Water-in-oil emulsion cosmetic

Abstract

Provided is a water-in-oil emulsion cosmetic that uses N-acylamino acid-treated microparticulate zinc oxide, hydrophobized microparticulate titanium oxide, polyhydroxystearic acid, an ester oil that is liquid at 25°C, and a nonionic surfactant having an HLB of 2-9, wherein the water-in-oil emulsion cosmetic has high UV protection ability, excellent usability, such as excellent squeak-free spreadability and cleansability, and excellent transparency after application, and excellent formulation stability. [Solution] The water-in-oil emulsion cosmetic contains the following components (A)-(E): (A) N-acylamino acid-treated microparticulate zinc oxide, (B) hydrophobized microparticulate titanium oxide, (C) polyhydroxystearic acid, (D) an ester oil that is liquid at 25°C, (E) a nonionic surfactant having an HLB of 2-9; and the total content of component (A) and component (B) is 15-40 mass%.

Description

[Technical Field]

[0001] This invention relates to a water-in-oil emulsion cosmetic. [Background technology]

[0002] In recent years, the demand for functional cosmetics has been increasing, and in foundations and sunscreens, cosmetics with high UV protection capabilities have been developed to protect the skin from UVA (long-wavelength ultraviolet rays with wavelengths of 320-400 nm) and UVB (medium-wavelength ultraviolet rays with wavelengths of 290-320 nm). Organic UV absorbers and metal oxides are used to obtain high UV protection capabilities, but some people do not like organic UV absorbers, and there are concerns about usability such as stickiness and a decrease in formulation stability due to precipitation over time. Therefore, in recent years, formulation development has been progressing to achieve the desired UV protection capabilities by combining metal oxides without incorporating organic UV absorbers. However, in order to obtain sufficient UV protection capabilities, it is necessary to incorporate a large amount of metal oxide, but metal oxides have high cohesiveness, and in particular, fine particles have very high cohesiveness due to their surface area which increases inversely with their particle size, making it difficult to uniformly disperse them in cosmetics. As a result, problems such as a strong squeaky feeling and an unnatural finish due to a white cast after application have occurred. Furthermore, the reduced dispersibility of metal oxides led to problems with formulation stability, such as UV protection and emulsification stability.

[0003] Furthermore, residual sunscreen can cause skin problems such as dryness and rashes, so cleansing ability (ease of washing) is also important. Therefore, there is a demand for sunscreen removers that are gentle on the skin and have excellent cleansing properties.

[0004] To date, attempts have been made to improve the usability and functionality of metal oxides by modifying their shape, particle size, and surface treatment. For example, by treating a hydrated titanium oxide aqueous suspension with alkali, then adding hydrochloric acid, and heating and aging, a material with a length of 0.15-0.25 μm, an axial ratio of 3-9, and a specific surface area of ​​80-120 m² has been obtained. 2A technology has been disclosed that uses rod-shaped titanium dioxide fine particles at a density of / g to achieve transparency and UV protection (for example, Patent Document 1). Furthermore, a technology has been disclosed for organosilicon compound treated pigments in which reactive alkylpolysiloxane is oriented and adsorbed onto the surface of a pigment or extender pigment by heat treatment, resulting in excellent smoothness and adhesion (for example, Patent Document 2). In addition, a technology has been disclosed for sunscreen cosmetics containing hydroxy fatty acid condensates, silicone-branched modified silicones, metal oxides, silicone resin-coated silicone rubber powders, oils, and water, resulting in good spreadability and no white cast upon application (for example, Patent Document 3). [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 9-175821 [Patent Document 2] Japanese Patent Application Publication No. 7-196946 [Patent Document 3] Japanese Patent Publication No. 2015-187090 [Overview of the project] [Problems that the invention aims to solve]

[0006] However, while the technology disclosed in Patent Document 1 offers excellent transparency, there were cases where it was desirable to further improve usability (such as squeaking), formulation stability (emulsification stability), and washability.

[0007] While the technologies disclosed in Patent Documents 2 and 3 offer excellent usability, such as smoothness and spreadability, and transparency, there were cases where it was desirable to further improve UV protection, metal oxide dispersibility, and cleanability.

[0008] Therefore, the present invention aims to provide a water-in-oil emulsion cosmetic that contains metal oxides such as zinc oxide and titanium oxide, has sufficient UV protection ability, and exhibits excellent transparency, formulation stability, and cleansing properties after application to the skin. [Means for solving the problem]

[0009] The inventors of the present invention, through diligent research to solve the above problems, arrived at the present invention by combining N-acyl amino acid-treated zinc oxide and hydrophobically treated titanium dioxide with polyhydroxystearic acid, a nonionic surfactant with HLB 2-9, and an ester that is liquid at 25°C to create a water-in-oil emulsion cosmetic.

[0010] In other words, the present invention provides the following: [1] The following components (A) to (E); (A)N-acylamino acid treated zinc oxide microparticles (B) Hydrophobically treated titanium oxide fine particles (C) Polyhydroxystearic acid (D) Ester oil that is liquid at 25°C (E) Nonionic surfactants with HLB 2-9 This is a water-in-oil emulsion cosmetic containing the above-mentioned (A) and (B), wherein the total content of the above-mentioned (A) and (B) is 15 to 40% by mass. [2] The water-in-oil emulsion cosmetic composition according to [1], wherein the mass ratio of component (A) and component (B) (A) / (B) is 1.5 to 6. [3] The water-in-oil emulsion cosmetic composition according to [1] or [2] above, wherein component (B) is triethoxyoctylsilane-treated fine-particle titanium dioxide and / or fatty acid-treated fine-particle titanium dioxide. [4] The water-in-oil emulsion cosmetic according to any one of [1] to [3] above, wherein component (A) is lauroyl lysine-treated fine particle zinc oxide and / or lauroyl glutamic acid-treated fine particle zinc oxide. [5] The oil-in-water emulsion cosmetic composition described in any one of the above [1] to [4], wherein the transmittance of light with a wavelength of 500 nm is 60% or more. [6] The water-in-oil emulsion cosmetic according to any one of [1] to [7], wherein the mass ratio [(A) + (B)] / (C) of the components (A) to (C) is 10 to 50. [7] The water-in-oil emulsion cosmetic according to any one of [1] to [6], wherein the component (E) is at least one selected from the group consisting of silicone surfactants and polyethylene glycol fatty acid esters. [8] The water-in-oil emulsion cosmetic according to any one of [1] to [6], wherein the component (E) contains a silicone surfactant and a polyethylene glycol fatty acid ester, and the mass ratio of the polyethylene glycol fatty acid ester to the silicone surfactant (polyethylene glycol fatty acid ester / silicone surfactant) is 0.7 or less. [9] The water-in-oil emulsion cosmetic according to [7] or [8], wherein the polyethylene glycol fatty acid ester component is PEG-30 dipolyhydroxystearate.

[10] The water-in-oil emulsion cosmetic according to any one of [1] to [9], which does not contain an organic ultraviolet absorber.

[0011] In addition, this technology can further adopt the following configurations.

[11] Furthermore, as component (F), at least one selected from the group consisting of cyclic silicone and silicone having a kinematic viscosity at 25 ° C of 10 mm 2 / s or less is contained in the water-in-oil emulsion cosmetic according to any one of [1] to

[10] .

[12] The water-in-oil emulsion cosmetic according to any one of [1] to

[11] , which further contains a water-soluble polysaccharide as component (G).

Embodiments for Carrying Out the Invention

[0012] Embodiments of the present invention will be described below. However, the present invention is not limited to the embodiments described below. In this specification, "X~Y" indicating a range includes X and Y, and means "X or greater and Y or less".

[0013] When water-in-oil emulsion cosmetics containing metal oxides are applied to the skin, the metal oxides aggregate, causing a white cast. However, by selecting (A) fine-particle zinc oxide surface-treated with N-acyl amino acids and (B) hydrophobically treated fine-particle titanium dioxide as metal oxides, and combining them with (C) polyhydroxystearic acid, (D) ester oil that is liquid at 25°C, and (E) nonionic surfactants with HLB 2-9, the dispersibility of the metal oxides is improved, resulting in good usability such as transparency when applied to the skin, smooth spreadability without stickiness, and cleansing properties. Furthermore, in water-in-oil emulsion cosmetics, there is a concern that the dispersibility of metal oxides may decrease due to changes in formulation stability such as the emulsification state, so ensuring formulation stability is important. In the present invention, by selecting (E) and combining it with other components (A) to (D), a water-in-oil emulsion cosmetic with excellent formulation stability over time is obtained.

[0014] The water-in-oil emulsion cosmetic of the present invention exhibits high UV protection and excellent transparency after application to the skin. Furthermore, the water-in-oil emulsion cosmetic of the present invention has excellent formulation stability, and also boasts excellent usability, including smooth spreadability and cleansing properties.

[0015] (Ingredient (A): N-acylamino acid-treated zinc oxide microparticles) The zinc oxide microparticles in component (A) N-acyl amino acid treated zinc oxide microparticles used in the present invention are powders that block ultraviolet rays by absorbing, scattering, reflecting, or quenching them, and their shape is not particularly limited. The average particle size of the zinc oxide microparticles before N-acyl amino acid treatment is preferably 1 to 200 nm, more preferably 3 to 100 nm, and even more preferably 5 to 35 nm, from the viewpoint of ultraviolet protection ability, formulation stability, and transparency. In the present invention, the average particle size is measured as the volume-average particle size (D50) using a laser scattering particle size distribution analyzer LA-960-V2 (manufactured by HORIBA Corporation).

[0016] The shape of the zinc oxide microparticles is not particularly limited, as long as it is a shape commonly used in cosmetics, quasi-drugs, pharmaceuticals, etc. Examples include granular, spherical, spindle-shaped, dendritic, balloon-shaped, etc., and in the present invention, granular, spherical, or spindle-shaped particles are preferred from the viewpoint of ultraviolet protection ability, formulation stability, transparency, etc. Examples of commercially available zinc oxide microparticles include FINEX-25, FINEX-50, FINEX-75 (manufactured by Sakai Chemical Co., Ltd.), MZ500 series, MZ700 series (manufactured by Teika Co., Ltd.), ZnO-350 (manufactured by Sumitomo Osaka Cement Co., Ltd.), etc.

[0017] The component (A) fine-particle zinc oxide used in the present invention is surface-treated (coated) with an N-acyl amino acid. In order to obtain a cosmetic composition with sufficient UV protection and excellent formulation stability, it is preferable to contain a large amount of zinc oxide, but there are concerns about deterioration of the texture due to a squeaky feeling. However, by surface-treating (coating) with an N-acyl amino acid, it is possible to achieve a smooth spread without squeaking. Examples of amino acids for N-acyl amino acid treatment include alanine, glycine, sarcosine, lysine, aspartic acid, glutamic acid, etc., and the amino acids for N-acyl amino acid treatment include salts of these. Furthermore, the fatty acid constituting the acyl group in the acyl amino acid treatment is preferably a fatty acid with 8 to 23 carbon atoms, and more preferably a fatty acid with 12 to 20 carbon atoms. In particular, in the present invention, it is even more preferable that the amino acid moiety is selected from aspartic acid, glutamic acid, and lysine, and the fatty acid moiety constituting the acyl group is an acyl amino acid selected from lauric acid and stearic acid. In particular, component (A) is preferably selected from stearoyl glutamic acid, lauroyl aspartic acid, dilauroyl glutamic acid lysine, lauroyl glutamic acid, and lauroyl lysine. From the viewpoint of smooth spreadability, formulation stability, and washability, lauroyl lysine and / or lauroyl glutamic acid are more preferred, and from the viewpoint of formulation stability and washability, lauroyl lysine is particularly preferred. A preferred embodiment of the present invention is that component (A) is lauroyl lysine-treated fine particle zinc oxide and / or lauroyl glutamic acid-treated fine particle zinc oxide. Examples of amino acid salts include Na, K, Ca, Al, Mg, and Zn salts of amino acids. One or more of these surface treatments can be appropriately selected and used.

[0018] The surface treatment method for component (A) is not particularly limited and can be manufactured by commonly known methods. For example, by adding an N-acyl amino acid treatment agent and the fine-particle zinc oxide to be treated to a solvent, stirring with a ball mill or the like, drying as necessary, washing with water, filtering repeatedly to remove impurities, drying, and grinding, the desired N-acyl amino acid treated fine-particle zinc oxide can be obtained. Furthermore, several types of surface treatment compounds can be used to surface treat simultaneously, or the surface can be pre-treated with one compound before applying other compounds.

[0019] The amount (mass) of the N-acyl amino acid treatment agent in component (A) is not particularly limited, but from the viewpoint of smooth spreadability and formulation stability, it is preferably 40% or less (hereinafter, "mass%" will be simply abbreviated as "%"; unless otherwise specified, the content is in mass%) relative to the mass of the powder before treatment, more preferably 35% or less, and even more preferably 30% or less. Furthermore, the amount (mass) of the N-acyl amino acid treatment agent is preferably 1% or more, more preferably 3% or more, and even more preferably 5% or more, relative to the mass of the powder before treatment. In particular, when the N-acyl amino acid treatment agent is lauroyl lysine, the amount (mass) of the N-acyl amino acid treatment agent is preferably 40% or less, more preferably 35% or less, and even more preferably 30% or less, relative to the mass of the powder before treatment. Furthermore, as a lower limit, it is preferably 5% or more, more preferably 10% or more, and even more preferably 15% or more, relative to the mass of the powder before treatment. This range is preferable because it allows for smoother spreadability and better formulation stability.

[0020] In the present invention, the content of component (A) is not particularly limited, but from the viewpoint of UV protection ability, it is preferably 5% or more, more preferably 10% or more, and even more preferably 20% or more in the water-in-oil emulsion cosmetic. Furthermore, from the viewpoint of usability such as smooth spreadability and transparency, it is preferably 35% or less, more preferably 30% or less, and even more preferably less than 28% from the viewpoint of transparency.

[0021] (Component (B): Hydrophobized titanium dioxide fine particles) The component (B) hydrophobically treated titanium dioxide fine particles used in the present invention refers to a powder that blocks ultraviolet light by absorbing, scattering, reflecting, or quenching it, and its shape is not particularly limited. The average particle size of the titanium dioxide fine particles before hydrophobization is not particularly limited, but from the viewpoint of ultraviolet protection ability, formulation stability and transparency, it is preferably 1 to 200 nm, more preferably 3 to 100 nm, more preferably 5 to 30 nm, even more preferably 5 to 15 nm, and particularly preferably 5 to 10 nm. From the viewpoint of transparency, it is particularly preferably 5 nm or more and less than 10 nm. The average particle size is measured as the volume-average particle size (D50) using a laser scattering particle size analyzer LA-960-V2 (manufactured by HORIBA).

[0022] The shape of the fine-particle titanium dioxide is not particularly limited, but examples include granular, spherical, spindle-shaped, dendritic, and balloon-shaped particles. From the viewpoint of UV protection, formulation stability, and transparency, granular, spherical, and spindle-shaped particles are preferred. Commercially available examples of these fine-particle titanium dioxide include TTO-51 (manufactured by Ishihara Sangyo Co., Ltd.), MT-500B (manufactured by Teika Co., Ltd.), and STR-100 (manufactured by Sakai Chemical Industry Co., Ltd.).

[0023] The hydrophobic treatment agent for component (B) is not particularly limited as long as it is commonly used in cosmetics, quasi-drugs, pharmaceuticals, etc., but examples include silicone treatment agents, fluorine treatment agents, organic titanate treatment agents, fatty acid treatment agents, lecithin treatment agents, and N-acyl amino acid treatment agents. These hydrophobic treatment agents may be used individually or in combination of two or more. Among these, from the viewpoint of UV protection ability, formulation stability, and smooth spreading, it is preferable to use one or more selected from silicone treatment agents, organic titanate treatment agents, and fatty acid treatment agents, more preferably one or more selected from silicone treatment agents and fatty acid treatment agents, and even more preferably a fatty acid treatment from the viewpoint of cleanability.

[0024] Examples of silicone treatment agents include chain-like silicones such as low-molecular-weight dimethylpolysiloxane, high-molecular-weight dimethylpolysiloxane, methylphenylpolysiloxane, and methylhydrogenpolysiloxane; modified silicones such as amino-modified silicones, alkyl-modified silicones, and alkoxy-modified silicones; silicone resins such as trimethylsiloxysilicate and acrylic-silicone graft copolymers; silicone rubbers; partially or fully crosslinked organopolysiloxanes; silylation agents; and silane coupling agents. One or more selected from this group can be used. Among these, the use of silane coupling agents is preferred.

[0025] Among silane coupling agents, trialkoxyalkylsilanes are preferred, although they are not particularly limited. Trialkoxyalkylsilanes are compounds in which three alkoxy groups and one alkyl group are bonded to a silicon atom. These alkoxy groups react with hydroxyl groups and other elements on the powder surface, thereby chemically modifying the powder surface. In the trialkoxyalkylsilane, the alkoxy groups are preferably alkoxy groups having 1 to 3 carbon atoms, such as methoxy, ethoxy, and propoxy. In the trialkoxyalkylsilane, the alkyl group is preferably an alkyl group having 6 to 18 carbon atoms, such as hexyl, octyl, decyl, and octadecyl groups. Examples of such trialkoxyalkylsilanes include trimethoxyhexylsilane, trimethoxyoctylsilane, trimethoxydecylsilane, trimethoxyoctadecylsilane, triethoxyhexylsilane, triethoxyoctylsilane, triethoxydecylsilane, and triethoxyoctadecylsilane. Among these, it is more preferable to select one or more from the group consisting of trimethoxyoctylsilane and triethoxyoctylsilane, from the viewpoint of UV protection ability, formulation stability, and ease of use such as smooth spreadability.

[0026] Examples of fatty acid treatment agents include fatty acids and their metal salts. Among these, from the viewpoint of UV protection ability and formulation stability, fatty acids with 12 to 22 carbon atoms are preferred, those with 16 to 20 carbon atoms are more preferred, those with 16 to 18 carbon atoms are even more preferred, and stearic acid with 18 carbon atoms is particularly preferred. Examples of fatty acid salts include Ca, Mg, Zn, and Al, with Al salts being more preferred.

[0027] The method for hydrophobic treatment in component (B) is not particularly limited and can be manufactured by commonly known methods. For example, the desired hydrophobic powder can be obtained by adding the hydrophobic treatment agent and the powder particles to be treated to a solvent, stirring with a ball mill or the like, drying as necessary, repeatedly washing with water and filtering to remove impurities, and then drying and grinding. Alternatively, several types of surface treatment compounds can be used for surface treatment simultaneously, or the surface can be pre-treated with one compound before applying other compounds.

[0028] As a hydrophobic treatment agent for component (B), from the viewpoint of ultraviolet protection ability, formulation stability, transparency, and washability, it is preferable that it be treated with triethoxyoctylsilane and / or fatty acid (salt), and more preferably one or more selected from triethoxyoctylsilane treatment and stearic acid (salt) treatment. That is, a preferred embodiment of the present invention is that component (B) is triethoxyoctylsilane-treated fine particle titanium dioxide and / or fatty acid-treated fine particle titanium dioxide.

[0029] The amount (mass) of the hydrophobic treatment agent in component (B) is not particularly limited, but from the viewpoint of formulation stability, it is preferably 30% or less, more preferably 25% or less, and even more preferably 20% or less, with a lower limit of 1% or more, more preferably 3% or more, and even more preferably 5% or more.

[0030] In the present invention, the content of component (B) is not particularly limited, but from the viewpoint of usability such as UV protection ability and smooth spreadability, it is preferably 0.5% or more, more preferably 1% or more, and even more preferably 5% or more in the water-in-oil emulsion cosmetic, and from the viewpoint of UV protection ability, it is particularly preferably 7% or more. Furthermore, from the viewpoint of smooth spreadability and transparency, the content of component (B) is preferably 25% or less, more preferably 20% or less, even more preferably 15% or less, and from the viewpoint of transparency, it is particularly preferably less than 12%.

[0031] In the present invention, the total content of components (A) and (B) ((A) + (B)) in the water-in-oil emulsion cosmetic composition is preferably 15% or more and 25% or more, from the viewpoint of usability such as UV protection ability, transparency, and smooth spreadability. Furthermore, the total content (A) + (B) is preferably 40% or less and 35% or less. If the total content (A) + (B) is less than 15%, the UV protection ability may be insufficient, and if the total content (A) + (B) exceeds 40%, the emulsion state becomes unstable, raising concerns about a decrease in formulation stability. In addition, a decrease in formulation stability can lead to a decrease in the dispersibility of fine particle zinc oxide and fine particle titanium dioxide, which may result in poor usability such as UV protection ability, transparency, and a stronger feeling of stiffness and cleanability.

[0032] Furthermore, while the mass ratio of component (A) and component (B) is not particularly limited, from the viewpoint of UV protection, transparency, and smooth spreadability, it is preferable that the mass ratio (A) / (B) in the water-in-oil emulsion cosmetic composition be 0.1 or more, more preferably 1 or more, even more preferably 1.5 or more, and particularly preferable 2 or more, from the viewpoint of excellent UV protection, transparency, and formulation stability. Also, from the viewpoint of UV protection, transparency, and smooth spreadability, it is preferable that the mass ratio (A) / (B) be 10 or less, more preferably 6 or less, and even more preferably 4 or less, from the viewpoint of excellent UV protection, transparency, and cleansing properties. A preferred embodiment of the present invention is one in which the mass ratio (A) / (B) of component (A) and component (B) is 1.5 to 6.

[0033] (Ingredient (C): Polyhydroxystearic acid) The component (C) polyhydroxystearic acid used in the present invention is a polymer of hydroxystearic acid having a hydroxyl group. In the present invention, from the viewpoint of improving the dispersibility of components (A) and (B) and improving formulation stability, the hydroxyl group of hydroxystearic acid is preferably at position 12, and the degree of polymerization of hydroxystearic acid is preferably 3 to 12, and more preferably 4 to 8. A commercially available product of component (C) is Saracos HS-6C (manufactured by Nisshin Oillio Group Co., Ltd.). Component (C) may be used alone or in combination of two or more types.

[0034] The content of component (C) in the present invention is not particularly limited, but from the viewpoint of usability such as UV protection ability and smooth spreadability, it is preferably 0.1% or more, more preferably 0.5% or more in the water-in-oil emulsion cosmetic, and from the viewpoint of cleansing properties, it is even more preferably 0.7% or more. Furthermore, from the viewpoint of smooth spreadability and transparency, it is preferably 5% or less, more preferably 4% or less, and from the viewpoint of cleansing properties, it is even more preferably 3.5% or less, particularly preferably 3% or less, and even more preferably 1.5% or less.

[0035] Furthermore, in the above components (A) to (C), since usability such as transparency and washability is suitably exhibited, it is preferable that the content mass ratio [(A)+(B)] / (C) is 10 or more, and more preferably 20 or more. Also, considering the effects of the present invention, it is preferable that the content mass ratio [(A)+(B)] / (C) is 60 or less, from the viewpoint of transparency and washability, it is preferable that the content mass ratio [(A)+(B)] / (C) is 50 or less, and from the viewpoint of UV protection ability and formulation stability, it is more preferable that it is 40 or less, and even more preferable that it is 35 or less. A preferred embodiment of the present invention is that [(A)+(B)] / (C) is 10 to 50.

[0036] (Component (D): Ester oil that is liquid at 25°C) The component (D) used in this invention, a liquid ester oil at 25°C, is an ester composed of a linear or branched fatty acid and a linear or branched monohydric or polyhydric alcohol. Here, "liquid at 25°C" refers to a viscosity value of 7000 mPa·s or less when measured with a B-type viscometer (rotor No. 2) at 25°C and 1 atmosphere. Component (D) may be used alone or in combination of two or more types.

[0037] In the present invention, component (D) is not particularly limited as long as it is an ester oil that is liquid at 25°C, but it is preferable that its IOB value is 0.1 to 0.5. The IOB value is an index that shows the degree of polarity of an organic compound in terms of the balance between inorganic and organic properties, and is expressed as IOB value = inorganic value / organic value. Compounds with a larger IOB value are more hydrophilic, and compounds with a smaller IOB value are more lipophilic. In the present invention, from the viewpoint of improving the dispersibility of components (A) and (B) in the water-in-oil emulsion cosmetic composition, and improving formulation stability and transparency, etc., it is more preferable that component (D) has an IOB value of 0.1 to 0.4.

[0038] Examples of ester oils with an IOB value of 0.1 to 0.4 include propylene glycol dicaprate (IOB: 0.26, organic value: 460), isotridecyl isononanoate (IOB: 0.16, organic value: 400), cetyl 2-ethylhexanoate (IOB: 0.13, organic value: 470), alkyl (C12-15) benzoate (IOB: 0.19, organic value: 410), and glyceryl tri-2-ethylhexanoate (IOB: 0.35, organic value: 510). Examples include neopentyl glycol dicaprate (IOB: 0.25, organic value: 450), neopentyl glycol diethylhexanoate (IOB: 0.32, organic value: 380), trimethylolpropane triethylhexanoate (IOB: 0.33, organic value: 550), pentaerythrityl tetraoctanoate (IOB: 0.35, organic value: 680), and tri(caprylic / capric acid) glyceryl (IOB: 0.35, organic value: 540). In particular, from the viewpoint of more favorably exhibiting the effects of the present invention, it is more preferable that the IOB value is 0.1 to 0.3, and even more preferable that the ester oil has an organic value of 500 or less (the lower limit is preferably 100 or more, more preferably 200 or more). Specifically, examples include propylene glycol dicaprate (IOB: 0.26, organic value: 460), isotridecyl isononanoate (IOB: 0.16, organic value: 400), cetyl 2-ethylhexanoate (IOB: 0.13, organic value: 470), and alkyl benzoate (C12-15) (IOB: 0.19, organic value: 410).

[0039] The content of component (D) in the present invention is not particularly limited, but from the viewpoint of UV protection ability, formulation stability, and transparency, it is preferably 1% or more, more preferably 5% or more, and even more preferably 10% or more in the water-in-oil emulsion cosmetic. Furthermore, it is preferably 35% or less, more preferably 30% or less, and even more preferably 25% or less. This range is preferable because it provides excellent smooth spreadability and transparency.

[0040] (Ingredient (E): Nonionic surfactant with HLB 2-9) The nonionic surfactants (E)HLB2-9 used in this invention are not particularly limited, as long as they are commonly used in cosmetics, quasi-drugs, pharmaceuticals, etc.

[0041] Here, HLB (Hydphile-Lipophile Balance) in this invention is an index that indicates the balance between hydrophilicity and lipophilicity, and is calculated by the following formula (Equation 1) by Oda, Teramura et al. HLB = "Inorganic value (IV) / Organic value (OV)" × 10 ... (Equation 1) (See Yoshio Koda, "Organic Concept Diagrams - Fundamentals and Applications," pp. 11-17, Sankyo Publishing, 1984).

[0042] Nonionic surfactants with an HLB of 2-9 include silicone-based surfactants, sorbitan fatty acid esters, glycerin fatty acid esters, and polyethylene glycol fatty acid esters. Specifically, nonionic surfactants with an HLB of 2-9 include PEG-9 methyl ether dimethicone, PEG-10 dimethicone, PEG-9 dimethicone, cetyl PEG / PPG-10 / 1 dimethicone, PEG-9 polydimethylsiloxyethyl dimethicone, lauryl PEG-9 polydimethylsiloxyethyl dimethicone, cetyl PEG-9 polydimethylsiloxyethyl dimethicone, lauryl polyglyceryl 3-polydimethylsiloxyethyl dimethicone, polyoxyethylene / butylene / dimethylpolysiloxane copolymer, polyoxyethylene / polyoxypropylene / butylene / dimethylpolysiloxane copolymer, PEG-30 dipolyhydroxystearate, sorbitan (mono)oleate, sorbitan sesquioleate, and sorbitan dioleate. Examples include sorbitan trioleate, sorbitan monoisostearate, sorbitan diisostearate, sorbitan triisostearate, sorbitan monostearate, sorbitan sesquistearate, sorbitan distearate, sorbitan triisostearate, sorbitan (mono)laurate, sorbitan sesquilaurate, sorbitan dilaurate, sorbitan trilaurate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene glycol monoisostearate, polyethylene glycol diisostearate, polyethylene glycol monolaurate, polyethylene glycol dilaurate, polyethylene glycol monooleate, and polyethylene glycol dioleate. These may be used individually or in combination of two or more.

[0043] Furthermore, in the present invention, component (E) is preferably a nonionic surfactant with an HLB of 2 to 6, from the viewpoint of formulation stability, smooth spreadability, and transparency. Even nonionic surfactants with an HLB exceeding 6 can be incorporated if they are combined with those with an HLB of 6 or less so that the overall surfactant has an HLB of 6 or less.

[0044] In the present invention, the total HLB is preferably 2 to 9, and more preferably 2 to 6.

[0045] The total HLB is the arithmetic mean of the HLB values ​​of each nonionic surfactant, based on their respective blending ratios (mass%).

[0046] Total HLB = Σ(HLB) A ×A(%) / 100) HLB A This indicates the HLB value of nonionic surfactant A.

[0047] A(%) is HLB A This shows the blending ratio of nonionic surfactant A having the value shown in the nonionic surfactants.

[0048] In the present invention, from the viewpoint of transparency and other factors, it is particularly preferable that component (E) is at least one selected from the group consisting of silicone-based surfactants and polyethylene glycol fatty acid esters. Specifically, as component (E), at least one selected from the group consisting of PEG-9 polydimethylsiloxyethyl dimethicone, lauryl PEG-9 polydimethylsiloxyethyl dimethicone, PEG-9 dimethicone, PEG-30 dipolyhydroxystearate, and polyethylene glycol stearate is preferred, and at least one selected from the group consisting of PEG-9 dimethicone, lauryl PEG-9 polydimethylsiloxyethyl dimethicone, and PEG-30 dipolyhydroxystearate is more preferred. Examples of these commercially available products include KF-6017, KF-6016, KF-6019 (manufactured by Shin-Etsu Chemical Co., Ltd.), KF-6048, KF-6028, KF-6038, KF-6105 (manufactured by Shin-Etsu Chemical Co., Ltd.), CITHROL® DPHS (manufactured by Croda Japan Co., Ltd.), NIKKOL MYS-2V (manufactured by Nikko Chemicals Co., Ltd.), and others.

[0049] The content of component (E) is not particularly limited, but from the viewpoint of UV protection, smooth spreadability, and transparency, it is preferably 0.5% or more, more preferably 1% or more, in the water-in-oil emulsion cosmetic, and from the viewpoint of cleansing properties and formulation stability, it is even more preferably more than 1%. Furthermore, from the viewpoint of formulation stability and transparency, it is preferably 10% or less, more preferably 6% or less, and from the viewpoint of cleansing properties, it is even more preferably 5% or less, and particularly preferably 4% or less.

[0050] Furthermore, component (E) preferably contains a silicone-based surfactant and a polyethylene glycol fatty acid ester, and more preferably contains a silicone-based surfactant and PEG-30 dipolyhydroxystearate. The mass ratio of polyethylene glycol fatty acid ester to silicone-based surfactant (polyethylene glycol fatty acid ester / silicone-based surfactant) is preferably 0.7 or less, and more preferably 0.5 or less, and even more preferably 0.4 or less, from the viewpoint of smooth, even spreadability. In the present invention, by using two types of silicone-based surfactants and polyethylene glycol fatty acid esters in combination, formulation stability and cleaning performance are improved, and the effects of the present invention, such as UV protection and transparency without white cast, can be more favorably exhibited. The lower limit of the mass ratio of polyethylene glycol fatty acid ester to silicone-based surfactant is, for example, 0.1 or more, and may be 0.2 or more.

[0051] (Component (F): Cyclic silicone with a kinematic viscosity of 10 mm at 25°C) 2 (At least one selected from the group consisting of silicones with a viscosity of / s or less) In the present invention, by further including component (F), it is possible to improve usability, such as smooth spreadability and lack of stickiness.

[0052] Component (F) used in the present invention is not particularly limited as long as it is usually used in cosmetics and can be used. Examples of cyclic silicones include octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane (cyclomethicone, cyclopentasiloxane), dodecamethylcyclohexasiloxane, diphenylsiloxyphenyltrimethicone, etc. From the viewpoint of usability such as a smooth spread, decamethylcyclopentasiloxane is preferred. Also, for silicones having a kinematic viscosity at 25°C of 10 mm 2 / s or less, examples include dimethicone, methylphenylpolysiloxane, etc. From the viewpoint of usability such as a smooth spread, dimethicone is preferred, and dimethicone having a kinematic viscosity at 25°C of 6 mm 2 / s or less is more preferred. Also, the lower limit of the kinematic viscosity of silicones having a kinematic viscosity at 25°C of 10 mm 2 / s or less is usually 1.5 mm 2 / s or more. In the present invention, one or more of these silicones may be used in combination, but it is particularly preferred to contain at least decamethylcyclopentasiloxane.

[0053] The kinematic viscosity of component (F) used in the present invention for silicones having a kinematic viscosity at 25°C of 10 mm 2 / s or less is measured according to the second method of the Cosmetic Raw Material Standard - Viscosity Measurement Method using a Brookfield viscometer.

[0054] The content of component (F) is not particularly limited, but in an oil-in-water type emulsified cosmetic, it is preferably 1% or more, more preferably 5% or more, and even more preferably 10% or more from the viewpoint of improving a smooth spread. Also, from the viewpoints of ultraviolet protection ability, formulation stability, and transparency, it is preferably 30% or less, and more preferably 20% or less.

[0055] Furthermore, the mass ratio (D) / (F) of component (D) to component (F) is preferably 0.1 or higher, and more preferably 0.5 or higher, from the viewpoint of UV protection ability, formulation stability, and transparency. In addition, the mass ratio (D) / (F) is preferably 5 or lower, more preferably 3 or lower, even more preferably 2 or lower, and particularly preferably less than 2, as this allows the cosmetic effect of the oil to be easily exhibited, such as smooth and even spreading.

[0056] (Component (G): Water-soluble polysaccharide) In the present invention, by further including component (G), formulation stability and transparency are improved, and usability is further enhanced, such as smooth spreadability and lack of stickiness.

[0057] The component (G) used in the present invention is not particularly limited as long as it is commonly used in cosmetics, but polysaccharides with glucuronic acid as a constituent sugar are preferred. Furthermore, it is also acceptable for a portion of the glucuronic acid to be neutralized, and monovalent or divalent inorganic salts are preferred, with salts of K, Na, and Ca being preferred.

[0058] Polysaccharides are a general term for substances in which multiple monosaccharide molecules are polymerized by glycosidic bonds. In the present invention, polysaccharides preferably refer to two or more sugars, such as glucuronic acid and other sugars, and more preferably to a polymer of 10 or more sugars. There are no particular limitations on the molecular weight, but a molecular weight of 10,000 to 20,000,000 is preferable as it is excellent in reducing stickiness. Furthermore, a molecular weight of 100,000 to 10,000,000 is preferable, and a molecular weight of 500,000 to 5,000,000 is particularly preferable. In this case, the molecular weight refers to the average molecular weight obtained by the viscosity method using GPC.

[0059] Polysaccharides containing glucuronic acid as part of their constituent sugars include, but are not limited to, Tremella fuciformis polysaccharide, hyaluronic acid, xanthan gum, gellan gum, Alcaligenes-producing polysaccharide, chondroitin sulfate, and heparin. Among these, Tremella fuciformis polysaccharide, xanthan gum, and hyaluronic acid are preferred, with Tremella fuciformis polysaccharide being particularly preferred. These polysaccharides can be used individually or in combination of two or more as appropriate.

[0060] Tremella fuciformis polysaccharides are high-molecular-weight polysaccharides obtained from plants belonging to the genus Tremella in the family Tremellaceae. While there are no particular limitations on such Tremella fuciformis polysaccharides, examples of commercially available products include Tremoist®-TP and Tremoist-SL (manufactured by Nippon Seika Co., Ltd.).

[0061] The content of component (G) is not particularly limited, but it is preferably 0.0005% or more, and more preferably 0.001% or more, in the water-in-oil emulsion cosmetic. Furthermore, the content of component (G) is preferably 0.02% or less, and more preferably 0.01% or less, in the water-in-oil emulsion cosmetic. Within this range, the effects of the present invention, such as UV protection and transparency, are suitably exhibited while ensuring smooth and even application.

[0062] In the present invention, the transparency evaluation described below makes it possible to evaluate the white cast after application to the skin. From the viewpoint of transparency that does not result in a white cast after application to the skin and provides a natural finish, it is preferable that the transmittance of light with a wavelength of 500 nm is 60% or more (up to 100%), and more preferably 80% or more.

[0063] Transparency was evaluated by placing each cosmetic product on a PMMA plate (HELIOPLATE HD6, manufactured by Labsphere) at a concentration of 2 mg / cm³. 2 After applying the sample by spreading it with your fingers and letting it stand for 20 minutes, the transmittance at a wavelength of 500 nm can be measured and evaluated using a UV-2600 ultraviolet-visible spectrophotometer (manufactured by Shimadzu Corporation).

[0064] Furthermore, considering formulation stability and skin safety, the present invention preferably substantially contains no organic UV absorbers. The organic UV absorbers may be either water-soluble or oil-soluble organic UV absorbers, and any that are commonly used in cosmetics are included. Specifically, for example, 2-hydroxy-4-methoxybenzophenone, 2,4,6-trianilino-p-(carbo-2'-ethylhexyl-1'-oxy)-1,3,5-triazine, 2-ethylhexyl salicylate, ethyl paradihydroxypropylbenzoate, 2-ethylhexyl paramethoxycinnamate, 4-tert-4'-methoxydibenzoylmethane, hexyl 2-[4-(diethylamino)-2-hydroxybenzoyl]benzoate, dimethoxybenzylidene dio Examples include 2-ethylhexyl xoimidazolidinepropionate, 2,2'-methylenebis[6-(2H-benzotriazole-2yl)-4-(1,1,3,3-tetramethylbutyl)phenol], 2,4-bis[{4-(2-ethylhexyloxy)-2-hydroxy}phenyl]-6-(4-methoxyphenyl)-1,3,5-triazine, dimethiconediethylbenzalmalonate, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its sodium salt. "Substantially free" means that organic UV absorbers are not included, at least intentionally. Therefore, if trace amounts of organic UV absorbers are inevitably included due to raw materials or manufacturing methods, they may be included in the concept of "substantially free of organic UV absorbers" as used herein. For example, the content of organic UV absorbers in water-in-oil emulsion cosmetics is 0.01% or less (lower limit 0%), 0.005% or less, and 0.0001% or less.

[0065] In addition to the essential components described above, the water-in-oil emulsion cosmetic of the present invention may contain, as necessary, components commonly used in cosmetics, within a quantitative and qualitative range that does not impair the effects of the present invention. For example, it may contain aqueous components for forming the water-in-oil emulsion cosmetic, oily components other than components (C) and (F), surfactants other than component (E), powders other than components (A) and (B), water-soluble polymers other than component (G), humectants, antioxidants, beauty ingredients, preservatives, fragrances, cooling agents, etc.

[0066] Any water-soluble component may be used as the aqueous component, for example, glycols such as propylene glycol, 1,3-butylene glycol, dipropylene glycol, and polyethylene glycol; glycerols such as glycerin, diglycerin, and polyglycerin; sugar alcohols such as sorbitol, maltitol, and glucose; and lower alcohols such as ethanol.

[0067] Furthermore, since the present invention is a water-in-oil emulsion cosmetic, it contains water. The water content is, for example, 15-75% and 20-60% of the water-in-oil emulsion cosmetic. The water is not particularly limited and includes tap water, purified water, hot spring water, deep sea water, and plant extracts such as aloe vera, witch hazel, witch hazel, cucumber, lemon, lavender, and rose, and one or more of these can be used.

[0068] The water-in-oil emulsion cosmetic composition of the present invention can be implemented in various forms, such as liquid, gel, emulsion, cream, semi-solid, solid, and mousse, with a cream form being preferable for obtaining the effects of the present invention. Here, a cream form is defined as having a viscosity of 100,000 mPa·s or less, measured using a Brookfield rotational viscometer at 25°C, preferably 90,000 mPa·s or less, more preferably 80,000 mPa·s or less, and even more preferably 70,000 mPa·s or less.

[0069] The water-in-oil emulsion cosmetic of the present invention is suitable for use as a lotion, cream, serum, massage cosmetic, face mask, hand cream, body lotion, body cream, makeup cosmetic, makeup base, eye cream, sunscreen, hair cream, hair wax, etc., and is particularly preferred as a sunscreen because its effects can be felt. Here, as a sunscreen, it can also be applied to bases, foundations, daytime serums, etc.

[0070] (Manufacturing method) The method for producing the water-in-oil emulsion cosmetic of the present invention can be carried out by a generally known method, and any general dispersion and emulsifying equipment such as a disperser can be used as the manufacturing equipment. [Examples]

[0071] Examples 1-22 and Comparative Examples 1-7: Water-in-oil emulsion cosmetics (sunscreen) Water-in-oil emulsion cosmetics with the compositions shown in Tables 1-3 below were prepared by the manufacturing method described below. Their UV protection ability, formulation stability, smooth spreadability, transparency, and washability were evaluated according to the evaluation methods and criteria described below, and the results are shown in Tables 1-3. The values ​​in parentheses in components (A) and (B) indicate the average particle size of fine zinc oxide or fine titanium dioxide before processing. The same applies hereafter.

[0072] [Table 1-1]

[0073] [Table 1-2]

[0074] [Table 2-1]

[0075] [Table 2-2]

[0076] [Table 3-1]

[0077] [Table 3-2]

[0078] (Manufacturing method) A: Mix components 1-10 and parts of 11-14 and disperse them in a roll mill. B: Mix the remaining components 11-14 and 15-23, add A, and mix and disperse. C: Components 24 and 25 were uniformly mixed and added to B, and emulsified to obtain a water-in-oil emulsion cosmetic.

[0079] [Evaluation Method 1] UV Protection Performance Regarding UV protection, each sample was placed on a PMMA plate (HELIOPLATE HD6, manufactured by Labsphere) at a concentration of 2 mg / cm². 2 After applying the sample by spreading it with a finger, the sample was left to stand for 20 minutes. SPF measurements were then performed using an SPF analyzer (UV-2000S, manufactured by Labsphere). Ten points on the plate were measured, the average SPF value was calculated, and the results were evaluated according to the following three-stage evaluation criteria.

[0080] 3-stage evaluation criteria [Judgment]: [Average SPF value] ◎: 25 or higher ○: 15 or more and less than 25 ×: Less than 15.

[0081] [Evaluation Method 2] Formulation Stability For formulation stability, each sample was filled into a No. 6 standard vial at 30g, stored in a constant temperature bath at 50°C for one month, and evaluated according to the following three-stage evaluation criteria based on the state of separation.

[0082] 3-stage evaluation criteria [Judgment]:[Evaluation] ◎: No separation and very good texture ○: Almost no separation, good texture ×: Clearly separated, poor texture [Evaluation Method 3] Smooth and unhindered expansion For smooth and even application, each sample was applied to the forearm of a panel of 20 cosmetic evaluation specialists. After 5 minutes of use (application), the smooth and even application was evaluated on a 5-point scale using the absolute evaluation method described below. A score was assigned, and the average score was calculated from the total scores of all panel members for each sample. The final evaluation was then conducted according to the 4-point evaluation criteria described below.

[0083] Absolute evaluation criteria [Rating]:[Evaluation Result] 5 points: very good 4 points: Good 3 points: normal 2 points: Slightly poor 1 point: Defective 4-level evaluation criteria [Judgment]: [Average score of the ratings] ◎: 4.0 or higher ○: 3.0 or higher, less than 4.0 △: 2.0 or higher, less than 3.0 ×: Less than 2.0.

[0084] [Evaluation Method 4] Transparency Regarding transparency, each sample was placed on a PMMA plate (HELIOPLATE HD6, manufactured by Labsphere) at a concentration of 2 mg / cm². 2 After applying the sample by spreading it with a finger, the sample was left to stand for 20 minutes. The transmittance at a wavelength of 500 nm was measured using a UV-2600 ultraviolet-visible spectrophotometer (manufactured by Shimadzu Corporation), and evaluated according to the following three-stage evaluation criteria.

[0085] 3-stage evaluation criteria [Judgment]:[Transmittance] ◎: 80% or more ○: 60% or more and less than 80% ×: Less than 60% [Evaluation Method 5] Cleanliness For cleansing properties, each sample was applied to the forearm of 20 cosmetic evaluation specialists. After 2 hours, they washed it off with bar soap and water, and the ease of removal was judged according to the following three-level evaluation criteria.

[0086] 4-level evaluation criteria [Judgment]:[Evaluation Result] ◎: More than 16 out of 20 people responded that it was good. ○: More than 10 out of 20 people responded that it was good. ×: Fewer than 10 out of 20 people reported a positive result. As is clear from the results in Tables 1 to 3, the water-in-oil emulsion cosmetics of Examples 1 to 22 of the present invention were superior to the water-in-oil emulsion cosmetics of Comparative Examples 1 to 7 in terms of UV protection ability, formulation stability, smooth spreadability, transparency, and washability.

[0087] In contrast, Comparative Example 1, where the total content (A)+(B) exceeded 40%, did not yield satisfactory results in terms of formulation stability, smooth spreadability, transparency, and washability. Furthermore, Comparative Example 2, where the total content (A)+(B) was less than 15%, showed insufficient UV protection. In Comparative Example 3, which used a surface treatment different from the N-acyl amino acid surface treatment of component (A), did not yield satisfactory results in terms of smooth spreadability and washability. In Comparative Example 4, which used unhydrophobized titanium dioxide fine particles instead of component (B), did not yield satisfactory results in any effect except washability. Furthermore, Comparative Example 5, which used a dispersant different from polyhydroxystearic acid of component (C), did not yield satisfactory results in terms of formulation stability, transparency, and washability. In addition, Comparative Example 6, which used hydrocarbon oil instead of ester oil of component (D), did not yield satisfactory results in any effect except UV protection. In Comparative Example 7, which used stearoyl glutamic acid, an anionic surfactant, instead of component (E), did not yield satisfactory results in any effect except washability.

[0088] Example 23: Sunscreen (water-in-oil emulsion) (Component) (mass%) 1. Stearic acid (10% by mass treatment) and aluminum hydroxide-treated fine particle titanium dioxide (10 nm) (Component (B)) 5 2. Lauroyl lysine-treated (20% by mass) fine particle zinc oxide (25 nm) (Component (A)) 15 3. Polyhydroxystearic acid (Note 17) (Component (C)) 2 4. Isononyl isononanoate (Note 10) (Component (D)) (IOB: 0.2) 10 5. Isopropyl palmitate (Note 11) (Component (D)) (IOB: 0.16) 8 6. PEG-30 Dipolyhydroxystearate (Note 5) (Component (E)) 0.8 7. PEG-9 Dimethicone (Component (E)) (Note 6) 2 8. Decamethylcyclopentasiloxane (Note 18) (Component (F)) 10 9. Purified water remaining amount 10.1,3-Butylene glycol 3 11. Glycerin 4 12. Sodium hyaluronate (Note 12) (Ingredient (G)) 3 (Note 10) Saracos 99 (manufactured by Nisshin Oillio Co., Ltd.) (Note 11) IPM-EX (manufactured by Japan Surfactant Industry Co., Ltd.) (Note 12) Hyaluronic acid FCH-SU (manufactured by Food Chemifa Co., Ltd.) (Note 18) KF-995 (manufactured by Shin-Etsu Chemical Co., Ltd.) (Manufacturing method) A: Mix components 1-4 and disperse them using a roll mill. B: Mix the remaining ingredients 5-8, add A, and mix and disperse. C: Ingredients 9-12 were uniformly mixed and added to B, and then emulsified to obtain a sunscreen (water-in-oil emulsion).

[0089] The sunscreen (water-in-oil emulsion) of Example 23 exhibited excellent UV protection, formulation stability, smooth spreadability, transparency, and washability. The values ​​were (A)+(B)=20% by mass, (A) / (B)=3.0, [(A)+(B)] / (C)=10, and (D) / (F)=1.8.

[0090] Example 24: Daytime beauty serum (water-in-oil emulsion) (Component) (mass%) 1. Triethoxyoctylsilane-treated (10% by mass) fine particle titanium dioxide (10 nm) (component (B)) 5 2. Lauroyl lysine-treated (20% by mass) fine particle zinc oxide (25 nm) (Component (A)) 17 3. Polyhydroxystearic acid (Note 17) (Component (C)) 2 4. Isotridecyl isononanoate (Component (D)) 10 5. Isopropyl palmitate (ingredient (D)) 8 6. PEG-30 Dipolyhydroxystearate (Component (E)) 1 7. PEG-9 Dimethicone (Component (E)) 2 8. Dimethicone (kinematic viscosity at 25°C: 10 mm) 2 / s)(component(F)) 10 9. Spherical anhydrous silicic acid (average particle size 4 μm) (Note 13) 3 10. Spherical anhydrous silicic acid (average particle size 20 μm) (Note 14) 3 11. Purified water remaining amount 12. DPG 5 13. Glycerin 4 14. Tremella fuciformis polysaccharide (Note 9) (Component (G)) 3 15. Ethanol 3 (Note 9) TREMOIST-TP (manufactured by Nippon Seika Co., Ltd.) (Note 13) Godball D-11C (manufactured by Suzuki Oil & Fat Industry Co., Ltd.) (Note 14) Sunsphere H-201 (manufactured by AGC SI-TEC) (Manufacturing method) A: Mix components 1-4 and disperse them using a roll mill. B: Mix the remaining 5-10 ingredients, add A, and mix and disperse. C: Ingredients 11-15 were uniformly mixed and added to B, and emulsified to obtain a daytime beauty serum (water-in-oil emulsion).

[0091] The daytime beauty serum (water-in-oil emulsion) of Example 24 exhibited excellent UV protection, formulation stability, smooth spreadability, transparency, and cleansing properties. The values ​​were (A)+(B)=22% by mass, (A) / (B)=3.4, [(A)+(B)] / (C)=11, and (D) / (F)=1.8.

[0092] Example 25: Liquid foundation (water-in-oil emulsion) (Component) (mass%) 1. Triethoxyoctylsilane-treated (10% by mass) fine particle titanium dioxide (10 nm) (component (B)) 5 2. Lauroyl lysine-treated (20% by mass) fine particle zinc oxide (25 nm) (Component (A)) 17 3. Polyhydroxystearic acid (Note 17) (Component (C)) 2 4. Isotridecyl isononanoate (Component (D)) 10 5. Neopentyl glycol diethylhexanoate (Note 15) (IOB: 0.32) (Component (D)) 8 6. PEG-30 Dipolyhydroxystearate (Component (E)) 1 7. PEG-9 Dimethicone (Component (E)) 2.5 8. Decamethylcyclopentasiloxane (Note 18) (Component (F)) 10 9. (Vinyl dimethicone / methicone silsesquioxane) crosspolymer (Note 19) 3 10. (Dimethicone / Phenylenyl Dimethicone) Crosspolymer (Note 16) 3 11. Diphenylsiloxyphenyl trimethicone (Note 20) (Component (F)) 0.5 12. Purified water remaining amount 13. Glycerin 5 14. Ethanol 8 15. Sodium chloride 0.1 (Note 15) Cosmoll 525 (manufactured by Nisshin Oillio Co., Ltd.) (Note 16) KSG-18 (manufactured by Shin-Etsu Chemical Co., Ltd.) (Note 19) KSP-100 (manufactured by Shin-Etsu Chemical Co., Ltd.) (Note 20) KF-56 (manufactured by Shin-Etsu Chemical Co., Ltd.) (Manufacturing method) A: Mix components 1-4 and disperse them using a roll mill. B: Mix the remaining ingredients 5-11, add A, and mix and disperse. C: Components 12-15 were uniformly mixed and added to B, and emulsified to obtain a liquid foundation (water-in-oil emulsion).

[0093] The liquid foundation (water-in-oil emulsion) of Example 25 exhibited excellent UV protection, formulation stability, smooth spreadability, transparency, and washability. (A)+(B)=22% by mass, (A) / (B)=3.4[(A)+(B)] / (C)=11, and (D) / (F)=1.7.

[0094] Example 26: Sunscreen (water-in-oil emulsion) (Component) (mass%) 1. Stearic acid (10% by mass treatment) and aluminum hydroxide-treated fine particle titanium dioxide (10 nm) (Component (B)) 5 2. Lauroyl lysine-treated (20% by mass) fine particle zinc oxide (25 nm) (Component (A)) 15 3. Polyhydroxystearic acid (Note 17) (Component (C)) 2 4. Isononyl isononanoate (Note 10) (Component (D)) (IOB: 0.2) 10 5. Isopropyl palmitate (Note 11) (Component (D)) (IOB: 0.16) 8 6. PEG-30 Dipolyhydroxystearate (Note 5) (Component (E)) 1 7. PEG-9 Dimethicone (Component (E)) (Note 6) 2 8. Decamethylcyclopentasiloxane (Note 18) (Component (F)) 10 9. Purified water remaining amount 10.1,3-Butylene glycol BG 3 11. Glycerin 4 12. Niacinamide 5 13. Tranexamic acid 2 (Manufacturing method) A: Mix components 1-4 and disperse them using a roll mill. B: Mix the remaining ingredients 5-8, add A, and mix and disperse. C: Ingredients 9-13 were uniformly mixed and added to B, and then emulsified to obtain a sunscreen (water-in-oil emulsion).

[0095] The sunscreen formulation (water-in-oil emulsion) of Example 26 exhibited excellent UV protection, formulation stability, smooth spreadability, transparency, and washability. The ratios were (A)+(B)=20% by mass, (A) / (B)=3.0, [(A)+(B)] / (C)=10, and (D) / (F)=1.8.

[0096] Example 27: Liquid foundation (water-in-oil emulsion) (Component) (mass%) 1. Triethoxyoctylsilane-treated (10% by mass) fine particle titanium dioxide (10 nm) (component (B)) 5 2. Lauroyl lysine-treated (20% by mass) fine particle zinc oxide (25 nm) (Component (A)) 17 3. Polyhydroxystearic acid (Note 17) (Component (C)) 2 4. Isotridecyl isononanoate (Component (D)) 10 5. Neopentyl glycol diethylhexanoate (Note 15) (IOB: 0.32) (Component (D)) 8 6. PEG-30 Dipolyhydroxystearate (Component (E)) 1 7. PEG-9 Dimethicone (Component (E)) 2 8. Decamethylcyclopentasiloxane (Note 18) (Component (F)) 10 9. (Vinyl dimethicone / methicone silsesquioxane) crosspolymer (Note 19) 3 10. (Dimethicone / Phenylenyl Dimethicone) Crosspolymer (Note 16) 3 11. Diphenylsiloxyphenyl trimethicone (Note 20) (Component (F)) 0.5 12. Purified water remaining amount 13. Glycerin 5 14. Ethanol 8 15. Sodium chloride 0.1 16. Niacinamide 5 17. Tranexamic acid 2 (Manufacturing method) A: Mix components 1-4 and disperse them using a roll mill. B: Mix the remaining ingredients 5-11, add A, and mix and disperse. C: Components 12-17 were uniformly mixed and added to B, and emulsified to obtain a liquid foundation (water-in-oil emulsion).

[0097] The liquid foundation (water-in-oil emulsion) of Example 27 exhibited excellent UV protection, formulation stability, smooth spreadability, transparency, and washability. (A)+(B)=22% by mass, (A) / (B)=3.4[(A)+(B)] / (C)=11, and (D) / (F)=1.7.

[0098] This application is based on Japanese Patent Application No. 2020-179435, filed on 27 October 2020, the disclosures of which are referenced and incorporated in whole.

Claims

1. The following components (A) to (E): (A) N-acylamino acid treated zinc oxide microparticles (B) Hydrophobized titanium oxide fine particles (C) Polyhydroxystearic acid (D) Ester oil that is liquid at 25°C (E) Nonionic surfactants with HLB 2-9 It contains the above, and the total content of component (A) and component (B) is 20 to 40% by mass, A water-in-oil emulsion cosmetic having an amount of component (D) of 10% by mass or more.

2. The water-in-oil emulsion cosmetic composition according to claim 1, wherein the mass ratio of component (A) and component (B) (A) / (B) is 1.5 to 6.

3. The water-in-oil emulsion cosmetic according to claim 1 or 2, wherein component (B) is triethoxyoctylsilane-treated fine particle titanium dioxide and / or fatty acid-treated fine particle titanium dioxide.

4. The water-in-oil emulsion cosmetic according to any one of claims 1 to 3, wherein component (A) is lauroyl lysine-treated fine particle zinc oxide and / or lauroyl glutamic acid-treated fine particle zinc oxide.

5. An oil-in-oil emulsion cosmetic composition according to any one of claims 1 to 4, wherein the transmittance of light with a wavelength of 500 nm is 60% or more.

6. The water-in-oil emulsion cosmetic composition according to any one of claims 1 to 5, wherein the mass content ratio of the components (A) to (C) [(A) + (B)] / (C) is 10 to 50.

7. The water-in-oil emulsion cosmetic composition according to any one of claims 1 to 6, wherein the component (E) is at least one selected from the group consisting of silicone surfactants and polyethylene glycol fatty acid esters.

8. The water-in-oil emulsion cosmetic composition according to any one of claims 1 to 6, wherein the component (E) comprises a silicone-based surfactant and a polyethylene glycol fatty acid ester, and the mass ratio of polyethylene glycol fatty acid ester to the silicone-based surfactant (polyethylene glycol fatty acid ester / silicone-based surfactant) is 0.7 or less.

9. The water-in-oil emulsion cosmetic according to claim 7 or 8, wherein the aforementioned polyethylene glycol fatty acid ester component is PEG-30 dipolyhydroxystearate.

10. The water-in-oil emulsion cosmetic according to any one of claims 1 to 9, wherein the water-in-oil emulsion cosmetic does not contain an organic ultraviolet absorber.

Images