Water-in-oil type emulsified cosmetic

Abstract

To provide a water-in-oil emulsion cosmetic in which an ultraviolet scattering agent is uniformly dispersed in a base agent, excellent ultraviolet protection effect is stably obtained, and whiteness is also suppressed.SOLUTION: A water-in-oil emulsion cosmetic contains the following components (a), (b), (c) and (d): (a) titanium oxide surface-treated with fatty acid and / or alkyl alkoxysilane, (b) an amphiphilic substance that is solid at room temperature, (c) chain silicone oil and (d) volatile hydrocarbon oil.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a water-in-oil type emulsified cosmetic useful as a sunscreen cosmetic.

Background Art

[0002] Sunscreen cosmetics are formulated with ultraviolet absorbers and ultraviolet scattering agents such as titanium oxide and zinc oxide. Among these, in recent years, efforts have been made to reduce the blending amount of ultraviolet absorbers because cosmetics that are gentler on the skin are in demand. On the other hand, in cosmetics formulated with an ultraviolet scattering agent such as titanium oxide, when an amount of the ultraviolet scattering agent sufficient to obtain a sufficient sunscreen effect is blended, there is a problem that the skin becomes white.

[0003] Therefore, cosmetics have been developed that ensure transparency while blending a sufficient amount of an ultraviolet scattering agent such as titanium oxide. For example, a sunscreen cosmetic containing titanium oxide treated with trimethylsiloxysilicate, crosslinked methylpolysiloxane, ester oil, squalane, and water (Patent Document 1); a water-in-oil type emulsified sunscreen cosmetic containing hydrophobized zinc oxide and hydrophobized titanium oxide, a lipophilic nonionic surfactant, an oil component such as N-lauroyl L-glutaminedi(phytosteryl, 2-octyldodecyl), a volatile silicone oil and / or a hydrocarbon oil, and water (Patent Document 2); a water-in-oil type sunscreen cosmetic containing a polyether-modified silicone, titanium oxide, and zinc oxide, a volatile oil agent, an elastomeric organosiloxane, and cetyl dimethicone and not containing an ultraviolet absorber (Patent Document 3); a water-in-oil type emulsified cosmetic containing a volatile oil agent, a silicone surfactant, a hydrophobic powder, a silicone film-forming agent, and a hydrophobic-modified polyether urethane (Patent Document 4) have been reported.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

[0005] However, in the cosmetics described in the above patent documents, special bases such as crosslinked methylpolysiloxane, N-lauroyl L-glutaminedi(phytosteryl, 2-octyldodecyl), elastomer organosiloxane, and hydrophobic modified polyetherurethane are used. The dispersibility of an ultraviolet scattering agent such as titanium oxide in the base is not necessarily good, a stable and high ultraviolet protection effect cannot be obtained, and the whiteness cannot be sufficiently suppressed. Therefore, an object of the present invention is to provide an oil-in-water emulsion cosmetic in which an ultraviolet scattering agent is uniformly dispersed in a base, an excellent ultraviolet protection effect is stably obtained, and whiteness is also suppressed. [Means for Solving the Problems]

[0006] Therefore, as a result of various studies to solve the above problems, the present inventors have found that by containing a specific hydrophobized titanium oxide as an ultraviolet scattering agent and combining it with an amphiphilic substance that is solid at normal temperature, a chain silicone oil, and a volatile hydrocarbon oil and uniformly emulsifying and dispersing them, the hydrophobized titanium oxide is uniformly dispersed in the base, an excellent ultraviolet protection effect is stably obtained, whiteness is also suppressed, and an oil-in-water emulsion cosmetic having good elongation and stability can be obtained.

[0007] That is, the present invention provides an oil-in-water emulsion cosmetic containing the following components (a), (b), (c) and (d). (a) Titanium oxide surface-treated with a fatty acid and / or an alkylalkoxysilane (b) An amphiphilic substance that is solid at normal temperature (c) Chain silicone oil (d) Volatile hydrocarbon oil [Advantages of the Invention]

[0008] According to the present invention, the hydrophobically treated titanium oxide is uniformly dispersed in the base, and an excellent ultraviolet protection effect can be stably obtained, and the whiteness is also suppressed, and an oil-in-water emulsion cosmetic having good elongation and stability can be provided. [Brief Description of the Drawings]

[0009]

Figure 1

Figure 2

Figure 3

[0010] The oil-in-water emulsion cosmetic of the present invention contains the following components (a), (b), (c) and (d). (a) Titanium oxide surface-treated with a fatty acid and / or an alkylalkoxysilane (b) Amphiphilic substance that is solid at normal temperature (c) Chain silicone oil (d) Volatile hydrocarbon oil

[0011] Component (a) is titanium oxide surface-treated with a fatty acid and / or an alkylalkoxysilane. From the viewpoint of obtaining a high ultraviolet ray protection effect and suppressing whiteness, titanium oxide preferably has an average particle diameter of 5 nm or more and 100 nm or less, more preferably 5 nm or more and 50 nm or less, and even more preferably 10 nm or more and 30 nm or less. In the present invention, the average particle diameter is obtained by observing primary particles with a transmission electron microscope and calculating the number average particle diameter by image analysis thereof.

[0012] The titanium oxide used in the present invention is surface-treated with a fatty acid and / or an alkylalkoxysilane. As the fatty acid used for the treatment, from the viewpoint of good dispersibility in component (b) of the surface-treated titanium oxide, a fatty acid having 10 to 22 carbon atoms is preferable, a fatty acid having 12 to 22 carbon atoms is more preferable, and a fatty acid having 12 to 20 carbon atoms is even more preferable. Specifically, it is preferable to use lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, and more preferably stearic acid and / or isostearic acid. Further, as the alkylalkoxysilane used for the treatment, from the viewpoint of good dispersibility in component (b) of the surface-treated titanium oxide, hexyltrimethoxysilane, octyltrimethoxysil rane, octyltriethoxysilane, decyltrimethoxysilane, octadecyltrimethoxysilane are preferably used, and octyltriethoxysilane is more preferably used. In addition, titanium oxide may be treated with aluminum hydroxide in addition to these surface treatment agents. The surface treatment of titanium oxide can be carried out, for example, by mixing and stirring titanium oxide in a fatty acid and / or an alkylalkoxysilane for a certain period of time.

[0013] From the viewpoint of the ultraviolet ray protection effect, the content of component (a) in the water-in-oil type emulsified cosmetic of the present invention is preferably 3% by mass or more, more preferably 5% by mass or more, and from the viewpoint of suppressing whiteness, it is preferably 20% by mass or less, more preferably 15% by mass or less. Specifically, 3% by mass or more and 20% by mass or less is preferable, 5% by mass or more and 20% by mass or less is more preferable, and 5% by mass or more and 15% by mass or less is even more preferable.

[0014] In addition, the water-in-oil emulsion cosmetic of the present invention may contain hydrophobized zinc oxide in addition to titanium oxide surface-treated with a fatty acid and / or an alkylalkoxysilane. From the viewpoints of obtaining a high ultraviolet ray protection effect and suppressing whiteness, the average particle diameter of zinc oxide in the hydrophobized zinc oxide is preferably 5 nm or more and 100 nm or less, more preferably 5 nm or more and 80 nm or less, and further preferably 10 nm or more and 50 nm or less. As the hydrophobizing treatment means for hydrophobized zinc oxide, fatty acid treatment, silane treatment, silicone treatment, etc. are preferable, silane treatment and silicone treatment are more preferable, and alkylalkoxysilane treatment such as octyltrimethoxysilane and octyltriethoxysilane, silicone treatment such as dimethicone and methicone, etc. are further preferable.

[0015] From the viewpoint of the ultraviolet ray protection effect, the content of hydrophobized zinc oxide in the water-in-oil emulsion cosmetic of the present invention is preferably 5% by mass or more, more preferably 8% by mass or more, and further preferably 10% by mass or more. From the viewpoint of suppressing whiteness, it is preferably 30% by mass or less, more preferably 25% by mass or less, and further preferably 23% by mass or less. Specifically, it is preferably 5% by mass or more and 30% by mass or less, more preferably 8% by mass or more and 25% by mass or less, and further preferably 10% by mass or more and 23% by mass or less.

[0016] Component (b) is an amphiphilic substance that is solid at normal temperature. Here, normal temperature refers to the range of 5°C to 35°C. Further, solid means that within this temperature range, it does not show fluidity and maintains a certain shape. Examples of such amphiphilic substances include ceramides, alcohols having 8 to 22 carbon atoms, glycerin esters of fatty acids having 8 to 22 carbon atoms, alkyl glyceryl ethers having 8 to 22 carbon atoms, sorbitan esters of fatty acids having 8 to 22 carbon atoms, polyoxyethylene sorbitan esters of fatty acids having 8 to 22 carbon atoms, etc. In the present invention, one or more selected from these amphiphilic substances can be used.

[0017] As the ceramides, one or more selected from natural ceramides and pseudo-ceramides can be used. From the viewpoints of stably dispersing component (a) and obtaining a high ultraviolet protection effect and a good feeling in use, specifically, the ceramides described in JP-A-2013-53146 are preferable.

[0018] Specific examples of natural ceramides include ceramides Type 1 to 7 in which sphingosine, dihydrosphingosine, phytosphingosine, or sphingadienine is amidated (for example, the ceramides of pigs and humans described in FIG. 2 of J. Lipid Res., 24:759 (1983) and FIG. 4 of J. Lipid. Res., 35:2069 (1994)).

[0019] Furthermore, these N-alkylated forms (for example, N-methyl form) are also included. These ceramides may be used as an optically active form of the natural type (D(-) form), an optically active form of the non-natural type (L(+) form), or a mixture of the natural type and the non-natural type. The relative configuration of the above compounds may be that of the natural configuration, that of other non-natural configurations, or that of a mixture thereof. In particular, compounds of CERAMIDE1, CERAMIDE2, CERAMIDE3, CERAMIDE5, CERAMIDE6II (above, INCI, 8th Edition) and those represented by the following formula are preferable.

[0020]

Chemical formula

[0021] These may be either extracts from nature or synthetic compounds, and commercially available products can be used. Examples of commercially available natural ceramides include Ceramide I, Ceramide III, Ceramide IIIA, Ceramide IIIB, Ceramide IIIC, Ceramide VI (Cosmopharm), Ceramide TIC-001 (Takasago Perfumery Co., Ltd.), CERAMIDE II (Quest International), DS-Ceramide VI, DS-CLA-Phytoceramide, C6-Phytoceramide, DS-ceramide Y3S (Doosan), and CERAMIDE2 (Sederma).

[0022] [Chemical formula]

[0023] As the pseudo-ceramide, from the viewpoints of stably dispersing the component (a) and obtaining a high ultraviolet protection effect and a good feeling in use, a pseudo-ceramide represented by the following general formula (1) is preferable.

[0024] [Chemical formula]

[0025] (In the formula, R 1 represents a linear, branched or cyclic saturated or unsaturated hydrocarbon group having 10 to 22 carbon atoms which may be substituted with a hydroxyl group, or a hydrogen atom; X 1 represents a hydrogen atom, an acetyl group or a glyceryl group; R 2 is a linear, branched or cyclic saturated or unsaturated hydrocarbon group having 5 to 22 carbon atoms which may be substituted with a hydroxyl group or an amino group, or a group in which a linear or branched saturated or unsaturated fatty acid having 8 to 22 carbon atoms which may be substituted with a hydroxyl group is ester-bonded to the ω-terminal of the hydrocarbon group; R 3represents a hydrogen atom or an alkyl group having 1 to 30 carbon atoms which may be substituted with a hydroxyl group, a hydroxyalkoxy group, an alkoxy group or an acetoxy group.)

[0026] Among these, from the viewpoints of stably dispersing component (a) and obtaining a high ultraviolet ray protection effect and a good feeling in use, a pseudo-ceramide represented by the following formula is more preferable.)

[0027]

Chemical formula

[0028] As the general formula (1), R in the following formula 1 is a hexadecyl group, X 1 is a hydrogen atom, R 2 is a pentadecyl group, R 3 is a hydroxyethyl group; R 1 is a hexadecyl group, X 1 is a hydrogen atom, R 2 is a nonyl group, and R3 is a hydroxyethyl group; a pseudo-ceramide of the formula is preferable. R in the general formula (1) 1 is a hexadecyl group, X 1 is a hydrogen atom, R 2 is a pentadecyl group, R 3 is a hydroxyethyl group (N-(hexadecyloxyhydroxypropyl)-N-hydroxyethylhexadecanamide) is even more preferable.)

[0029]

Chemical formula

[0030] In addition, examples of the alcohol having 8 to 22 carbon atoms include myristyl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, oleyl alcohol and the like. Among these, those having a linear alkyl group are preferable, alcohols having 16 to 18 carbon atoms are more preferable, one or more selected from cetyl alcohol and stearyl alcohol are even more preferable, and it is even more preferable to contain cetyl alcohol and stearyl alcohol.

[0031] Examples of the fatty acid glycerin ester having 8 to 22 carbon atoms include glycerin monocaprylate, glycerin monolaurate, glycerin monomyristate, glycerin monopalmitate, glycerin monostearate, glycerin monobehenate, glycerin monooleate, glycerin monoisostearate, glycerin dicaprylate and the like. Among these, one or more selected from glycerin monocaprylate, glycerin monooleate, glycerin monobehenate, glycerin monostearate, and glycerin monopalmitate are preferable, and glycerin monocaprylate, glycerin monooleate, and glycerin monostearate are more preferable.

[0032] Examples of the alkyl glyceryl ether having 8 to 22 carbon atoms include monodecyl glyceryl ether, monolauryl glyceryl ether, monomyristyl glyceryl ether, monocetyl glyceryl ether, monostearyl glyceryl ether, monobehenyl glyceryl ether and the like.

[0033] Examples of the fatty acid sorbitan ester having 8 to 22 carbon atoms include sorbitan monolaurate, sorbitan monomyristate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan monobehenate, sorbitan dioleate and the like. Preferably, sorbitan monooleate, sorbitan dioleate, sorbitan monostearate and the like are included.

[0034] Examples of the fatty acid polyoxyethylene sorbitan esters having 8 to 22 carbon atoms include polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monomyristate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monobehenate, and the like.

[0035] Among these, as component (b), from the viewpoints of stably dispersing component (a) and obtaining a high ultraviolet ray protection effect and a good feeling in use, one or more selected from ceramides, sorbitan fatty acid esters having 8 to 22 carbon atoms, and fatty acid polyoxyethylene sorbitan esters having 8 to 22 carbon atoms are preferable. Further, as component (b), one or more selected from ceramides, sorbitan monofatty acids having 14 to 22 carbon atoms, and polyoxyethylene sorbitan monofatty acids having 14 to 22 carbon atoms are more preferable.

[0036] The content of component (b) in the water-in-oil emulsion cosmetic of the present invention is preferably 0.5% by mass or more, more preferably 0.8% by mass or more, and still more preferably 1% by mass or more, from the viewpoints of stably dispersing component (a) and obtaining a high ultraviolet ray protection effect and a good feeling in use. Further, from the same viewpoints, it is preferably 7.5% by mass or less, more preferably 5% by mass or less, and still more preferably 3% by mass or less. Specifically, the content of component (b) is preferably 0.5% by mass or more and 7.5% by mass or less, more preferably 0.8% by mass or more and 5% by mass or less, and still more preferably 1% by mass or more and 3% by mass or less.

[0037] Component (c) is a chain silicone oil. Chain silicone oil is silicone oil whose main chain is chain-like dimethylpolysiloxane and includes silicone oil containing an alkyl group, a phenyl group, etc. in the side chain. Also, the chain silicone oil may be a liquid chain silicone oil at normal temperature. Specifically, dimethylpolysiloxane, alkyl-modified silicone oil, phenyl-modified silicone oil, etc. may be mentioned. Preferably, the kinematic viscosity at 25°C is 1 mm 2 / s or more and 20 mm 2 / s or less of dimethylpolysiloxane may be mentioned. More preferably, the kinematic viscosity at 25°C is 1 mm 2 / s or more and 10 mm 2 / s or less of dimethylpolysiloxane may be mentioned.

[0038] From the viewpoints of stably dispersing component (a) and obtaining a high ultraviolet ray protection effect, and obtaining a good feeling in use such as the spread of the cosmetic, the content of component (c) in the water-in-oil emulsion cosmetic of the present invention is preferably 10% by mass or more, more preferably 15% by mass or more, and still more preferably 20% by mass or more. Also, from the same viewpoints, it is preferably 50% by mass or less, more preferably 40% by mass or less, and still more preferably 35% by mass or less. Specifically, the content of component (c) is preferably 10% by mass or more and 50% by mass or less, more preferably 15% by mass or more and 40% by mass or less, and still more preferably 20% by mass or more and 35% by mass or less.

[0039] Component (d) is a volatile hydrocarbon oil. Examples of the volatile hydrocarbon oil used in the present invention include hydrocarbon oils having a flash point of 35°C or higher and 100°C or lower. Specifically, one or more selected from hydrogenated polyisobutene and isododecane can be used, and those commercially available as light liquid isoparaffin can usually be used. By using (d) volatile hydrocarbon oil as a volatile oil agent in addition to component (b) and component (c), component (a) can be more stably dispersed in the oily component containing component (b), an excellent ultraviolet ray protection effect can be stably obtained, whitening is also suppressed, and a water-in-oil emulsion cosmetic having good spread and stability can be obtained.

[0040] The content of component (d) in the water-in-oil emulsion cosmetic of the present invention is preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 3% by mass or more from the viewpoints of more stably dispersing component (a) and obtaining a high ultraviolet ray protection effect, and obtaining a good usability such as the spread of the cosmetic. Further, from the same viewpoints, it is preferably 10% by mass or less, more preferably 8% by mass or less, and even more preferably 7% by mass or less. Specifically, the content of component (d) is preferably 1% by mass or more and 10% by mass or less, more preferably 2% by mass or more and 8% by mass or less, and even more preferably 3% by mass or more and 7% by mass or less.

[0041] In the water-in-oil emulsion cosmetic of the present invention, in addition to the above components, oil agents other than the component (c) and (d), surfactants other than the component (b), thickeners, humectants, powders other than the component (a), alcohols, chelating agents, pH adjusters, preservatives, pigments, fragrances, ultraviolet absorbers, water, etc. can be combined and contained.

[0042] The water-in-oil emulsion cosmetic of the present invention can obtain a high ultraviolet ray protection effect even when the content of the ultraviolet absorber is reduced or when the ultraviolet absorber is not contained. The content of the ultraviolet absorber is preferably 0% by mass or more and 20% by mass or less, more preferably 0% by mass or more and 12% by mass or less, and further can be 0% by mass or more and 5% by mass or less, 0% by mass or more and 2.5% by mass or less, 0% by mass or more and 1% by mass or less, 0% by mass or more and 0.5% by mass or less in the water-in-oil emulsion cosmetic of the present invention.

[0043] Examples of the oil agents other than those described above include non-silicone oil agents that are liquid at normal temperature, such as non-volatile hydrocarbon oils such as squalane, liquid isoparaffin, and liquid paraffin, and ester oils such as cetyl 2-ethylhexanoate, isononyl isononanoate, isotridecyl isononanoate, isopropyl myristate, isopropyl palmitate, 2-ethylhexyl palmitate, 2-ethylhexyl stearate, stearyl stearate, alkyl (C12-15) benzoate, glyceryl tri(caprylate / caprate), glyceryl tri(2-ethylhexanoate), neopentyl glycol dicaprate, and neopentyl glycol diethylhexanoate.

[0044] As the surfactant, any surfactant capable of forming a water-in-oil emulsion system may be used, but nonionic surfactants are preferred. Further, lipophilic nonionic surfactants with an HLB of 8 or less are preferred, and examples include polyoxyethylene fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene-methyl polysiloxane copolymers, glycerin fatty acid esters, glycerin alkyl ethers, sorbitan fatty acid esters, polyether-modified silicones, and the like. The content of these surfactants is preferably 0% by mass or more and 5% by mass or less, more preferably 0.1% by mass or more and 4% by mass or less, and even more preferably 0.3% by mass or more and 3% by mass or less in the water-in-oil emulsified cosmetic of the present invention.

[0045] As the thickener, an oil-soluble thickener is preferred. As the oil-soluble thickener, dextrin fatty acid esters are preferred, and examples include esters of dextrin such as lauric acid dextrin, palmitic acid dextrin, myristic acid dextrin, stearic acid dextrin, isostearic acid dextrin, behenic acid dextrin, and coconut oil fatty acid dextrin with fatty acids having 10 to 24 carbon atoms. Among these, palmitic acid dextrin is preferred from the viewpoint of stability. In addition, as the dextrin fatty acid ester, commercially available products such as Rheopearl KL2, Rheopearl TL, and Unifilma HVY (manufactured by Chiba Flour Milling Co., Ltd.) can be used. The thickener can be used alone or in combination of two or more, and the content is preferably 0.01% by mass or more and 2% by mass or less, more preferably 0.05% by mass or more and 1% by mass or less in the water-in-oil emulsified cosmetic of the present invention.

[0046] In addition to water, the aqueous phase of the water-in-oil emulsified cosmetic of the present invention may contain polyhydric alcohols such as glycerin, 1,3-butylene glycol, propylene glycol, dipropylene glycol, and polyethylene glycol, and plant extracts.

[0047] The content of component (e) water in the water-in-oil type emulsified cosmetic of the present invention is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 3% by mass or more from the viewpoints of elongation and stability, and preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less from the same viewpoints. Specifically, 1% by mass or more and 20% by mass or less is preferable, 2% by mass or more and 15% by mass or less is more preferable, and 3% by mass or more and 10% by mass or less is still more preferable.

[0048] In addition, the content mass ratio [(a) / (e)] of component (a) to component (e) is preferably 0.5 or more, more preferably 1 or more, still more preferably 2 or more, and preferably 10 or less, more preferably 6 or less, still more preferably 5 or less from the viewpoints of stably dispersing component (a), stably obtaining the ultraviolet ray protection effect, suppressing whiteness, and being excellent in elongation and stability. As a specific range, 0.5 or more and 10 or less is preferable, 1 or more and 6 or less is more preferable, and 2 or more and 5 or less is still more preferable.

[0049] In addition, the content mass ratio [(b) / (e)] of component (b) to component (e) is preferably 0.03 or more, more preferably 0.06 or more, still more preferably 0.1 or more, and preferably 6 or less, more preferably 2 or less, still more preferably 1 or less from the viewpoints of stably dispersing component (a), stably obtaining the ultraviolet ray protection effect, suppressing whiteness, and being excellent in elongation and stability. As a specific range, 0.03 or more and 6 or less is preferable, 0.06 or more and 2 or less is more preferable, and 0.1 or more and 1 or less is still more preferable.

[0050] The form of the cosmetic of the present invention is a water-in-oil type emulsified cosmetic, and it can be produced according to a usual method. For example, it can be produced by dispersing a powder component in an oil phase component, adding a previously mixed water phase component thereto, and mixing and stirring. More preferably, from the viewpoint of stably dispersing component (a) and obtaining a high ultraviolet ray protection effect, component (a) is dispersed in a state where a non-volatile oil agent containing component (b) is heated and dissolved, further mixed with other oil agents containing component (c) and component (d), and then cooled and mixed with the water phase component to be emulsified into a water-in-oil type.

[0051] Therefore, the present invention provides a water-in-oil emulsion cosmetic obtained by heating and dissolving an oil phase containing component (a) and component (b), mixing component (c) and component (d), cooling the mixture, and then mixing an aqueous phase component. (a) Titanium oxide surface-treated with a fatty acid and / or an alkylalkoxysilane (b) Amphiphilic substance that is solid at normal temperature (c) Linear silicone oil (d) Volatile hydrocarbon oil

[0052] The dosage forms of the water-in-oil emulsion cosmetic of the present invention include emulsion form, cream form, gel form, and the like.

[0053] In the water-in-oil emulsion cosmetic of the present invention, titanium oxide surface-treated with a fatty acid and / or an alkylalkoxysilane is uniformly emulsified and dispersed in the base, and an excellent ultraviolet ray protection effect can be stably obtained, and whiteness is also suppressed, and elongation and stability are good. Therefore, the water-in-oil emulsion cosmetic of the present invention is particularly useful as a sunscreen cosmetic.

[0054] Regarding the above-described embodiments, the present invention further discloses the following compositions and methods.

[0055] <1>A water-in-oil emulsion cosmetic containing the following components (a), (b), (c) and (d). (a) Titanium oxide surface-treated with a fatty acid and / or an alkylalkoxysilane (b) Amphiphilic substance that is solid at normal temperature (c) Linear silicone oil (d) Volatile hydrocarbon oil

[0056] (2) The water-in-oil emulsion cosmetic according to <1>, wherein the content of component (a) is 3% by mass or more and 20% by mass or less, preferably 5% by mass or more and 20% by mass or less, more preferably 5% by mass or more and 15% by mass. The water-in-oil type emulsified cosmetic according to <1> or <2>, wherein the average particle diameter of titanium oxide in component (a) is 5 nm or more and 100 nm or less, preferably 5 nm or more and 50 nm or less, more preferably 10 nm or more and 30 nm or less. The water-in-oil type emulsified cosmetic according to any one of <1> to <3>, further containing hydrophobized zinc oxide. The water-in-oil type emulsified cosmetic according to <4>, wherein the content of hydrophobized zinc oxide is 5% by mass or more and 30% by mass or less, preferably 8% by mass or more and 25% by mass or less, more preferably 10% by mass or more and 23% by mass or less. The water-in-oil type emulsified cosmetic according to any one of <1> to <5>, wherein component (b) is at least one selected from ceramides, alcohols having 8 to 22 carbon atoms, glycerin esters of fatty acids having 8 to 22 carbon atoms, alkyl glyceryl ethers having 8 to 22 carbon atoms, sorbitan esters of fatty acids having 8 to 22 carbon atoms, and polyoxyethylene sorbitan esters of fatty acids having 8 to 22 carbon atoms. The water-in-oil type emulsified cosmetic according to any one of <1> to <6>, wherein the content of component (b) is 0.5% by mass or more and 7.5% by mass or less, preferably 0.8% by mass or more and 5% by mass or less, more preferably 1% by mass or more and 3% by mass or less. The water-in-oil type emulsified cosmetic according to any one of <1> to <7>, wherein component (c) is a chain silicone oil that is liquid at normal temperature. The water-in-oil type emulsified cosmetic according to any one of <1> to <8>, wherein the content of component (c) is 10% by mass or more and 50% by mass or less, preferably 15% by mass or more and 40% by mass or less, more preferably 20% by mass or more and 35% by mass or less. The water-in-oil type emulsified cosmetic according to any one of <1> to <9>, wherein component (d) is at least one selected from hydrogenated polyisobutene and isododecane. The water-in-oil type emulsified cosmetic according to any one of <1> to <10>, wherein the content of component (d) is 1% by mass or more and 10% by mass or less, preferably 2% by mass or more and 8% by mass or less, more preferably 3% by mass or more and 7% by mass or less. The water-in-oil type emulsified cosmetic according to any one of <1> to <11>, further containing an ultraviolet absorber. <13>The content of the ultraviolet absorber is 0% by mass or more and 20% by mass or less, preferably 0% by mass or more and 12% by mass or less, more preferably 0% by mass or more and 5% by mass or less, still more preferably 0% by mass or more and 2.5% by mass or less, still more preferably 0% by mass or more and 1% by mass or less, still more preferably 0% by mass or more and 0.5% by mass or less, and is the water-in-oil type emulsified cosmetic according to <12>. <14>Furthermore, the water-in-oil type emulsified cosmetic according to any one of <1> to <13>, which contains one or more selected from non-silicone oils that are liquid at normal temperature, non-volatile hydrocarbon oils, and ester oils. <15>Furthermore, the water-in-oil type emulsified cosmetic according to any one of <1> to <14>, which contains a nonionic surfactant. <16>Furthermore, the water-in-oil type emulsified cosmetic according to any one of <1> to <15>, which contains a thickener. <17>Furthermore, the water-in-oil type emulsified cosmetic according to any one of <1> to <16>, which contains component (e) water. <18>The content of component (e) water is 1% by mass or more and 20% by mass or less, preferably 2% by mass or more and 15% by mass or less, more preferably 3% by mass or more and 10% by mass or less, and is the water-in-oil type emulsified cosmetic according to <17>. <19>The content mass ratio [(a) / (e)] of component (a) to component (e) is 0.5 or more and 10 or less, preferably 1 or more and 6 or less, more preferably 2 or more and 5 or less, and is the water-in-oil type emulsified cosmetic according to <17> or <18>. <20>The content mass ratio [(b) / (e)] of component (b) to component (e) is 0.03 or more and 6 or less, preferably 0.06 or more and 2 or less, more preferably 0.1 or more and 1 or less, and is the water-in-oil type emulsified cosmetic according to any one of <17> to <19>. <21>The water-in-oil type emulsified sunscreen cosmetic according to any one of <1> to <20> is the water-in-oil type emulsified cosmetic. <22>The water-in-oil type emulsified cosmetic obtained by heating and dissolving the oil phase containing component (a) and component (b), then mixing component (c) and component (d), and then cooling and mixing the aqueous phase components. (a) Titanium oxide surface-treated with a fatty acid and / or an alkylalkoxysilane (b) Amphiphilic substance that is solid at normal temperature (c) Chain silicone oil (d) Volatile hydrocarbon oil <23> A method for producing an oil-in-water type emulsified cosmetic, comprising heating and dissolving an oil phase containing component (a) and component (b), mixing component (c) and component (d), then cooling, and mixing an aqueous phase component. (a) Titanium oxide surface-treated with a fatty acid and / or an alkylalkoxysilane (b) Amphiphilic substance that is solid at room temperature (c) Chain silicone oil (d) Volatile hydrocarbon oil

Examples

[0057] Next, the present invention will be described in more detail with reference to examples. In the following examples, the content of each component is shown as mass% based on the total amount of the composition.

[0058] Emulsions, which are oil-in-water type emulsified cosmetics, were produced according to the preferred methods described above with the formulations shown in Table 1 and Table 2, and the following evaluations were carried out.

[0059] (1) UV protection ability The emulsions obtained in the examples and comparative examples were uniformly coated with 28.5 g on a PAMM plate (5 cm × 5 cm), dried for 15 minutes, the spectra at 9 points on the PAMM plate were measured with an SPF analyzer (UV2000s, manufactured by Labsphere), the average value was calculated, and the determination was made according to the following evaluation criteria. ◎: in vitro SPF 100 or more 〇: in vitro SPF 60 or more and less than 100 △: in vitro SPF 40 or more and less than 60 ×: in vitro SPF less than 40

[0060] (2) Elongation of the cosmetic The viscosities of the emulsions obtained in the examples and comparative examples were measured at room temperature using a B-type viscometer (No. 3 - 6 rpm), and the determination was made according to the following evaluation criteria. ◎: Viscosity less than 5000 mPa·s 〇: Viscosity 5000 mPa·s or more and less than 6000 mPa·s △: Viscosity is 6000 mPa·s or more and less than 8000 mPa·s ×: Viscosity is 8000 mPa·s or more

[0061] (3) Whiteness The emulsions obtained in the examples and comparative examples were dropped at 0.2 mL onto black leather (12 cm × 7 cm), uniformly coated with a 25-μm bar coater, and ΔL was measured with a color difference meter and judged according to the following evaluation criteria. ◎: ΔL is less than 3 〇: ΔL is 3 or more and less than 5 △: ΔL is 5 or more and less than 6 ×: ΔL is 6 or more

[0062]

Table 1

[0063]

Table 2

[0064] *1: N-(Hexadecyloxyhydroxypropyl)-N-hydroxyethylhexadecanamide (Sphingolipid E, manufactured by Kao Corporation) *2: Leodol TW-S120V (manufactured by Kao Corporation) *3: Leodol SP-S10V (manufactured by Kao Corporation) *4: Silicone KF-6015 (manufactured by Shin-Etsu Chemical Co., Ltd.) *5: Leopal KL2 (manufactured by Chiba Flour Milling Co., Ltd.) *6: Nikkol Squalane (Nippon Surfactant Industry Co., Ltd.) *7: Pearl Ream EX (manufactured by NOF Corporation) *8: Pearl Ream 4 (manufactured by NOF Corporation) *9: Clearasil ID CG (manufactured by Cosmetics Innovations and Technologies Sarl) *10: Estol N-01 (manufactured by Nisshin Oillio Group, Ltd.) *11: Silicone KF-96L-2CS (-G) (manufactured by Shin-Etsu Chemical Co., Ltd.) *12: MT-100TV (manufactured by Teika Corporation) *13: STR-100W-OTS (manufactured by Sakai Chemical Industry Co., Ltd.) *14: MT-150EX (manufactured by Teika Corporation) *15: MTY-100SAS (manufactured by Teika Corporation) *16: MZX-300M (manufactured by Teika Corporation) *17: MZX-304R3M (manufactured by Teika Corporation) *18: MZX-304OTS (manufactured by Teika Corporation) *19: 86% Glycerin V (manufactured by Kao Corporation) *20: 1,3-Butylene Glycol-P (manufactured by KH Neochem Co., Ltd.)

[0065] From Tables 1 and 2, the water-in-oil emulsion cosmetics containing components (a), (b), (c), and (d) of the present invention exhibited extremely high UV protection ability, the applied skin did not turn white, and the makeup spread well with good usability. Also, it was confirmed by microscopic observation that component (a) of the present invention was uniformly dispersed in the base.

[0066] 2.5% by mass of pseudo-ceramide (Sphingolipid E, manufactured by Kao Corporation) was dissolved by heating with 14% by mass of liquid isoparaffin (Pearl Ream EX, manufactured by NOF Corporation) and 5% by mass of neopentyl glycol dicaprate (Estemol N-01, manufactured by Nisshin Oillio Group, Ltd.). After adding 12% by mass of stearic acid-treated titanium oxide (MT-100Z, manufactured by Teika Corporation), it was dispersed for 15 minutes with a disper (2500 rpm), and 66.5% by mass of dimethicone (Silicone KF-96L-2CS (-G), manufactured by Shin-Etsu Chemical Co., Ltd.) was added and stirred with a propeller for 10 minutes. The obtained dispersion was observed with a microscope. The results are shown in Figure 1. Also, the microscopic observation results of the dispersion obtained using capric acid triglyceride (Coconutard RK, manufactured by Kao Corporation), an amphiphilic substance that is liquid at room temperature, instead of pseudo-ceramide, are shown in Figure 2. In addition, in the dispersion described above, the microscopic observation results of the dispersion produced in the same manner are shown in Fig. 3, except that pseudo-ceramide (component (b)) is not blended. From the results of Figs. 1 to 3, it was confirmed that if an amphiphilic substance (component (b)) that is solid at normal temperature is blended, the dispersion effect of component (a) is high.

Claims

1. An oil-in-water type emulsified cosmetic containing the following components (a), (b), (c) and (d). (a) Titanium oxide surface-treated with either a fatty acid or an alkylalkoxysilane (b) One or more amphiphilic substances that are solid at normal temperature, selected from ceramides, fatty acid glycerin esters having 8 to 22 carbon atoms, alkyl glyceryl ethers having 8 to 22 carbon atoms, fatty acid sorbitan esters having 8 to 22 carbon atoms, and polyoxyethylene sorbitan fatty acid esters having 8 to 22 carbon atoms (c) Linear silicone oil (d) Volatile hydrocarbon oil

2. The oil-in-water type emulsified cosmetic according to Claim 1, wherein component (b) is one or more selected from ceramides, fatty acid sorbitan esters having 8 to 22 carbon atoms, and polyoxyethylene sorbitan fatty acid esters having 8 to 22 carbon atoms.

3. The oil-in-water type emulsified cosmetic according to Claim 1 or 2, wherein component (c) is a linear silicone oil that is liquid at normal temperature.

4. The oil-in-water type emulsified cosmetic according to any one of Claims 1 to 3, wherein component (d) is one or more selected from hydrogenated polyisobutene and isododecane.

5. The oil-in-water type emulsified cosmetic according to any one of Claims 1 to 4, wherein the content of component (d) is 1% by mass or more and 10% by mass or less.

6. The oil-in-water type emulsified cosmetic according to any one of Claims 1 to 5, which is an oil-in-water type emulsified sunscreen cosmetic.

7. A method for producing an oil-in-water type emulsified cosmetic, comprising heating and dissolving an oil phase containing component (a) and component (b), mixing component (c) and component (d), then cooling, and mixing an aqueous phase component. (a) Titanium oxide surface-treated with either a fatty acid or an alkylalkoxysilane (b) One or more amphiphilic substances that are solid at normal temperature, selected from ceramides, fatty acid glycerin esters having 8 to 22 carbon atoms, alkyl glyceryl ethers having 8 to 22 carbon atoms, fatty acid sorbitan esters having 8 to 22 carbon atoms, and polyoxyethylene sorbitan fatty acid esters having 8 to 22 carbon atoms (c) Linear silicone oil (d) Volatile hydrocarbon oil

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