-A region as well and prevents the coloring tendency of 2-ethylhexyl p-methoxycinnamate thus improving stability of the ultraviolet absorption effect has been developed by adding a benzotriazole derivative represented by the general formula (I) to an endermic liniment containing 2-ethylhexyl p-methoxycinnamate as an ultraviolet absorbent in the UV-B region (Patent document 1).
Patent Citation 1: Japanese Patent Laid-Open 2005-206473 bulletin
4-(1,1-dimethylethyl)-4′-methoxydibenzoylmethane is a useful ultraviolet absorbent in the UV-A region, but there is a problem in that the addition of this to a sunscreen cosmetic tends to result in staining clothing from secondary adhesion. Therefore, 4-(1,1-dimethylethyl)-4′-methoxydibenzoylmethane cannot be added to a sunscreen cosmetic at a high blend ratio.
In view of the aforementioned problem, the inventors conducted earnest research and discovered that a sunscreen cosmetic that reduces the staining tendency of 4-(1,1-dimethylethyl)-4′-methoxydibenzoylmethane on clothing and exhibits exceptional ultraviolet absorption properties in the UV-A region and UV-B region can be provided by adding 4-(1,1-dimethylethyl)-4′-methoxydibenzoylmethane, a benzotriazole derivative of a specific structure, and ethylhexyl 2-cyano-3,3-diphenylacrylate to a sunscreen cosmetic, thus completing the present invention.
The object of the present invention is to provide a sunscreen cosmetic that reduces the staining tendency of 4-(1,1-dimethylethyl)-4′-methoxydibenzoylmethane on clothing and exhibits superior ultraviolet absorption properties in the UV-A region and UV-B region.
Hexyl diethylaminohydroxybenzoylbenzoate is a useful ultraviolet absorbent in the UV-A region, but there is a problem in that the addition of this to a sunscreen cosmetic tends to result in staining clothing from secondary adhesion. Therefore, hexyl diethylaminohydroxybenzoylbenzoate cannot be added to a sunscreen cosmetic at a high blend ratio.
In view of the aforementioned problem, the inventors conducted earnest research and discovered that a sunscreen cosmetic that reduces the staining tendency of hexyl diethylaminohydroxybenzoylbenzoate on clothing can be provided by adding hexyl diethylaminohydroxybenzoylbenzoate and a benzotriazole derivative of a specific structure to a sunscreen cosmetic, thus completing the present invention.
The object of the present invention is to provide a sunscreen cosmetic that reduces the staining tendency of hexyl diethylaminohydroxybenzoylbenzoate on clothing and works well particularly in the UV-A region.
That is, the present invention provides a sunscreen cosmetic comprising 4-(1,1-dimethylethyl)-4′-methoxydibenzoylmethane, a benzotriazole derivative represented by the following general formula (I), and ethylhexyl 2-cyano-3,3-diphenylacrylate.
(In this formula, R′=a straight chain alkyl group of C1-C6 and R″=a straight chain alkyl group of C1-C3.)
Also, the present invention provides the aforementioned sunscreen cosmetic wherein said benzotriazole derivative is one, two or more chosen from a group consisting of 2-[4-(2-ethylhexyloxy)-2-hydroxyphenyl]-2H-benzotriazole and 2-(2-hydroxy-4-isobuthoxyphenyl)-2H-benzotriazole.
That is, the present invention provides a sunscreen cosmetic comprising hexyl diethylaminohydroxybenzoylbenzoate and a benzotriazole derivative represented by the following general formula (I).
(In this formula, R′=a straight chain alkyl group of C1-C6 and R″=a straight chain alkyl group of C1-C3.)
Also, the present invention provides the aforementioned sunscreen cosmetic wherein said benzotriazole derivative is one, two or more chosen from a group consisting of 2-[4-(2-ethylhexyloxy)-2-hydroxyphenyl]-2H-benzotriazole and 2-(2-hydroxy-4-isobuthoxyphenyl)-2H-benzotriazole.
Furthermore, the present invention provides the aforementioned sunscreen cosmetic also comprising ethylhexyl 2-cyano-3,3-diphenylacrylate.
(1) The sunscreen cosmetic of the present invention reduces the staining tendency of 4-(1,1-dimethylethyl)-4′-methoxydibenzoylmethane on clothing. Therefore, it can be added to a sunscreen cosmetic at a high blend ratio.
(2) The sunscreen cosmetic of the present invention exhibits high ultraviolet absorption capacity in a broad region from UV-A to UV-B.
The present invention is described in detail below.
The dibenzoylmethane derivative used in the present invention is 4-(1,1-dimethylethyl)-4′-methoxydibenzoylmethane. In the present invention, a commercial product (Parsol 1789 from DSM Nutritional Products) can be used.
The benzotriazole derivative of general formula (I) is a prior art chemical compound, which is synthesized in the following manner. A common method is to use sodium nitrite and such to turn o-nitroaniline into a diazonium salt and then couple this with phenol to synthesize a monoazo compound, and reduce it to obtain benzotriazole.
(In this formula, 2,3-DCN denotes 2,3-dichloro-1,4-naphthoquinone.)
(In this formula, R=H or CH3, R′=a straight chain alkyl group of C1-C6 and R″=a straight chain alkyl group of C1-C3.)
(In this formula, R′=a straight chain alkyl group of C1-C6 and R″=a straight chain alkyl group of C1-C3. 2,3-DCN denotes 2,3-dichloro-1,4-naphthoquinone.)
Refluxing a corresponding benzotriazole and alkylated halogen in a mixed solvent of methylisobutylketone and dimethylformamide produces the compound of general formula (I) with a particularly high yield.
Specifically, 6-(2H-bonzotriazole-2-yl) resorcinol is put into a four-neck flask equipped with a thermometer and refluxing cooler, to which methylisobutylketone and dimethylformamide are added and the mixture is stirred. To this, sodium carbonate and 2-ethylhexyl bromide are added and the temperature is raised to the refluxing temperature while stirring. After the mixture is stirred while the refluxing temperature is maintained for a prescribed amount of time, methylisobutylketone is recovered under normal pressure; the remaining oil is then rinsed with water to remove excess sodium carbonate and inorganic byproducts to obtain liquid 2-[4-(2-ethylhexyloxy)-2-hydroxyphenyl]-2H-benzotriazole at a high yield.
Ethylhexyl 2-cyano-3,3-diphenylacrylate is a prior art ultraviolet absorbent represented by the following formula. In the present invention, a commercial product (Octocrylene from DSM Nutrition Co., Ltd.) can be used.
The blend ratio of 4-(1,1-dimethylethyl)-4′-methoxydibenzoylmethane is chosen as appropriate for the target product; it is preferably 0.5-5 wt %, more preferably 1-3 wt %, of the total amount of the sunscreen cosmetic. The significance of the present invention is particularly great when the blend ratio is high, i.e. 2 wt % or more.
The blend ratio of the benzotriazole derivative represented by general formula (I) is chosen as appropriate for the target product; it is preferably 0.5-10 wt %, more preferably 1-5 wt %, of the total amount of the sunscreen cosmetic.
The blend ratio of ethylhexyl 2-cyano-3,3-diphenylacrylate is chosen as appropriate for the target product; it is preferably 0.5-10 wt %, more preferably 1-5 wt %, of the total amount of the sunscreen cosmetic.
Hexyl diethylaminohydroxybenzoylbenzoate used in the present invention is an ultraviolet absorbent in the UV-A region represented by the following formula. In the present invention, a commercial product (Uvinul A plus from BASF) can be used.
The benzotriazole represented by general formula (I) is the same as described in [First invention].
Ethylhexyl 2-cyano-3,3-diphenylacrylate is a prior art ultraviolet absorbent in the UV-B region represented by the following formula. By additionally blending in this ultraviolet absorbent, a sunscreen cosmetic that has an exceptional ultraviolet absorption capacity in the UV-A region as well as high ultraviolet absorption capacity in a broad region including the UV-B region can be provided. In the present invention, a commercial product (Octocrylene from DSM Nutrition Co., Ltd.) can be used.
The blend ratio of hexyl diethylaminohydroxybenzoylbenzoate is chosen as appropriate for the target product; it is preferably 0.5-5 wt %, more preferably 1-3 wt %, of the total amount of the sunscreen cosmetic. The significance of the present invention is particularly great when the blend ratio is high, i.e. 2 wt % or more.
The blend ratio of the benzotriazole derivative represented by general formula (I) is chosen as appropriate for the target product; it is preferably 0.5-10 wt %, more preferably 1-5 wt %, of the total amount of the sunscreen cosmetic.
The blend ratio of ethylhexyl 2-cyano-3,3-diphenylacrylate is chosen as appropriate for the target product; it is preferably 0.5-10 wt %, more preferably 1-5 wt %, of the total amount of the sunscreen cosmetic.
In addition to the aforementioned essential ingredients, other ingredients commonly used in cosmetics can be blended in as necessary in the sunscreen cosmetic of the present invention; examples of such ingredients include whitening agents, humectants, antioxidants, oil-based ingredients, other ultraviolet absorbents, surfactants, thickeners, alcohols, powder ingredients, coloring agents, water-based ingredients, water, and various skin nutrients, and the sunscreen cosmetic can be prepared with a conventional method. Specific examples include the following ingredients:
Oil components such as avocado oil, macadamia nut oil, corn oil, olive oil, rapeseed oil, evening primrose oil, castor oil, sunflower oil, tea seed oil, rice bran oil, jojoba oil, cacao oil, coconut oil, squalene, beef tallow, Japanese core wax, beeswax, candelilla wax, carnauba wax, whale wax, lanolin, liquid paraffin, polyoxyethylene (8 mole) oleyl alcohol ether, glyceryl monooleate, cyclomethicone, dimethylpolysiloxane, and diphenylpolysiloxane.
Higher alcohols such as caprylic alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, cholesterol, and phytosterol.
Higher fatty acids such as caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, lanolin fatty acid, linoleic acid, and linolenic acid.
Humectants such as polyethylene glycol, glycerin, sorbitol, xylitol, maltitol, mucopolysaccharide, hyaluronic acid, chondroitin sulfate, and chitosan.
Thickeners such as methyl cellulose, ethyl cellulose, Arabic gum, and polyvinyl alcohol.
Organic solvents such as ethanol and 1,3-butylene glycol.
Antioxidants such as butylhydroxytoluene, tocopherol, and phytic acid.
Antibacterial preservatives such as benzoic acid, salicylic acid, sorbic acid, paraoxybenzoic esters (ethylparaben and butylparaben, for example), and hexachlorophene.
Amino acids such as glycine, alanine, valine, leucine, serine, threonine, phenyalanine, tyrosine, aspartic acid, asparagine, glutamine, taurine, arginine, and histidine, as well as hydrochlorides thereof.
Organic acids such as acyl sarcosinic acid (sodium lauroyl sarcosinate, for example), glutathione, citric acid, malic acid, tartaric acid, and lactic acid.
Vitamins such as vitamin A and its derivatives, vitamin B's including vitamin B6 hydrochloride, vitamin B6 tripalmitate, vitamin B6 dioctanoate, vitamin B2 and its derivatives, vitamin B12, and vitamin B15 and its derivatives, vitamin C's including ascorbic acid, ascorbic malic esters (salts), and ascorbic dipalmitate, vitamin E's including α-tocopherol, β-tocopherol, γ-tocopherol, vitamin E acetate, and vitamin E nicotinate, vitamin D's, vitamin H, pantothenic acid, and pantethine.
Various drugs such as nicotinamide, benzyl nicotinate, γ-oryzanol, allantoin, glycyrrhizic acid (salt), glycyrrhizic acid and its derivatives, hinokitiol, musidine, bisabolol, eucalyptol, thymol, inositol, saponins (saikosaponin, carrot saponin, gourd saponin, soapberry saponin, etc.) pantothenylethyl ether, ethynylestradiol, tranexamic acid, cepharanthine, and placenta extract.
Natural extracts from Rumex japonicus, Sophora flavescens, Nuphar japonica, orange, sage, thyme, yarrow, mallow, smilax, swertia, Ligusticum acutilobum, bitter orange peel, birch, horsetail, gourd, horse chestnut, creeping saxifrage, arnica, lily, mugwort, Paeonia lactiflora, aloe, gardenia, Chamaecyparis pisifera, etc. extracted by using an organic solvent, alcohol, polyhydric alcohol, water, hydroalcohol, etc.
Cation surfactants such as stearyltrimethylammonium chloride, benzalkonium chloride, and lauryl amine oxide.
Sequestering agents such as disodium edetate, trisodium edetate, sodium citrate, sodium polyphosphate, sodium metaphosphate, and gluconic acid.
Perfumes, scrubbing agents, purified water, etc.
Particularly preferable base agents for the sunscreen cosmetic of the present invention are oil components including decamethylcyclopentasiloxane, isononyl isononanoate, dimethylpolysiloxane, heptamethyloctyltrisiloxane, trimethylsiloxysilicic acid, liquid paraffin, squalane, cetyl isooctanoate, triglyceride octanoate, and di-2-ethylhexyl succinate. The present invention is used preferably in sunscreen cosmetics that use decamethylcyclopentasiloxane as the main base agent.
The sunscreen cosmetic of the present invention can be used in any product form such as ointments, cream, emulsion, and lotions. The dosage form is not limited either.
The invention is described in specific detail through Examples. The present invention is not limited to these Examples.
45.4 g (0.20 moles) of 6-(2H-benzotriazole-2-yl) resorcinol, synthesized by using a conventional method, was put into a 500-ml four neck flask equipped with a thermometer and a reflux cooling apparatus, to which 50 ml of methylisobutylketone and 4.0 g of dimethylformamide were added, followed by stirring. Into this, 25.4 g (0.24 moles) of sodium carbonate and 77.2 g (0.40 moles) of 2-ethylhexyl bromide were added and the mixture was heated up to the refluxing temperature while being stirred. After stirring the mixture for 15 hours while maintaining the refluxing temperature, methylisobutylketone was recovered under normal pressure and the remaining oil was then rinsed with water to remove excess sodium carbonate and inorganic byproducts. This oil was distilled under a reduced pressure to obtain 52.1 g of a 220-225° C./0.2-0.3 mmHg fraction, which was yellow and transparent. This compound was liquid at ordinary temperatures; the yield was 76.7% and the HPLC purity was 99.0%.
Instead of 2-ethylhexyl bromide, the equal number of moles of isobutyl bromide was used in the same manner as in Synthesis example 1. Slightly yellow-gray-white powdery crystals were obtained at a yield of 72.5%. The m. p. was 120.0-120.8° C., λmax=345.6 nm, and ε=21750.
W/O sunscreens shown in Table 1-1 were prepared using a conventional method and the staining tendency due to secondary adhesion was investigated.
As shown in
The following are formulation examples of the sunscreen cosmetic of the present invention. Each of these examples is a sunscreen cosmetic that has a reduced staining tendency on clothing and exhibits superior ultraviolet absorption capacity in a broad region from UV-A to UV-B.
Sophora flavescens extract
The water phase was gradually added to the oil phase; after the addition a stirrer was used to homogenize the emulsified particles to complete the preparation.
The water phase, 11-20, was prepared, which was then gradually added to the oil phase, 1-10, followed by stirring by means of a homomixer.
The oil phase, 1-6, was gradually added to the water phase, 11-19, to obtain an O/W preparation. This preparation was gradually added to the oil phase consisting of 7-10, followed by stirring using a homomixer to obtain the target emulsion.
Disodium edetate, dihydroacetone, glycerin, and paraben heated and dissolved in 1,3-butylene glycol were added to the ion-exchanged water of part A. Each ingredient of part B was thoroughly dissolved and heated, and then added to part A, followed by emulsification. This was cooled to obtain the self tanning cream.
45.4 g (0.20 moles) of 6-(2H-benzotriazole-2-yl) resorcinol, synthesized by using a conventional method, was put into a 500-ml four neck flask equipped with a thermometer and a reflux cooling apparatus, to which 50 ml of methylisobutylketone and 4.0 g of dimethylformamide were added, followed by stirring. Into this, 25.4 g (0.24 moles) of sodium carbonate and 77.2 g (0.40 moles) of 2-ethylhexyl bromide were added and the mixture was heated up to the refluxing temperature while being stirred. After stirring the mixture for 15 hours while maintaining the refluxing temperature, methylisobutylketone was recovered under normal pressure and the remaining oil was then rinsed with water to remove excess sodium carbonate and inorganic byproducts. This oil was distilled under a reduced pressure to obtain 52.1 g of a 220-225° C./0.2-0.3 mmHg fraction, which was yellow and transparent. This compound was liquid at ordinary temperatures; the yield was 76.7% and the HPLC purity was 99.0%.
Instead of 2-ethylhexyl bromide, the equal number of moles of isobutyl bromide was used in the same manner as in Synthesis example 1. Slightly yellow-gray-white powdery crystals were obtained at a yield of 72.5%. The m. p. was 120.0-120.8° C., λmax=345.6 nm, and ε=21750.
W/O sunscreens shown in Table 2-1 were prepared using a conventional method and the staining tendency due to secondary adhesion was investigated.
As shown in
The following are formulation examples of the sunscreen cosmetic of the present invention. Each of these examples is a sunscreen cosmetic that has a reduced staining tendency on clothing and exhibits superior ultraviolet absorption capacity.
Sophora flavescens extract
The water phase was gradually added to the oil phase; after the addition a stirrer was used to homogenize the emulsified particles to complete the preparation.
After preparing the water phase, 10-19, it was gradually added to the oil phase, 1-9, followed by stirring by means of a homomixer.
The oil phase, 1-5, was gradually added to the water phase, 10-18, to obtain an O/W preparation. This preparation was gradually added to the oil phase consisting of 6-9, followed by stirring using a homomixer to obtain the target emulsion.
Disodium edetate, dihydroacetone, glycerin, and Paraben heated and dissolved in 1,3-butylene glycol were added to the ion-exchanged water of part A. Each ingredient of part B was thoroughly dissolved and heated, and then added to part A, followed by emulsification. This was cooled to obtain the self tanning cream.
Sophora flavescens extract
The water phase was gradually added to the oil phase; after the addition a stirrer was used to homogenize the emulsified particles to complete the preparation.
The water phase, 11-20, was prepared, which was then gradually added to the oil phase, 1-10, followed by stirring by means of a homomixer.
The oil phase, 1-6, was gradually added to the water phase, 11-19, to obtain an O/W preparation. This preparation was gradually added to the oil phase consisting of 7-10, followed by stirring using a homomixer to obtain the target emulsion.
The present invention can provide a sunscreen cosmetic that reduces the staining tendency of 4-(1,1-dimethylethyl)-4′-methoxydibenzoylmethane on clothing and exhibits superior ultraviolet absorption properties in the UV-A region and UV-B region.
The present invention can provide a sunscreen cosmetic that reduces the staining tendency of ethylhexyl 2-cyano-3,3-diphenylacrylate on clothing and exhibits superior ultraviolet absorption properties in the UV-A region or UV-A-to-B region.
Since the staining tendency on clothing decreases, 4-(1,1-dimethylethyl)-4′-methoxydibenzoylmethane can be added at a high blend ratio and therefore SPF (Sun Protection Factor:UVB protection) and PF (Protection Grade of UVA:UVA protection) can be improved.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2005-380696 | Dec 2005 | JP | national |
| 2005-380697 | Dec 2005 | JP | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/JP2006/325268 | 12/19/2006 | WO | 00 | 5/30/2008 |
