JP2024092002A - Oil-in-water emulsion composition containing ultraviolet wavelength conversion material - Google Patents

Abstract

The present invention provides a novel oil-in-water emulsion composition suitable for cell activation.
The present invention relates to an oil-in-water emulsion composition comprising an ultraviolet wavelength converting substance and a water-soluble alkyl-substituted polysaccharide derivative.
[Selected figure] Figure 5

Description

The present invention relates to a composition containing an ultraviolet wavelength conversion substance that has a cell activation effect.

UV rays are believed to generate free radicals in the body, which can cause the oxidation of sebum and damage to cellular DNA. The harmful effects of UV rays on the skin include skin cancer, photoaging, age spots, wrinkles, and inflammation, and are undesirable from the standpoint of health and beauty. Although UV rays are used for the purpose of sterilization, considering the balance with the harmful effects of UV rays, the current situation is that the focus is on defense against UV rays rather than actively using them.

Therefore, many measures are taken to protect the skin from UV rays. For example, this includes using sunscreen, staying indoors to avoid exposure to sunlight, using hats and clothing with UV protection, and using UV-blocking film.

For example, in Patent Document 12, Formulation Example 2 describes an oil-in-water type skin cosmetic that contains fluorescent zinc oxide, but does not contain a water-soluble alkyl-substituted polysaccharide derivative, and there is no description of an ultraviolet wavelength conversion substance to achieve a cell activation effect.

Patent No. 6424656 Patent No. 6361416 International Publication No. 2018/004006 JP 2018-131422 A Japanese Patent Application Laid-Open No. 5-117127 Patent No. 4048420 Patent No. 4677250 Patent No. 3303942 JP 2017-88719 A International Publication No. 2018/117117 JP 2015-120682 A JP 2017-122075 A

The objective of the present invention is to provide a novel oil-in-water emulsion composition that utilizes ultraviolet light to activate cells.

The inventors of the present invention have conducted extensive research into how to utilize ultraviolet light effectively on the skin. As a result, they have come up with the idea of an oil-in-water emulsion composition containing an ultraviolet wavelength conversion substance that has excellent cell activation effects.

The present application provides the following inventions.
(1) An oil-in-water emulsion composition comprising (A) an ultraviolet wavelength converting substance and (B) a water-soluble alkyl-substituted polysaccharide derivative.
(2) The oil-in-water emulsion composition according to (1), wherein the water-soluble alkyl-substituted polysaccharide derivative (B) is a C14-22 alkyl-substituted polysaccharide derivative.
(3) The oil-in-water emulsion composition according to (1) or (2), wherein the water-soluble alkyl-substituted polysaccharide derivative (B) is stearoxyhydroxypropylmethylcellulose.
(4) The oil-in-water emulsion composition according to any one of (1) to (3), further comprising (C) an ultraviolet absorbing agent and/or (D) an ultraviolet scattering agent.
(5) The oil-in-water emulsion composition according to any one of (1) to (4), wherein the ultraviolet wavelength conversion substance (A) is an inorganic ultraviolet wavelength conversion substance.
(6) The oil-in-water emulsion composition according to (5), wherein the inorganic ultraviolet wavelength conversion material is a zinc oxide phosphor.
(7) The oil-in-water emulsion composition according to any one of (1) to (4), wherein the ultraviolet wavelength conversion substance (A) is an organic fluorescent substance.
(8) The oil-in-water emulsion composition according to (7), wherein the organic fluorescent substance is phycocyanin.
(9) The oil-in-water emulsion composition according to any one of (1) to (8), wherein a powder is dispersed in an oil phase.
(10) The medium-oil type emulsion composition according to any one of (1) to (9), which is a sunscreen cosmetic.
(11) The medium-oil type emulsion composition according to any one of (1) to (10), which exhibits a fluorescence intensity enhancing effect.
(12) The medium-oil type emulsion composition according to any one of (1) to (11), which exhibits a cell activation effect.

The ultraviolet wavelength conversion substance according to the present invention is suitable for effectively utilizing ultraviolet rays to activate skin cells, and the component composition of the composition of the present invention is suitable for the ultraviolet wavelength conversion substance to convert ultraviolet rays into visible light. In particular, the oil-in-water emulsion composition of the present invention can provide a refreshing feeling when used compared to the oil-in-water type. Conventionally, ultraviolet rays are not good for the skin, so it is common knowledge in the field to take measures to avoid exposing the skin to ultraviolet rays as much as possible. On the other hand, the present invention is based on the knowledge that the ultraviolet wavelength conversion substance exerts a favorable effect on the skin by using ultraviolet rays in the opposite way to activate cells, which is very surprising. Therefore, the composition of the present invention can also lead to an improvement in the quality of life, such as making people who have avoided ultraviolet rays as much as possible for beauty or health reasons feel like going outside more.

FIG. 1 is a schematic diagram of Experiments 1 and 2. Figure 2 shows the cell activity when irradiated with UV using each ultraviolet ray in Experiment 1. The vertical axis shows the relative fluorescence intensity (au). Figure 3 shows the cell activity as relative fluorescence intensity (au) when irradiated with UV of various intensities using C-phycocyanin at various concentrations in experiment 2. FIG. 4 is a schematic diagram of Experiment 3. Fig. 5 shows the relative fluorescence intensity (au) of the cells whose cell activity had been reduced in Experiment 3 when they were irradiated with UV light using C-phycocyanin (P test).

The present invention will be described in detail below with reference to specific embodiments. However, the present invention is not limited to the following embodiments, and can be implemented in any form without departing from the spirit of the present invention.

All patent publications, patent application publications, and non-patent literature cited in this disclosure are hereby incorporated by reference in their entirety into this disclosure for all purposes.

In this disclosure, when applied to a numerical value, "to" refers to a range of values that is equal to or greater than the specified reference value and is equal to or less than the specified reference value.

(A) Ultraviolet Wavelength Conversion Material The composition of the present invention contains an ultraviolet wavelength conversion material as an active ingredient. The ultraviolet wavelength conversion material refers to a material that converts the wavelength of ultraviolet rays contained in incident light and emits outgoing light with a wavelength longer than that of the ultraviolet rays.

The ultraviolet light may include UVA, UVB, UVC, etc. In one embodiment, the ultraviolet light is light having a peak wavelength between 200 nm and 400 nm. The ultraviolet light may also be included in the incident light, e.g., sunlight. Alternatively, the incident light may be ultraviolet light, or artificially generated ultraviolet light may be used.

The emitted light emitted by the ultraviolet wavelength conversion material has a longer wavelength than ultraviolet light, and preferably has a peak wavelength of 500 nm to 700 nm. The emitted light may have one or more peaks, for example, but not limited to, 510 nm, 520 nm, 530 nm, 540 nm, 550 nm, 560 nm, 570 nm, 580 nm, 590 nm, 600 nm, 610 nm, 620 nm, 630 nm, 640 nm, 650 nm, 660 nm, 670 nm, 680 nm, 690 nm, 700 nm, or within any range of these values, or may be red light, orange light, green light, blue light, etc. In one embodiment, the ultraviolet wavelength conversion material exhibits a dominant wavelength of 500 nm to 700 nm when excited with excitation light of 200 nm to 400 nm.

Examples of UV-converting substances include phycobiliproteins such as allophycocyanin, C-phycocyanin (e.g., LinaBlue), R-phycocyanin, phycoerythrocyanin, B-phycoerythrin, b-phycoerythrin, C-phycoerythrin, and R-phycoerythrin; vitamin A, beta-carotene, vitamin K, vitamin B1, vitamin B2, vitamin B6, and vitamin B12. Natural or synthetic ingredients such as folic acid, niacin, lycopene, gardenia, safflower, turmeric, cochineal, perilla, red cabbage, flavonoids, carotenoids, quinoids, porphyrins, anthocyanins, and polyphenols; Red No. 401, Red No. 227, Red No. 504, Red No. 218, Orange No. 205 P, Yellow No. 4, Yellow No. 5, Green No. 201, Pyranine Concentrate, Blue No. 1, 2,4-Diaminophenol Hydrochloride Dyes such as xyethanol, alizurin purple SS, purple 401, black 401, herringbone pink, yellow 401, benzidine yellow G, blue 404, red 104, and meta-aminophenol; phosphors doped with inorganic compounds to give them fluorescence, such as the blue phosphor containing amorphous silica particles, cerium, phosphorus, and/or magnesium described in Japanese Patent No. 6424656 and the red phosphor containing a compound in which a mixed crystal of an alkaline earth metal sulfide and a gallium compound is activated with europium described in Japanese Patent No. 6361416, zinc oxide phosphors described in International Publication No. 2018/004006, zinc oxide phosphors described in Japanese Patent Publication No. 2018-131422, inorganic phosphors described in Japanese Patent Publication No. 5-117127, and the like (hereinafter, phosphors derived from zinc oxide are referred to as "zinc oxide phosphors"; for example, Lumate G). In one embodiment, the inorganic phosphor is one or more phosphors selected from phosphors in which zinc oxide, which can be expressed as ZnO:Zn, Zn1 _+z , ZnO1 _-x, is doped with a sulfur-containing compound, e.g., zinc sulfide, zinc sulfate, or other sulfide salt and/or sulfate salt, as described in WO 2018/004006; magnesium titanate phosphors in which magnesium titanate, e.g. _{, MgTiO3} , _Mg2TiO4 , is doped with _manganese (hereinafter, phosphors derived from magnesium _titanate are referred to as "magnesium titanate phosphors", e.g., LumateR); and calcium phosphate phosphors in which calcium phosphate, e.g., Ca( _H2PO4 ) ₂ , _CaHPO4 , _Ca3 ( _PO4 ) ₂ , is doped with cerium.

The ultraviolet wavelength conversion substance may be obtained by a method such as extraction from natural products such as animals, plants, and algae, or by an artificial method such as chemical synthesis. For example, phycobiliprotein may be prepared by extracting algae such as blue-green algae such as Spirulina platensis and red algae such as Porphyridium purpureum by a method such as that described in Patent No. 4048420, Patent No. 4677250, Patent No. 3303942, etc. Zinc oxide phosphor may be produced by a method such as that described in International Publication No. 2018/004006, JP 2018-131422, and JP 5-117127. Magnesium titanate phosphor may be produced by a method described in JP 2017-88719. Calcium phosphate phosphor may be produced by a method described in International Publication No. 2018/117117.

As long as the wavelength conversion effect of the present invention is not impaired, these ultraviolet wavelength conversion substances may be composed of or contain the components exemplified above, and may be used alone or in combination with multiple types. For example, the above phycobiliproteins or inorganic phosphors may be mixed with other ultraviolet wavelength conversion substances, such as vitamin B (vitamin B1, vitamin B2, vitamin B6, vitamin B12, etc.), to achieve a synergistic effect. However, these components are merely examples, and any substance that provides the wavelength conversion effect of the present invention may be used.

The content of the ultraviolet wavelength conversion substance in the composition of the present invention is not particularly limited as long as it does not impair the wavelength conversion effect of the present invention, and can be appropriately determined depending on the type of ultraviolet wavelength conversion substance and the application of the composition containing the ultraviolet wavelength conversion substance. For example, it can be any content within the range of 0.01 to 99.99% by weight, 0.1% to 99.9% by weight, etc.

In one embodiment of the present invention, the ultraviolet wavelength conversion material in the composition is a zinc oxide phosphor, and the content of the zinc oxide phosphor in the composition of the present invention is preferably 0.1% by weight or more, preferably 1.0% by weight or more, more preferably 1.5% by weight or more, and even more preferably 2% by weight or more, and is preferably 20% by weight or less, preferably 15% by weight or less, more preferably 10% by weight or less, and even more preferably 5% by weight or less, and is 0.01 to 99.99% by weight, 0.1 to 99.9% by weight, 0.1 to 50% by weight, 0.1 to 40% by weight, 0.1 to 30% by weight, 0.1 to 20% by weight, 0.1 to 10% by weight, or 1 to 10% by weight, based on the total composition.

In one embodiment of the present invention, the ultraviolet wavelength conversion material in the composition is a magnesium titanate oxide phosphor (e.g., LumateR), and the content of the magnesium titanate phosphor in the composition of the present invention is preferably 0.1% by weight or more, preferably 1.0% by weight or more, more preferably 1.5% by weight or more, even more preferably 2% by weight or more, and 20% by weight or less, preferably 15% by weight or less, more preferably 10% by weight or less, even more preferably 5% by weight or less, and 0.01 to 99.99% by weight, 0.1 to 99.9% by weight, 0.1 to 50% by weight, 0.1 to 40% by weight, 0.1 to 30% by weight, 0.1 to 20% by weight, 0.1 to 10% by weight, or 1 to 10% by weight, based on the total composition.

In one embodiment of the present invention, the ultraviolet wavelength conversion substance in the composition is phycocyanin, and the preferred content of phycocyanin in the composition of the present invention is 0.00001% by weight or more, preferably 0.0001% by mass or more, and 20% by weight or less, preferably 15% by weight or less, more preferably 10% by weight or less, and even more preferably 5% by weight or less, and is 0.00001 to 99.99% by weight, 0.0001 to 99.9% by weight, 0.0001 to 50% by weight, 0.0001 to 40% by weight, 0.0001 to 30% by weight, 0.0001 to 20% by weight, 0.0001 to 10% by weight, or 0.0001 to 5% by weight.

Cell activation includes, but is not limited to, the promotion of metabolism and turnover of animal cells, including human cells, such as skin fibroblasts and/or keratinocytes, improving function, promoting proliferation, inhibiting oxidation, improving resistance to fatigue and external stimuli, and inhibiting decline in function and activity. Activating skin cells is expected to have effects such as preventing and improving wrinkles, age spots, skin aging, photoaging, etc.

The cell activation effect can be measured, for example, by measuring the viability, reducing capacity, and proliferation of live cells using Alamar Blue as in the Examples, or any other method can be used, such as other dye assays, mitochondrial membrane potential-dependent dye assays, intracellular cytochrome c assays, elastase cleavage dye assays, ATP, ADE assays, glycolytic flux and oxygen consumption assays, etc.

Fluorescence intensity can be measured, for example, as in the examples, by forming a coating of the composition on the surface of a substrate and irradiating it with ultraviolet light, and then measuring the fluorescence intensity using a spectrofluorometer. As the substrate, a resin substrate such as polymethylmethacrylate (PMMA), nylon, or acrylic plate, or an inorganic plate such as glass or quartz can be used, and for example, a PMMA plate with a V-shaped groove on the surface (also called an "S plate": see Patent No. 4453995) can be used. The fluorescence intensity can be measured as the fluorescence value of a specific single wavelength, or as the integrated value of a specific wavelength range.

(B) Water-soluble alkyl-substituted polysaccharide derivative The composition of the present invention contains a water-soluble alkyl-substituted polysaccharide derivative. The term "water-soluble alkyl-substituted polysaccharide derivative" refers to a polysaccharide substituted with an alkyl group that functions as a water-soluble thickener in an oil-in-water composition. The "alkyl group" of the water-soluble alkyl-substituted polysaccharide derivative is not particularly limited as long as the alkyl-substituted polysaccharide derivative is water-soluble, and may have, for example, 1 to 35, 5 to 30, 6 to 26, 10 to 25, or 14 to 22 carbon atoms, and may be directly bonded to the polysaccharide or may be bonded to the polysaccharide as an indirect substituent. The "polysaccharide" of the water-soluble alkyl-substituted polysaccharide derivative is a compound in which multiple monosaccharides are bonded, and examples thereof include sclerotium gum, gum arabic, Alcaligenes-producing polysaccharide, cellulose, guar gum, carrageenan, hyaluronic acid, chondroitin sulfate, tuberose polysaccharide, Tremella fuciformis polysaccharide, locust bean gum, dextrin, chitosan, inulin, and starch. The polysaccharide may also be modified to attach alkyl groups, such as methyl cellulose, ethyl cellulose, propyl cellulose, butyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, carboxymethyl cellulose, carboxyethyl cellulose, and hydroxypropyl starch phosphate, which may have one or more hydroxyl groups. The number of saccharides constituting the polysaccharide is not particularly limited as long as the alkyl-substituted polysaccharide derivative is water-soluble, and may be, for example, 100 to 100,000, 100 to 10,000, or 1,000 to 4,000.

A preferred embodiment of the water-soluble alkyl-substituted polysaccharide derivative contained in the composition of the present invention is alkylcellulose hydrophobically modified with an alkyl group having 14 to 22 carbon atoms (hereinafter referred to as "hydrophobically modified alkylcellulose"), which is disclosed in Patent Document 11 (JP Patent Publication 2015-120682 A). This hydrophobically modified alkylcellulose is a compound in which a long-chain alkyl group, which is a hydrophobic group, has been introduced into a water-soluble cellulose ether modification, and is represented by the following general formula (I).
[wherein, R may be the same or different and is one or more groups selected from a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a -[CH2CH(CH3)O]m-H group (wherein m is an integer of 1 to 5, preferably 1 to 3), a -CH2CH2OH group, and a -CH2CH(OH)CH2OR' group (wherein R' is an alkyl group having 14 to 22 carbon atoms), but the -CH2CH(OH)CH2OR' group is always included. In addition, A is a -(CH2)q- group (wherein q is an integer of 1 to 3, preferably 1), and n is an integer of 100 to 10,000, preferably 500 to 5,000.]
The hydrophobically modified alkylcellulose can be produced by the method described in Patent Document 11.

A preferred embodiment of the water-soluble alkyl-substituted polysaccharide derivative contained in the composition of the present invention is stearoxyhydroxypropylmethylcellulose. For example, there is Sangelose (registered trademark) manufactured by Daido Kasei Kogyo Co., Ltd., and a hydrophobically modified alkylcellulose (Sangelose (registered trademark) 60 series) having a weight average molecular weight (Mw) of about 300,000 to 500,000, a hydrophobically modified alkylcellulose (Sangelose (registered trademark) 90 series) having a weight average molecular weight (Mw) of about 700,000 to 900,000, or a mixture of these can be used. A preferred embodiment of the water-soluble alkyl-substituted polysaccharide derivative contained in the composition of the present invention is Sangelose (registered trademark) 60L or Sangelose (registered trademark) 90L, and a more preferred embodiment is Sangelose (registered trademark) 90L.

(C) Ultraviolet absorber Since an ultraviolet absorber absorbs incident ultraviolet light, it is thought that the ultraviolet absorber indirectly inhibits the function of the ultraviolet wavelength conversion material. However, surprisingly, the composition of the present invention can contain an ultraviolet absorber and can exhibit the function of the ultraviolet wavelength conversion material.

The composition of the present invention contains an ultraviolet absorber. The ultraviolet absorber refers to a substance that absorbs ultraviolet rays, converts them into energy such as heat or infrared rays, and then releases the energy. The ultraviolet absorber that can be used in the present invention is not particularly limited as long as it does not directly impair the function of the ultraviolet wavelength conversion substance, and examples of such ultraviolet absorbers include salicylic acid-based ultraviolet absorbers such as homomenthyl salicylate, ethylhexyl salicylate (octyl salicylate), homosalate, and triethanolamine salicylate;
cinnamic acid-based ultraviolet absorbers such as 2-ethylhexyl paramethoxycinnamate, glyceryl di-paramethoxycinnamate mono-2-ethylhexanoate, methyl 2,5-diisopropylcinnamate, 2,4,6-tris[4-(2-ethylhexyloxycarbonyl)anilino]-1,3,5-triazine (hereinafter also referred to as "ethylhexyl triazone"), methyl bis(trimethylsiloxy)silylisopentyl trimethoxycinnamate, a mixture of isopropyl paramethoxycinnamate and diisopropyl cinnamate, and diethanolamine p-methoxyhydrocinnamate;
Benzoylmethane-based ultraviolet absorbers such as 2-phenyl-benzimidazole-5-sulfuric acid, 4-isopropyldibenzoylmethane, and 4-tert-butyl-4'-methoxydibenzoylmethane;
Examples of the benzotriazolidine dibenzoate include octocrylene, 2-ethylhexyl dimethoxybenzylidene dioxoimidazolidinepropionate, 1-(3,4-dimethoxyphenyl)-4,4-dimethyl-1,3-pentanedione, cinoxate, methyl-O-aminobenzoate, 3-(4-methylbenzylidene)camphor, octyl triazone, diethylamino hydroxybenzoyl hexyl benzoate, bisethylhexyloxyphenol methoxyphenyl triazine and methylene bisbenzotriazolyl tetramethylbutylphenol. One or more selected from these may be contained in the composition.

The content of the (each) ultraviolet absorber in the composition of the present invention is 30% by weight or less, preferably 20% by weight or less, more preferably 15% by weight or less, and even more preferably 5% by weight or less, based on the total composition, in order not to absorb too much ultraviolet light contained in incident light.

(D) Ultraviolet Scattering Agent Since ultraviolet scattering agents scatter incident ultraviolet light, they are thought to indirectly inhibit the function of the ultraviolet wavelength conversion material. However, surprisingly, the composition of the present invention can contain an ultraviolet scattering agent and can exhibit the function of the ultraviolet wavelength conversion material.

The composition of the present invention may contain an ultraviolet scattering agent. The ultraviolet scattering agent refers to a substance that can reflect and scatter ultraviolet rays to protect the skin, etc. from ultraviolet rays. Examples of ultraviolet scattering agent materials that can be used in the present invention include titanium oxide, zinc oxide other than component (A), iron oxide, zirconium oxide, aluminum oxide, etc. Furthermore, examples of ultraviolet scattering agents include those in which these materials are made into fine particles or composites. The ultraviolet scattering agent preferably contains one or more types selected from titanium oxide and zinc oxide other than component (A).

The titanium oxide and zinc oxide used as the UV scattering agent may be the titanium oxide and zinc oxide that are commonly used in cosmetics. Preferably, the titanium oxide and zinc oxide have better dispersibility, for example, the surface of which has been treated, specifically hydrophobized, by a known method as necessary, may be contained in the composition.

Surface treatment methods include silicone treatment with methylhydrogenpolysiloxane, methylpolysiloxane, etc.; fluorine treatment with perfluoroalkyl phosphate ester, perfluoroalcohol, etc.; amino acid treatment with N-acylglutamic acid, etc.; alkylalkoxysilane treatment with octyltriethoxysilane, octyltrimethoxysilane, etc.; lecithin treatment; metal soap treatment; fatty acid treatment; alkyl phosphate ester treatment, etc. Among these, zinc oxide with a silicone-treated surface is preferably used.

The silicone used for the surface treatment is not limited, but examples include various silicone oils such as methylpolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, methylcyclopolysiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, octamethyltrisiloxane, tetradecamethylhexasiloxane, dimethylsiloxane-methyl(polyoxyethylene)siloxane-methyl(polyoxypropylene)siloxane copolymer, dimethylsiloxane-methyl(polyoxyethylene)siloxane copolymer, dimethylsiloxane-methyl(polyoxypropylene)siloxane copolymer, dimethylsiloxane-methylcetyloxysiloxane copolymer, and dimethylsiloxane-methylstearoxysiloxane copolymer. Methylhydrogenpolysiloxane and methylpolysiloxane are preferred.

The content of the (each) ultraviolet scattering agent in the composition of the present invention is 20% by weight or less, preferably 15% by weight or less, more preferably 10% by weight or less, and even more preferably 5% by weight or less, based on the total composition, in order not to scatter the ultraviolet rays contained in the incident light too much.

Dispersant The composition of the present invention may contain a dispersant. A dispersant refers to a substance that can be adsorbed to the surface of particles dispersed in an aqueous or oily phase, thereby dispersing the particles uniformly in an aqueous or oily medium. The dispersant that can be used in the present invention is not particularly limited as long as it does not impair the function of the ultraviolet wavelength conversion material, and is preferably an oil-based dispersant. Examples of the oil-based dispersant include nonionic surfactants, cationic surfactants, anionic surfactants, silicone-based surfactants, fatty acids, etc. In the present invention, it is particularly preferable to use nonionic surfactants, silicone-based surfactants, and/or fatty acids that are commonly used in cosmetics and pharmaceuticals.

Preferred dispersants included in the compositions of the present invention include PEG-10 dimethicone, bis-butyl dimethicone polyglyceryl-3, PEG-polydimethylpolysiloxane ethyl dimethicone, lauryl PEG-polydimethylpolysiloxane ethyl dimethicone, cetyl PEG/PPG-10/dimethicone, isostearic acid, polyglyceryl-2 diisostearate, carboxydecyl trisiloxane, PEG-12 dimethicone, or polyoxyethylene sorbitan monostearate, or a combination of two or more of these.

Preferred examples of dispersants contained in the composition of the present invention, which enhance the function of the ultraviolet wavelength conversion substance, include PEG-10 dimethicone, bisbutyldimethicone polyglyceryl-3, PEG-9 polydimethylpolysiloxyethyl dimethicone, lauryl PEG-9 polydimethylpolysiloxyethyl dimethicone, cetyl PEG/PPG-10/1 dimethicone, isostearic acid, carboxydecyltrisiloxane, or a combination of two or more of these.

The content of the dispersant in the composition of the present invention is not particularly limited as long as it does not impair the wavelength conversion effect of the present invention, and can be appropriately determined depending on the type of ultraviolet wavelength conversion substance and the application of the composition containing the ultraviolet wavelength conversion substance. For example, it can be any content within the range of 0.01 to 10% by weight, 0.1% to 99.9% by weight, etc.

The preferred content of the dispersant in the composition of the present invention is 0.1% by weight or more, preferably 0.3% by weight or more, more preferably 0.5% by weight or more, and 20% by weight or less, preferably 10% by weight or less, more preferably 5% by weight or less, and even more preferably 2% by weight or less, and is 0.01 to 99.99% by weight, 0.1 to 99.9% by weight, 0.1 to 20% by weight, 0.1 to 10% by weight, 0.1 to 5% by weight, 0.1 to 3% by weight, 0.1 to 2% by weight, 0.1 to 1% by weight, 0.5 to 10% by weight, 0.5 to 5% by weight, or 0.5 to 2% by weight, based on the total composition.

In one embodiment of the present invention, the dispersant in the composition is bisbutyldimethicone polyglyceryl-3 (such as KF-6109 manufactured by Shin-Etsu Chemical Co., Ltd.), and the content of the dispersant in the composition is 0.1% by weight or more, preferably 0.3% by weight or more, more preferably 0.5% by weight or more, and 20% by weight or less, preferably 10% by weight or less, more preferably 5% by weight or less, and even more preferably 2% by weight or less, and is 0.01 to 99.99% by weight, 0.1 to 99.9% by weight, 0.1 to 20% by weight, 0.1 to 10% by weight, 0.1 to 5% by weight, 0.1 to 3% by weight, 0.1 to 2% by weight, 0.1 to 1% by weight, 0.5 to 10% by weight, 0.5 to 5% by weight, or 0.5 to 2% by weight.

(E) Oil The composition of the present invention contains an oil. The oil refers to a hydrophobic substance that is a component of the composition of the present invention and undergoes phase separation from water. The oil that can be used in the present invention is not particularly limited, and includes, for example, at least one of hydrocarbon oil, ester oil, silicone oil, liquid oil, solid oil, and higher alcohol.

Examples of hydrocarbon oils include liquid paraffin, tetraisobutane, hydrogenated polydecene, olefin oligomer, isododecane, isohexadecane, squalane, hydrogenated polyisobutene, etc.

Ester oils include diisopropyl sebacate, octyl palmitate, cetyl isooctanoate (cetyl 2-ethylhexanoate), triethylhexanoin, neopentyl glycol dicaprate, triisostearin, diisostearyl malate, PPG-3 dipivalate, di-2-ethylhexyl succinate, 2-ethylhexyl 2-ethylhexanoate, polyglyceryl-6 octacaprylate, and tri(caprylic/capric acid)glyceryl.

Examples of silicone oils include caprylyl methicone, dimethicone, amino-modified polysiloxane, polyether-modified polysiloxane, alkyl-modified polysiloxane, and fluorine-modified polysiloxane.

Liquid oils include avocado oil, camellia oil, macadamia nut oil, mink oil, olive oil, castor oil, jojoba oil, triglycerin, glycerin trioctanoate, isostearic acid, etc.

Examples of solid fats and oils include coconut oil, hardened coconut oil, palm oil, beef tallow, mutton tallow, Japan wax, and hardened castor oil.

Examples of higher alcohols include isostearyl alcohol, oleyl alcohol, and copolymers of butylene glycol and propylene glycol (e.g., PBG/PPG-9/1 copolymer).

The total oil content of the composition of the present invention is 5% by weight or more, preferably 10% by weight or more, and more preferably 15% by weight or more, based on the total composition.

Aqueous phase thickener The composition of the present invention may contain an aqueous phase thickener in addition to the water-soluble alkyl-substituted polysaccharide derivative. The aqueous phase thickener is an additive that can increase the viscosity of the aqueous phase liquid by dissolving in water (aqueous phase). Examples of aqueous phase thickeners include cellulose-based thickeners such as (dimethylacrylamide/sodium acryloyldimethyltaurate) crosspolymer, succinoglycan, acrylic thickeners, cellulose gum, hydroxyethyl cellulose, hydroxypropyl methylcellulose, stearoxy hydroxypropyl methylcellulose, hydroxypropyl guar hydroxypropyltrimonium chloride, and cationic cellulose obtained by adding a cationic functional group to cellulose, vinyl-based thickeners such as polyvinyl alcohol, and clay minerals such as bentonite, and one or more selected from these may be included in the composition.

Oil phase thickener The composition of the present invention may contain an oil phase thickener. The oil phase thickener is an additive that can increase the viscosity of the liquid in the oil phase by dissolving it in the oil phase of the composition. Examples of the oil phase thickener include sugar fatty acid esters, solid oils, metal soaps, inorganic polymers such as 12-hydroxystearic acid, bentonite, and hectorite. Examples of the sugar fatty acid esters include esters of fatty acids having 10 to 22 carbon atoms and dextrin, sucrose, inulin, and the like, and specific examples thereof include dextrin palmitate, dextrin myristate, dextrin (palmitate/ethylhexanoate), dextrin stearate, dextrin behenate, dextrin laurate, coconut oil fatty acid dextrin, sucrose palmitate, sucrose stearate, and inulin stearate. Among these, dextrin palmitate, dextrin myristate, dextrin (palmitate/ethylhexanoate), and inulin stearate are particularly preferred in terms of usability, stability, etc. One or more selected from these may be contained in the composition.

(Other ingredients)
The composition of the present invention can be appropriately blended with various components within the range that does not affect the effects of the present invention. Examples of various components include additives that can be normally blended into cosmetics, such as powders (polymethylmethacrylate, crosslinked silicone/network silicone block copolymers, silica, hydrophobized talc, corn starch, hydrophobized polyurethane, etc.), chelating agents, fragrances, moisturizing agents (glycerin, dipropylene glycol, etc.), preservatives, anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, moisturizing agents, water-soluble polymers, film-forming agents such as silicone-modified polysaccharides, sequestering agents, lower alcohols, polyhydric alcohols, various extracts, sugars, amino acids, organic amines, polymer emulsions, pH adjusters, skin nutrients, vitamins, water-soluble drugs applicable to medicines, quasi-drugs, cosmetics, etc., antioxidants, buffers, antioxidant assistants, propellants, organic powders, pigments, dyes, colorants, water, acid components, alkali components, etc. These optional components can be appropriately blended into the oil phase and the water phase. Furthermore, in order to enhance the effects of the present invention, other cell activating agents may be contained or used in combination.

The composition of the present invention is an oil-in-water emulsion composition. The oil-in-water emulsion composition of the present invention can be produced according to a conventional production method.
Specifically, the composition of this embodiment can be obtained by the following procedure: Component (B) is mixed with water, etc. to prepare an aqueous phase, and (A) the ultraviolet wavelength conversion substance is mixed in if the aqueous phase is to be dispersed in the aqueous phase. An oily component such as oil is mixed in to prepare an oil phase, and (A) the ultraviolet wavelength conversion substance is mixed in if the aqueous phase is to be dispersed in the oil phase. The oil phase and other components are added to the aqueous phase and stirred to obtain a composition.

One embodiment of the composition of the present invention is an oil-in-water emulsion composition containing a powder. Examples of powders include silica, polymethyl methacrylate, crosslinked silicone/network silicone block copolymers, talc, corn starch, polyurethane, etc., and the oil-in-water emulsion composition containing the powder of the present invention can be produced according to a conventional production method.

The composition of the present invention includes sunscreen cosmetics such as sunscreen cream. The formulation may be, for example, a milky lotion or cream. The oil-in-water emulsion composition of the present invention provides a refreshing feel when used compared to the oil-in-water type, and has a unique, refreshing feel when applied to the skin, melting and crumbling.

The composition of the present invention can be used by applying, preferably coating, the skin, particularly the skin excluding hair, preferably the face, body, hands, feet, etc. For example, applying, preferably coating, the composition of the present embodiment to the skin not only protects against ultraviolet rays and suppresses adverse effects on the skin, but also activates skin cells to give the skin a natural and desirable appearance.

The present invention will now be described in more detail with reference to examples. Note that the present invention is not limited to these examples.

Experiment 1: Cell activation effects of various ultraviolet wavelength conversion substances Experiment 1-1: Preparation of ultraviolet wavelength conversion substance Ultraviolet wavelength conversion substances were prepared as follows.
(1) B-phycoerythrin
B-phycoerythrin was obtained from an extract of Porphiridium Cruentum, and its absorption spectrum had a peak wavelength at 305 nm, and its emission spectrum had peak wavelengths at 570 nm and 610 nm.
(2) C-phycocyanin
C-phycocyanin was obtained from an extract of Spirulina platensis, and its absorption spectrum had a peak wavelength at 350 nm, and its emission spectrum had peak wavelengths at 640 nm and 700 nm. Linablue manufactured by DIC was used.
(3) Zinc oxide phosphor Lumate G manufactured by Sakai Chemical Industry Co., Ltd. was used. Lumate G is a zinc oxide phosphor in which ZnO is doped with a sulfur-containing compound as described in International Publication No. 2018/004006, and its absorption spectrum had a peak wavelength at 365 nm and its emission spectrum had a peak wavelength at 510 nm.
(4) Magnesium titanate phosphor Lumate R manufactured by Sakai Chemical Industry Co., Ltd. was used. Lumate R is a magnesium titanate phosphor in which _MgTiO3 is doped with manganese, and its absorption spectrum has a peak wavelength at 365 nm, and its emission spectrum has a peak wavelength in the 660 to 680 nm band.
The ultraviolet wavelength conversion substances (1) and (2) were dissolved in water to prepare solutions with concentrations of 1% and 5%.
The ultraviolet wavelength conversion substances (3) and (4) were dispersed in alcohol to prepare 5% and 10% dispersions.

Experiment 1-2: Preparation of cell samples Cell samples were prepared as follows.
1. Human skin fibroblasts and human skin keratinocytes purchased from Kurabo Co., Ltd. Cell suspension (1 mL) stored in liquid nitrogen was thawed in a water bath (37°C) until a small ice pellet remained, and then diluted with 9 mL of warm medium.
2. The dilutions were mixed gently and then transferred to T75 flasks and incubated overnight at 37°C.
3. The next day, the medium was replaced with 10 mL of fresh medium.
4. The medium was changed periodically (once every 2 days for fibroblasts and once every 2-3 days for keratinocytes) to allow the cells to continue growing. During this time, the cells were observed under a microscope to confirm that they were growing with the correct morphology.
5. When the cells reached approximately 80% confluence, they were passaged by washing the cells once with 10 mL of warm PBS, adding 5 mL of warm trypsin to a T75 flask, covering the bottom of the flask with the trypsin solution, leaving it at room temperature for 1 minute, and then aspirating.
6. The flasks were placed in a 37°C oven for 2 minutes (max) for fibroblasts and 7 minutes (max) for keratinocytes. The cells were observed under a microscope to confirm that they were small and oval in shape.
7. The cells were then loosened by gently tapping the side of the T75 flask and observed under a microscope to confirm that the cells were moving freely.
8. Fibroblasts were resuspended in 5mL of warm FGM (containing 10% serum) and transferred to a sterile 50mL Falcon tube. The flask was rinsed with an additional 5mL of warm FGM and added to the Falcon tube to ensure all cells were transferred.
9. The cells were centrifuged at 10,000 rpm for 5 minutes (4°C) and the supernatant was removed, being careful not to disturb the cell pellet.
10. Depending on the type of cells, fibroblasts were resuspended in FGM or KGM at a concentration of 2 x 10 ⁴ cells/well (500 μL) and keratinocytes were resuspended at a concentration of 4 x 10 ⁴ cells/well (500 μL) and plated in a 24-well plate.
11. Seed the cells in 24-well plates and grow them with regular medium changes (every 2 days for fibroblasts, every 2-3 days for keratinocytes) until they reach 60-70% confluency (depending on the type of experiment). (Note: fibroblasts should reach the desired confluency in 24 hours at a cell density of ^2x104 cells/well. If the cell density is lower, e.g., ^1x104 cells/well, it will take 48 hours for fibroblasts to reach the desired confluency.)
12. 24 hours before irradiation, the medium was changed to supplement-free (for keratinocytes) or to medium containing low concentrations of serum (0.5% FCS) (for fibroblasts).

Experiment 1-3: UV irradiation
1. The solar simulator was turned on to warm up the lamp at least 30 minutes before irradiation. The solar simulator was set to use the UG11 filter. The UG11 filter is a filter that passes only UVB and blocks other wavelengths of light. The UV light that passed through the UG11 filter had a peak wavelength of 300nm to 385nm.
2. The temperature control plate was turned on and set to 33°C.
3. The cells prepared in Experiment 1-2 were washed once with warm PBS.
4. 0.5 mL of warmed Martinez solution (145 mM NaCl, 5.5 mM KCl, 1.2 _mM MgCl2.6H2O, _1.2 mM NaH2PO4.2H2O _, 7.5 _mM HEPES, 1 mM _CaCl2 , 10 mM D _- glucose) was added to each well.
5. As shown in Figure 1, the cell wells were placed on a plate, and 0.4 ml of the solution containing the ultraviolet wavelength conversion substances (1) to (4) prepared in Experiment 1-1 was poured into each well of the 24-well plate, and the wells containing the cells were then placed so as to cover them. This was done so that the solution of the ultraviolet wavelength conversion substance did not come into direct contact with the cell solution, and UV light was irradiated onto the cell solution through the solution of the ultraviolet wavelength conversion substance.
6. The total dose was 100 mJ/ ^cm2 . As controls, a sample was prepared in which the cells were directly irradiated with UV light without placing a plate of UV wavelength conversion material on the cell well, and a sample was prepared in which the cells were cultured in the dark without being irradiated with UV light.
7. After irradiation, the Martinez was replaced with warmed KGM (no supplements) or FGM (containing 0.5% FCS) and the plates were returned to the 37°C incubator.

Experiment 1-4: Measurement of cell activity After Experiment 1-3, cells were kept in an incubator for 48 hours and their activity was measured by the following method.
1. 10% Alamar Blue was added to the culture medium (KGM medium without supplements or FGM medium containing 0.5% FCS) and warmed to 37°C (the solution was kept in the dark).
2. The medium in the wells was replaced with 500 μL of the above 10% Alamar Blue solution, and the plate was returned to the 37°C incubator for approximately 3 hours. The control wells were also kept in the incubator. These solutions were kept in the dark to protect them from light.
3. After 3 hours, a 100 μL aliquot was removed and transferred to a black 96-well plate.
4. Fluorescence measurements were taken at 544 nm/590 nm using a fluorometer (OPwave+, Ocean Photonics).

The results are shown in Figure 2. Cell activity was reduced when exposed to UV light compared to the non-irradiated control. However, the activity of cells exposed to UV light through a UV wavelength conversion substance was increased for all UV wavelength conversion substances compared to the non-irradiated control. These results show that although UV irradiation reduces cell activity, the use of a UV wavelength conversion substance can suppress the reduction in cell activity.

Example 2: Effects of different concentrations of ultraviolet wavelength conversion substance and UV intensity on cell activity The same method as in Experiment 1 was used, except that the cell culture was covered with a plate containing a solution containing 0%, 0.4%, or 2% C-phycocyanin as an ultraviolet wavelength conversion substance, and UV was irradiated at doses of 0, 10, 25, 50, 75, and 100 mJ/ ^cm2 .

The results are shown in Figure 3. When no ultraviolet wavelength conversion substance was used, the higher the UV irradiation dose, the lower the cell activity. However, when 0.4% C-phycocyanin was added, the lowering of cell activity was suppressed even with UV irradiation, and when 2% C-phycocyanin was added, cell activity was actually enhanced compared to when no UV irradiation was used. These results show that, although UV irradiation reduces cell activity, the use of an ultraviolet wavelength conversion substance not only suppresses the lowering of cell activity in a concentration-dependent manner, but also enhances cell activity.

Example 3: Restoration of cell activity reduced by UV irradiation As shown in Fig. 4, the same method as in Experiment 1 was used except that, after UV irradiation was performed without using an ultraviolet wavelength conversion substance until the irradiation dose reached 400 mJ/ ^cm2 to reduce cell activity, the cell culture was covered with a plate containing a solution containing 0%, 0.4%, and 2% C-phycocyanin as an ultraviolet wavelength conversion substance, and UV irradiation was performed until the dose reached 0, 10, 25, 50, 75, 100, and 200 mJ/ ^cm2 .

The results are shown in Figure 5. It can be seen that even in cells whose activity had once decreased due to UV irradiation without the use of an ultraviolet wavelength conversion substance, cellular activity was restored by UV irradiation using an ultraviolet wavelength conversion substance. Furthermore, this effect was the same even at a concentration of 0.4% C-phycocyanin as at 2%, suggesting that even at 0.4%, sufficient cell activation is achieved. On the other hand, when UV irradiation was performed without the use of an ultraviolet wavelength conversion substance, cellular activity decreased in a UV dose-dependent manner.

The above results were shown for human skin fibroblasts, but similar results were also seen for keratinocytes (data not shown). These results demonstrate that UV wavelength conversion substances not only suppress the decline in cell activity caused by UV exposure, but also have the effect of activating cells using UV light. Activating skin cells is expected to help prevent and improve wrinkles, age spots, skin aging, photoaging, and more.

From the above Examples 1 to 3, it was believed that the ultraviolet wavelength conversion substance converts the wavelength of ultraviolet light, and the emitted visible light (fluorescence with a dominant wavelength of 500 nm to 700 nm) activates skin cells such as fibroblasts and keratinocytes. Therefore, various compositions containing the ultraviolet wavelength conversion substance were produced as described below, and the amount of fluorescence emitted when irradiated with ultraviolet light was evaluated.

The amount of fluorescence was measured by applying the composition to an S plate (see Japanese Patent No. 4453995) at 2 mg/ ^cm2 and drying the composition to prepare a coating film. The resulting coating film was irradiated with 365 nm ultraviolet light, and the integrated fluorescence value in the wavelength range of 400-600 nm was measured using a spectrofluorophotometer RF-5300PC (Shimadzu Corporation).

Example 4: Oil-in-water emulsion composition Oil-in-water emulsion compositions (Formulation Examples 1 to 4) having the compositions shown in Table 1 were produced according to a conventional manufacturing method. Formulation Example 1 (Comparative Example) did not contain stearoxyhydroxypropylmethylcellulose, while Formulation Examples 2 to 4 contained 0.04, 0.1, and 0.2% by weight of stearoxyhydroxypropylmethylcellulose, respectively, based on the total composition. All formulation examples contained zinc oxide phosphor (Lumate G), which is an ultraviolet wavelength conversion material. In addition, the oil-in-water emulsion composition provided a refreshing feel when used. The obtained compositions were irradiated with 365 nm ultraviolet light, and the fluorescence integrated value at wavelengths of 400 to 600 nm was measured. The fluorescence integrated value for the comparative example was 3268, while the fluorescence integrated values for formulation examples 2, 3, and 4 were 3783, 4149, and 3627, respectively. This indicates that the addition of stearoxyhydroxypropyl methylcellulose enhanced the wavelength conversion function of the zinc oxide phosphor at all concentrations, with the concentration of 0.1 wt% stearoxyhydroxypropyl methylcellulose being the peak for enhanced wavelength conversion function.

The above describes the embodiments of the composition of the present invention. However, the present invention is not limited to these, and can be modified as appropriate without departing from the spirit of the invention.

Claims (12)

An oil-in-water emulsion composition comprising (A) an ultraviolet wavelength conversion substance and (B) a water-soluble alkyl-substituted polysaccharide derivative. The oil-in-water emulsion composition according to claim 1, wherein the water-soluble alkyl-substituted polysaccharide derivative (B) is a C14-22 alkyl-substituted polysaccharide derivative. The oil-in-water emulsion composition according to claim 1 or 2, wherein the water-soluble alkyl-substituted polysaccharide derivative (B) is stearoxyhydroxypropylmethylcellulose. The oil-in-water emulsion composition according to any one of claims 1 to 3, further comprising (C) an ultraviolet absorbing agent and/or (D) an ultraviolet scattering agent. The oil-in-water emulsion composition according to any one of claims 1 to 4, wherein the ultraviolet wavelength conversion substance (A) is an inorganic ultraviolet wavelength conversion substance. The oil-in-water emulsion composition according to claim 5, wherein the inorganic ultraviolet wavelength conversion material is a zinc oxide phosphor. The oil-in-water emulsion composition according to any one of claims 1 to 4, wherein the ultraviolet wavelength conversion substance (A) is an organic fluorescent material. The oil-in-water emulsion composition according to claim 7, wherein the organic fluorescent substance is phycocyanin. The oil-in-water emulsion composition according to any one of claims 1 to 8, in which a powder is dispersed in an oil phase. The oil-in-water emulsion composition according to any one of claims 1 to 9, which is a sunscreen cosmetic. The oil-in-water emulsion composition according to any one of claims 1 to 10, which exhibits a fluorescence intensity enhancing effect. The oil-in-water emulsion composition according to any one of claims 1 to 11, which exhibits a cell activation effect.

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