Oil-in-water emulsion cosmetics

Abstract

To provide an oil-in-water emulsion cosmetic that has high UV protection performance and water resistance, also has a refreshing, nonsticky feeling of use and good stability over time, and is further effective in preventing secondary attachment.SOLUTION: An oil-in-water emulsion cosmetic contains following components (A)-(E): (A) acrylates / beheneth-25 methacrylate copolymer: 0.15-1 mass%, (B) PEG-240 / HDI copolymer bis-decyltetradeceth-20 ether: 0.05-1 mass%, (C) liquid oil comprising oil-soluble ultraviolet absorber: 8-20 mass%, (D) hydrophobic metal oxide: 5-20 mass% and (E) water, with the mass content ratio of the component (A) to component (B), (A) / (B), of 0.15-20, and the cosmetic being substantially free of surfactant.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to an oil-in-water type emulsified cosmetic.

Background Art

[0002] In recent years, various types of cosmetic formulations have been developed. Among them, oil-in-water type emulsified cosmetics are widely used in creams, sunscreen products, etc. because they have a high moisturizing feeling and an excellent usability such as a fresh touch. So far, the development of oil-in-water type emulsified cosmetics having various functions has been advanced. For example, oil-in-water type emulsified cosmetics having a high ultraviolet ray protection ability to protect the skin from UVA (long wavelength ultraviolet rays with a wavelength of 320 to 400 nm) and UVB (medium wavelength ultraviolet rays with a wavelength of 290 to 320 nm), and oil-in-water type emulsified cosmetics having an excellent water resistance so that the cosmetic film does not flow down due to water, sweat, etc. while having an ultraviolet ray protection ability have been reported, assuming various usage scenes. However, in order to achieve satisfactory ultraviolet ray protection ability and water resistance, appropriate selection of ultraviolet ray protectants, polymers, and oils is required. Depending on their types and contents, there are concerns about destabilization of the emulsified state over time and deterioration of usability such as a fresh spread and lack of stickiness. So far, various techniques for exhibiting a satisfactory ultraviolet ray protection ability have been studied. For example, as a technique having an ultraviolet ray protection ability and excellent usability, an oil-in-water type emulsified composition containing a (meth)acrylic acid / (meth)acrylic acid alkyl / (meth)acrylic acid POE monoalkyl ether ester copolymer, an ultraviolet ray protectant, a nonionic surfactant, and a higher alcohol (see, for example, Patent Document 1) is known.

[0003]

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

[0005] However, in the technology disclosed in Patent Document 1, the coating film would deform due to friction, making it difficult to achieve sufficient UV protection and water resistance. Furthermore, to suppress the decrease in UV protection, a secondary adhesion-free effect that prevents transfer to clothing and other materials is also an important function, but this secondary adhesion-free effect had not been considered. Therefore, the present invention aims to provide an oil-in-water emulsion cosmetic that has high UV protection and water resistance, a fresh and non-sticky feel, excellent stability over time, and also excellent secondary adhesion-free effect. [Means for solving the problem]

[0006] The inventors conducted diligent research to solve the above problems. Since it is necessary to minimize the surfactant content in order to exhibit water resistance and secondary adhesion prevention effects, they investigated using (sodium acrylate / sodium acryloyldimethyl taurate) copolymer and polyacrylamide, which are known to be salt-resistant water-soluble polymers with emulsifying properties. However, oil-in-water emulsion cosmetics using the above water-soluble polymers did not have good stability at high temperatures, and the inclusion of surfactants became indispensable, resulting in a decrease in water resistance and secondary adhesion prevention effects, as well as stickiness due to the inclusion of surfactants, making it difficult to obtain a satisfactory product. Therefore, after further diligent research, they found that stability could be ensured by combining (acrylates / beheneth-25 methacrylate) copolymer and (PEG-240 / decyltetradeceth-20 / HDI) copolymer among water-soluble polymers. This is thought to be because the inclusion of (acrylates / beheneth-25 methacrylate) copolymer enhances the emulsifying power of the oil-in-water emulsion cosmetic, provides a fresh and easily spreadable feel, and furthermore, the rheological properties of (PEG-240 / decyltetradeceth-20 / HDI) copolymer impart a thickening effect at high temperatures, thereby improving stability. By combining the above two polymers, it is possible to stably incorporate oil-soluble UV absorbers and hydrophobized metal oxides into the oil-in-water emulsion cosmetic without substantially containing surfactants, thereby effectively exhibiting water resistance and secondary adhesion-free effects. In short, the present invention is based on the discovery that, among the many water-soluble polymers, it is important to combine (acrylates / beheneth-25 methacrylate) copolymer and (PEG-240 / decyltetradeceth-20 / HDI) copolymer. The present invention was reached by creating an oil-in-water emulsion cosmetic containing (acrylates / beheneth-25 methacrylate) copolymer, (PEG-240 / decyltetradeceth-20 / HDI) copolymer, a liquid oil containing an oil-soluble ultraviolet absorber, a hydrophobized metal oxide, and water, and substantially free of surfactants.

[0007] In other words, the present invention provides the following: The following components (A) to (E); (A) (Acrylates / Beheneth-25 Methacrylate) Copolymer 0.15-1% by mass (B) (PEG-240 / Decyltetradeceth-20 / HDI) Copolymer 0.05~1% by mass (C) Liquid oil containing oil-soluble UV absorber 8-20% by mass (D) Hydrophobized metal oxide 5-20% by mass (E)Water This is an oil-in-water emulsion cosmetic containing the above-mentioned component (A) and component (B), with a mass ratio (A) / (B) of 0.15 to 20, and substantially free of surfactants. The content of the oil-soluble ultraviolet absorber relative to the total amount of component (C) may be 60% by mass or more. The aforementioned component (C) may contain ethylhexyl methoxycinnamate, and the content of ethylhexyl methoxycinnamate relative to the total amount of component (C) may be 40 to 80% by mass. The hydrophobic treatment agent for component (D) may be one or more treatment agents selected from the group consisting of trialkoxyalkylsilane, alkyl titanate, dimethylpolysiloxane, and methylhydrogenpolysiloxane. Furthermore, it may also contain component (F) inulin fatty acid ester. The mass ratio of component (C) to the total content of component (A) and component (B) (C) / {(A)+(B)} may be between 5 and 50. [Effects of the Invention]

[0008] The oil-in-water emulsion cosmetic composition of the present invention exhibits excellent UV protection, water resistance, and secondary adhesion-free effects. Furthermore, the oil-in-water emulsion cosmetic composition of the present invention exhibits excellent stability over time and a refreshing, non-sticky feel. The effects described herein are not necessarily limited, and any of the effects described herein may also be present. [Modes for carrying out the invention]

[0009] 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".

[0010] (Ingredient (A): (Acrylates / Beheneth-25 Methacrylate) Copolymer)

[0011] The component (A) (acrylates / beheneth-25 methacrylate) copolymer used in the present invention is a copolymer comprising an ester of methacrylic acid and beheneth-25 and one or more monomers selected from acrylic acid, methacrylic acid, or their simple esters. Examples of commercially available components (A) include Novethix L-10 (manufactured by Lubrizol Advanced Materials) and ACULYN28 (manufactured by Dow Chemical Group).

[0012] The content of component (A) in the oil-in-water emulsion cosmetic is, at a lower limit, 0.15% by mass (hereinafter sometimes simply abbreviated as "%") or more, preferably 0.3% or more, and more preferably 0.4% or more. Furthermore, the upper limit is 1% or less, preferably 0.8% or less, and more preferably 0.7% or less. In addition, the content of component (A) is 0.15 to 1%, preferably 0.3 to 0.8%, and more preferably 0.4 to 0.7%. This range is preferable because it provides superior water resistance, long-term stability, a fresh and non-sticky feel, and a secondary adhesion-free effect.

[0013] (Component (B): (PEG-240 / Decyltetradeceth-20 / HDI) Copolymer)

[0014] Component (B) (PEG-240 / decyltetradeceth-20 / HDI copolymer) used in the present invention is a copolymer of PEG-240, decyltetradeceth-20 and hexamethylene diisocyanate (HDI). Examples of commercially available products of component (B) include Adekanol GT-700 (manufactured by ADEKA Corporation), Avalure Flex-6 CC Polymer (manufactured by Lubrizol Advanced Materials), and the like.

[0015] In the present invention, the content of component (B) in the oil-in-water type emulsified cosmetic is 0.05% or more, preferably​​​​​​​​​​​The liquid oil containing component (C) an oil-soluble ultraviolet absorber used in the present invention is a liquid oil containing an oil-soluble ultraviolet absorber, and the oil-soluble ultraviolet absorber is not particularly limited as long as it is an ultraviolet absorber that is insoluble in water. Here, "liquid" refers to a substance whose viscosity value, measured with a B-type viscometer (rotor No. 2) at 25°C and 1 atmosphere, is 7000 mPa·s or less.

[0019] The liquid oil in component (C) is not particularly limited as long as it is commonly used in cosmetics, etc., but examples include hydrocarbons such as isododecane, isohexadecane, light isoparaffin, liquid paraffin (mineral oil), squalane, squalene, α-olefin oligomer, polybutene, liquid isoparaffin, heavy liquid isoparaffin, polyisobutylene, hydrogenated polyisobutene; rapeseed oil, avocado oil, almond oil, apricot kernel oil, perilla oil, orange oil, olive oil, kiwi seed oil, sesame oil, and wheat germ oil. , animal and vegetable oils such as rice germ oil, rice bran oil, safflower oil, sage oil, soybean oil, tea seed oil, corn oil, rapeseed oil, evening primrose oil, camellia oil, peach kernel oil, Job's tears oil, peanut oil, sunflower oil, grape seed oil, meadowfoam oil, rosemary oil, jojoba oil, macadamia nut oil, lavender oil, rosehip oil, mink oil, etc; glyceryl tri-2-ethylhexanoate, isotridecyl isononanoate, isononyl isononanoate, cetyl 2-ethylhexanoate, isopropyl myristate, isopropyl palmitate, 2-Ethylhexyl Palmitate, Octyldodecyl Myristate, Glyceryl Trioctanoate, Caprylic / Capric Triglyceride, Glyceryl Diisostearate, Glyceryl Triisostearate, Decaglyceryl Decaisostearate (Polyglyceryl-10 Decaisostearate), Propylene Glycol Dicaprate, Neopentyl Glycol Dicaprate, Polyglyceryl Triisostearate, Diisostearyl Malate, Neopentyl Glycol Diethylhexanoate, Tetraisostearyl Esters such as pentaerythritol tetraethylhexanoate, pentaerythritol tetra-2-ethylhexanoate, dipentaerythritol pentaisostearate, dialkyl carbonate, bisethoxydiglycol cyclohexane-1,4-dicarboxylic acid, hydrogenated rosin dimer dilinoleyl condensate, and alkyl (C12-15) benzoate; fatty acids such as oleic acid and isostearic acid; higher alcohols such as oleyl alcohol, 2-octyldodecanol, 2-decyltetradecanol, isostearyl alcohol, and 2-hexyldecanol;Silicone oils such as dimethylpolysiloxane (dimethicone), methyltrimethicone, methylphenylpolysiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, tetramethyltetrahydrogenocyclotetrasiloxane, tetramethyltetraphenylcyclotetrasiloxane, tetramethyltetratrifluoropropylcyclotetrasiloxane, pentamethylpentatrifluoropropylcyclopentasiloxane, polyether-modified methylpolysiloxane, oleyl-modified methylpolysiloxane, polyvinylpyrrolidone-modified methylpolysiloxane; fluorine-based oils such as perfluoropolyether, perfluorodecane, perfluorooctane; lanolin derivatives such as lanolin acetate, isopropyl lanolin fatty acid, lanolin alcohol; etc. can be mentioned, and one or more of these can be used.;

[0020] In the present invention, the liquid oil of component (C) is preferably an ester oil from the viewpoints of stability over time and a feeling of use without stickiness, and among them, it is more preferably one or more selected from the group consisting of isononyl isononanoate, isotridecyl isononanoate, cetyl 2-ethylhexanoate, propylene glycol dicaprate, alkyl (C12-15) benzoate.

[0021] The oil-soluble UV absorber contained in component (C) is not particularly limited as long as it is commonly used in cosmetics and the like, and may be in solid, paste, or liquid form. In the present invention, liquid organic UV absorbers are preferred from the viewpoint of UV protection ability and long-term stability, and specifically, examples include ethylhexyl methoxycinnamate, ethoxyethyl methoxycinnamate, isopropyl methoxycinnamate / diisopropyl cinnamate ester mixture, methylbis(trimethylsiloxy)silylisopentyl trimethoxycinnamate, amyl paradimethylamino acid benzoate, 2-ethylhexyl paradimethylamino acid benzoate, polysilicone 15, ethylene glycol salicylate, ethylhexyl salicylate, benzyl salicylate, homomenthyl salicylate, octocrylene, dimethyldiethyl benzalmalonate, and the like. Of these, it is more preferable that one or more are selected from the group consisting of ethylhexyl methoxycinnamate, ethylhexyl salicylate, homomenthyl salicylate, octocrylene, and polysilicone 15, and from the viewpoint of long-term stability, ethylhexyl methoxycinnamate and / or polysilicone 15 are even more preferable.

[0022] The content of component (C) in the oil-in-water emulsion cosmetic is preferably 8% or more, more preferably 9% or more, and more preferably 10% or more, with an upper limit of 20% or less, preferably 15% or less, and more preferably 13% or less. Furthermore, the content of component (C) is preferably 8-20%, more preferably 9-15%, and more preferably 10-13%. This range is preferable because it provides superior UV protection, water resistance, and a fresh, non-sticky feel.

[0023] Furthermore, in the present invention, the content of the oil-soluble ultraviolet absorber relative to the total amount of component (C) is preferably 30% or more, more preferably 40% or more, even more preferably 50% or more, and even more preferably 60% or more. As an upper limit, it is preferably 100% or less, more preferably 90% or less, and even more preferably 80% or less. Furthermore, the content of the oil-soluble ultraviolet absorber relative to the total amount of component (C) is preferably 30-100%, more preferably 40-100%, even more preferably 50-100%, even more preferably 60-90%, and particularly preferably 60-80%. This range is more preferable because it provides superior ultraviolet protection and water resistance.

[0024] Furthermore, in the present invention, from the viewpoint of UV protection ability and stability over time, it is particularly preferable to include at least ethylhexyl methoxycinnamate as an oil-soluble UV absorber. The lower limit of the content of ethylhexyl methoxycinnamate relative to the total amount of component (C) is preferably 30% or more, more preferably 35% or more, and even more preferably 40% or more. The upper limit is preferably 80% or less, more preferably 75% or less, even more preferably 70% or less, even more preferably 60% or less, and particularly preferably 55% or less. In addition, the content of ethylhexyl methoxycinnamate relative to the total amount of component (C) is preferably 30-80%, more preferably 35-75%, even more preferably 40-70%, even more preferably 40-60%, and particularly preferably 40-55%. This range is preferable because it improves the solubility of the solid UV absorber, resulting in superior UV protection ability, water resistance, and a fresh, non-sticky feel.

[0025] As described above, in the present invention, by combining components (A) and (B), it is possible to obtain an oil-in-water emulsion cosmetic that exhibits excellent emulsifying ability for oils such as component (C) without containing a surfactant, and that exhibits superior effects of the present invention. Although the present invention can be obtained by appropriately including components (A) to (E), it is preferable to specify the mass ratio of components (A) to (C) so that high effects can be expected in terms of water resistance, stability over time, a fresh and non-sticky feel, and a secondary adhesion-free effect. In the present invention, the mass ratio of component (C) / {(A)+(B)} to the total content of components (A) and (B) is not particularly limited, but as a lower limit, it is preferably 5 or more, more preferably 8 or more, even more preferably 10 or more, and still preferably 12 or more. Also, as an upper limit, it is preferably 55 or less, more preferably 50 or less, even more preferably 40 or less, and particularly preferably 30 or less. Furthermore, the mass ratio of (C) / {(A)+(B)} is preferably 5 to 55, more preferably 5 to 50, even more preferably 8 to 50, even more preferably 10 to 40, and particularly preferably 12 to 30.

[0026] (Component (D): Hydrophobized metal oxide)

[0027] The component (D) hydrophobized metal oxide used in the present invention improves its dispersibility in the oil phase by coating the surface of the metal oxide with a hydrophobized agent.

[0028] The hydrophobic treated fine particle oxide of the present invention is a metal oxide that blocks ultraviolet rays by absorbing, scattering, reflecting, quenching, etc., ultraviolet rays over a wide range of UVB to UVA (290 to 400 nm). In particular, from the viewpoint of having a high effect in blocking ultraviolet rays, it is preferable that it be one or more selected from hydrophobic treated zinc oxide, hydrophobic treated titanium oxide, and hydrophobic treated cerium oxide, more preferably hydrophobic treated zinc oxide and / or hydrophobic treated titanium oxide, and even more preferably hydrophobic treated zinc oxide.

[0029] The shape of the metal oxide is not particularly limited, but examples include granular, spherical, fusiform, dendritic, and balloon-shaped forms. From the viewpoint of reducing white cast due to improved dispersibility in the formulation, as well as UV protection and water resistance, granular, spherical, and fusiform forms are preferred.

[0030] The hydrophobic treated metal oxide is not particularly limited, but from the viewpoint of ultraviolet protection and water resistance, it is preferable that the average particle size is 1 nm to 1 μm, more preferably 3 nm to 100 nm, and even more preferably 5 nm to 50 nm. In this invention, the average particle size can be measured as the average particle size by image analysis of transmission electron microscope images. Approximately 10 mg of the sample is thoroughly mixed and dispersed on a glass slide with 1-propanol to obtain a dispersion. The dispersion is stretched to obtain a thin film sample. The thin film of the sample is placed on a transmission electron microscope (TEM) mesh with a support film. The mesh (dried coating) is set in a transmission electron microscope (S-4800, Hitachi High-Technologies Corporation) and observed to obtain an image of the dried coating film showing individual particles. The image of this dried coating film surface is processed using an image analysis particle size distribution analyzer (Mac-View, Mountec Co., Ltd.) with 1000 particles each to measure, and the particle size is measured. This allows us to obtain the average particle size D50 of the sample (powder) through image analysis of transmission electron microscope (TEM) images.

[0031] The hydrophobic treatment agent for component (D) 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, amino acid treatment agents, and acyl amino acid treatment agents. Among these, from the viewpoint of water resistance and stability over time, it is preferable to have one or more selected from silicone treatment agents and organic titanate treatment agents, more preferably one or more selected from trialkoxyalkylsilane, alkyl titanate, dimethylpolysiloxane, and methylhydrogenpolysiloxane, and even more preferably one or more selected from triethoxycaprylylsilane, isopropyl titanium triisostearate, dimethylpolysiloxane, and methylhydrogenpolysiloxane.

[0032] Examples of silicone treatment agents include hydrogen-modified silicones such as methylhydrogenpolysiloxane, linear silicones such as dimethylpolysiloxane, methylpolysiloxane, and methylphenylpolysiloxane, 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. In particular, from the viewpoint of UV protection ability and long-term stability, it is more preferable to use one or more selected from the group consisting of hydrogen-modified silicones, linear silicones, and silane coupling agents. Methylhydrogenpolysiloxane is more preferable as the hydrogen-modified silicone, and dimethylpolysiloxane is more preferable as the linear silicone. The silane coupling agent is not particularly limited, but trialkoxyalkylsilane is preferred. 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 use one or more selected from the group consisting of trimethoxyoctylsilane and triethoxyoctylsilane, from the viewpoint of UV protection ability, stability over time, water resistance, and secondary adhesion prevention effect.

[0033] Examples of organic titanate treatment agents include alkyl titanates such as long-chain carboxylic acid type, pyrophosphate type, phosphorous acid type, and amino acid type, with alkyl titanates having an alkyl group with 8 to 24 carbon atoms being preferred. Specifically, examples of the alkyl titanates include isopropyl triisostearoyl titanate, isopropyl trioctanoyl titanate, isopropyl dimethacrylate isostearoyl titanate, isopropyl isostearoyl diacrylic titanate, and diisostearoylethylene titanate as long-chain carboxylic acid type alkyl titanates, and tetraisopropyl bis(dioctyl phosphite) titanate and tetraoctyl bis(ditridecyl phosphate) titanate as pyrophosphate type alkyl titanates. Examples of alkyl titanates include tetra(2,2-diallyloxymethyl-1-butyl)bis(ditridecylphosphite) titanate, isopropyltri(dioctyl pyrophosphate) titanate, bis(dioctyl pyrophosphate) oxyacetate titanate, and bis(dioctyl pyrophosphate) ethylene titanate as examples of phosphite-type alkyl titanates, and isopropyltri(N-amidoethyl-aminoethyl) titanate as an example of amino acid-type alkyl titanate. In the present invention, among these alkyl titanates, long-chain carboxylic acid-type alkyl titanates are preferred from the viewpoint of UV protection ability, long-term stability, water resistance, and secondary adhesion-free effect, and isopropyltriisostearoyl titanate is more preferred.

[0034] The method for hydrophobic treatment in component (D) 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 to surface-treat simultaneously, or the surface can be pre-treated with one compound before applying other compounds.

[0035] The mass of the hydrophobic treatment agent in component (D) is not particularly limited, but from the viewpoint of UV protection ability and water resistance stability over time, it is preferably 60% or less as an upper limit, more preferably 50% or less, and even more preferably 30% or less as an upper limit, and 10% or more as a lower limit, more preferably 12% or more, and even more preferably 15% or more as a lower limit.

[0036] The content of component (D) in the oil-in-water emulsion cosmetic is preferably 5% or more, more preferably 7% or more, and more preferably 9% or more, with an upper limit of 20% or less, preferably 18% or less, and more preferably 16% or less. Furthermore, the content of component (D) is preferably 5-20%, more preferably 7-20%, more preferably 7-18%, and even more preferably 9-16%. This range is preferable because it provides superior UV protection, a fresh and non-sticky feel, and a reduced secondary adhesion effect.

[0037] (Ingredient (E): Water)

[0038] The component (E) water used in the present invention is not particularly limited as long as it is commonly used in cosmetics and the like, but examples include purified water, hot spring water, ion-exchanged water, deep sea water, tap water, or steam-distilled water from plants such as rose water or lavender water, and one or more of these can be appropriately selected and used as needed.

[0039] The content of component (E) in the present invention is not particularly limited, but in the oil-in-water emulsion cosmetic composition, it is preferably 40% or more at the lower limit, more preferably 50% or more, and even more preferably 60% or more. At the upper limit, it is preferably 80% or less, and even more preferably 70% or less. Furthermore, the content of component (E) is preferably 40-80%, more preferably 50-70%, and even more preferably 60-70%. This range is preferable because it provides a fresh, non-sticky feel and superior stability over time.

[0040] (Ingredient (F): Inulin fatty acid ester)

[0041] In the present invention, further inclusion of component (F) inulin fatty acid ester is preferable because it is possible to improve water resistance and secondary adhesion-free effect. The inulin fatty acid ester is an ester of inulin with a linear or branched saturated or unsaturated fatty acid having 8 to 32 carbon atoms, and the average molecular weight of inulin is preferably in the range of 300 to 10,000, and more preferably inulin stearate. Examples of commercially available products include Leopal ISK2 (manufactured by Chiba Flour Milling Co., Ltd.).

[0042] The content of component (F) in the present invention is not particularly limited, but in an oil-in-water emulsion cosmetic, the lower limit is preferably 0.01% or more, more preferably 0.05% or more, even more preferably 0.1% or more, and even more preferably 0.5%. The upper limit is preferably 5% or less, more preferably 3% or less, even more preferably 2% or less, and even more preferably 1.5%. Furthermore, the content of component (F) is preferably 0.01 to 5%, more preferably 0.05 to 3%, even more preferably 0.05 to 2%, even more preferably 0.1 to 2%, and particularly preferably 0.5 to 1.5%. This range is preferable because it provides superior water resistance, a fresh and non-sticky feel, and a secondary adhesion-free effect.

[0043] Furthermore, in the present invention, it is preferable that the product is substantially free of surfactants from the viewpoint of more favorably exhibiting water resistance and a fresh, non-sticky feel. The surfactants can be any surfactant commonly used in cosmetics, including nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants. In the present invention, from the viewpoint of water resistance, it is more preferable that the product is substantially free of anionic surfactants, cationic surfactants, and amphoteric surfactants. Here, "substantially free" in the present invention means 0.1% or less in the oil-in-water emulsion cosmetic, more preferably 0.08% or less, even more preferably 0.05% or less, and particularly preferably 0.02% or less. This range is preferable because it provides superior water resistance and a fresh, non-sticky feel.

[0044] In addition to the components described above, the oil-in-water emulsion cosmetic composition 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 surfactants, oils other than components (C) and (F), water-soluble polymers other than components (A) and (B), powders other than component (D), aqueous components, film-forming agents, antioxidants, pH adjusters, chelating agents, cosmetic ingredients, preservatives, fragrances, cooling agents, etc.

[0045] The aqueous component can be any component that is soluble in water, such as 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; lower alcohols such as ethanol; and glycerin derivatives such as polyoxybutylene polyoxyethylene polyoxypropylene glyceryl ether (3BO)(8EO)(5PO) and polyoxypropylene (9) diglyceryl.

[0046] The oil-in-water 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 50,000 mPa·s or less, measured using a Brookfield rotational viscometer at 25°C, preferably 40,000 mPa·s or less, more preferably 35,000 mPa·s or less, and even more preferably 30,000 mPa·s or less. The lower limit is 10,000 mPa·s or more, preferably 15,000 mPa·s or more, and more preferably 20,000 mPa·s or more.

[0047] The oil-in-water 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.

[0048] (Manufacturing method) The oil-in-water emulsion cosmetic of the present invention can be manufactured by commonly known methods, and any general dispersion and emulsification equipment such as a dispersion machine can be used as the manufacturing equipment. For example, it can be obtained by uniformly mixing components (A), (B), and (E) in a dispersion machine, adding and mixing components (C), (D), and (F) after heating, dissolving, and dispersing them, and then cooling. [Examples]

[0049] The effects of the present invention will be explained using the following examples and comparative examples. However, the technical scope of the present invention is not limited to the following examples. Unless otherwise specified, each operation is performed at room temperature (25°C). In the examples, the units "parts" or "%" may be used, but unless otherwise specified, they represent "parts by mass" or "mass%".

[0050] Examples 1-20 and Comparative Examples 1-14: Oil-in-water emulsion cosmetics (sunscreens) Oil-in-water emulsion cosmetics with the compositions shown in Tables 1-3 below were prepared by the following manufacturing method, and evaluated for (a) UV protection ability, (b) water resistance, (c) formulation stability (50°C / 1 month), (d) fresh and non-sticky feel, and (e) secondary adhesion-free effect according to the evaluation method and criteria shown below. The results are also shown in Tables 1-3.

[0051] Table 1 JPEG0007838957000001.jpg140170

[0052] Table 2 JPEG0007838957000002.jpg142170

[0053] Table 3 JPEG0007838957000003.jpg118170 (Note 1) NOVETHIX L-10 POLYMER (manufactured by Lubrizol Advanced Materials) (Note 2) AVALUREFLEX-6CC (manufactured by Lubrizol Advanced Materials) (Note 3) SIMULGEL EG QD (manufactured by SEPPIC) (Note 4) UVINUL MC80 (manufactured by BASF) (Note 5) Ubinal A PLUS GRANULAR (manufactured by BASF) (Note 6) TINOSORB S (manufactured by BASF) (Note 7) PARSOL SLX (manufactured by DSM) (Note 8) KF-96-6CS (manufactured by Shin-Etsu Chemical Co., Ltd.) (Note 9) MZY-505M (Dimethicone treatment: 5%, average particle size: 25nm) (Manufactured by Teika Co., Ltd.) (Note 10) MZX-508OTS (triethoxysilane treatment: 8%, average particle size: 25 nm) (manufactured by Teika Corporation) (Note 11) MZY-505S (Hydrogen dimethicone treatment: 5%, average particle size: 25nm) (Manufactured by Teika Co., Ltd.) (Note 12) Zinc oxide was processed using MZ-500 (manufactured by Teika Co., Ltd.), and the ITT treatment amount was set to 6% of the mass of zinc oxide. (Note 13) Leopard ISK2 (manufactured by Chiba Flour Milling Co., Ltd.)

[0054] (Manufacturing method) A: Mix components 14-17 and 20% of components 5-13, and disperse them using a three-roll mill. B: Disperse A and the remaining components 19-25 and 5-13 uniformly at 70°C. C: Disperse components 1-4, 50% of component 18, and component 26 uniformly at 70°C. Place B in D:C and distribute evenly. E:D was cooled to room temperature, and the remainder of component 18 and component 27 were added to obtain an oil-in-water emulsion cosmetic (sunscreen).

[0055] (Evaluation method 1: (a) UV protection ability) Each cosmetic ingredient is placed 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 a finger, and letting it stand for 20 minutes, the SPF was measured using an SPF analyzer (UV-2000S, Labsphere). Ten points were measured on the PMMA plate, and the UV protection performance was determined from the average value obtained according to the following four-stage evaluation criteria (see Reference 1: Journal of the Japanese Society of Cosmetic Science, 41(1):44-48 (2017)). <4-stage evaluation criteria> [Average score] : [Judgment] 25 or above: A (Excellent) 20 or more but less than 25: B (Good) 10 or more but less than 20: C (acceptable) Less than 10: D (Not acceptable)

[0056] (Evaluation method 2: (b) Water resistance) Each cosmetic ingredient is placed on a PMMA plate (HELIOPLATE HD6, manufactured by Labsphere) at a concentration of 2 mg / cm³. 2 After applying the coating by spreading it with a finger, the sample was left to stand for 20 minutes. SPF measurement was then performed using an SPF analyzer (UV-2000S, Labsphere) to determine the SPF value before the water bath. Next, the sample was subjected to a water bath. The water bath conditions were 25°C, 100 mL of water was placed in a container, the sample was attached to the side, and the container was shaken for 1 minute using a paint shaker. After the water bath, the sample was left to dry at room temperature for 20 minutes, and then the SPF value after the water bath was measured using the same SPF analyzer. Based on the ratio of the SPF values ​​before and after the water bath (SPF value after water bath) / (SPF value before water bath), the water resistance was determined according to the following four-stage evaluation criteria. <4-stage evaluation criteria> [Ratio (SPF measurement after bathing) / (SPF measurement before bathing)] : [Judgment] 0.8 or higher: A (Excellent) 0.7 or higher and less than 0.8: B (Good) 0.6 or higher but less than 0.7: C (Acceptable) Less than 0.6: D (Not acceptable)

[0057] (Evaluation method: (c) Stability over time (50°C / 1 month)) Each cosmetic product was placed in a 30g glass bottle (size 6, manufactured by Kawaguchi Pharmaceutical Co., Ltd.) and stored in a 50°C constant temperature bath for one month. The condition after one month was observed. Based on the results, the long-term stability was determined according to the following four-stage evaluation criteria (c). <4-stage evaluation criteria> [Evaluation] :[Judgment] No changes in appearance are observed: A (Excellent) Almost no changes in appearance: B (Good) No separation is observed, but deterioration of skin texture or the appearance of blemishes is seen: C (Acceptable) Separation is observed, the texture is very poor, and blemishes are visible: D (Unacceptable)

[0058] (Evaluation method 3: (d) A refreshing and non-sticky feel) Each cosmetic product was applied to the forearm of 20 cosmetic product evaluation panel members (10g each). They evaluated the "moisture" and "non-stickiness" of the product using the following 5-point scale and assigned scores. The average score was calculated from the total scores of all panel members for each cosmetic product, and the final evaluation was made using the following 4-point scale. <5-point rating scale> [Rating] :[Score] Very good: 5 points Good: 4 points Average: 3 points Slightly poor: 2 points Defective: 1 point <4-stage evaluation criteria> [Average score] : [Judgment] A score of 4.5 or higher: A (Excellent) A score above 4.0 and below 4.5: B (Good) A score above 3.0 and below 4.0: C (Acceptable) 3.0 points or less: D (impossible)

[0059] (Evaluation method: (e) Secondary adhesion reduction effect) 50 mg of each cosmetic was spread by finger over a 2 cm square area on artificial leather A (manufactured by Viewlux Co., Ltd.), and another artificial leather B was pressed onto it with a load of 100 gwt for 10 seconds. The transfer resistance (secondary adhesion-free effect) when peeled off was evaluated by yr, and the difference in brightness ΔL before and after transfer of artificial leather B was calculated using a colorimeter (CM-700d, manufactured by Konica Minolta Corporation), and judged according to the following four judgment criteria. <4-stage evaluation criteria> [Evaluation] :[Judgment] ΔL≦2 : A (Excellent) 2 < ΔL < 3 : B (Good) 3≦L<4 : C (possible) 4≦ΔL: D (not possible)

[0060] As is clear from the results in Tables 1-3, the oil-in-water emulsion cosmetics (sunscreens) of Examples 1-20 had higher UV protection and water resistance compared to the oil-in-water emulsion cosmetics (sunscreens) of Comparative Examples 1-14, as well as superior fresh, non-sticky feel, long-term stability, and excellent secondary adhesion-free effect.

[0061] On the other hand, in Comparative Example 1, which did not contain ingredient (A), satisfactory results were not obtained in terms of long-term stability and a fresh, non-sticky feel. In Comparative Example 2, where the mass ratio of component (A) to component (B) (A) / (B) exceeded 20, satisfactory results were not obtained in terms of water resistance, long-term stability, and secondary adhesion reduction effect. In Comparative Example 3, where the content of component (A) exceeded 1%, satisfactory water resistance could not be obtained. In Comparative Example 4, where the content of component (A) was less than 0.15%, satisfactory results were not obtained in terms of long-term stability and a fresh, non-sticky feel. In Comparative Example 5, where a salt-resistant, water-soluble polymer (sodium acrylate / sodium acryloyldimethyl taurate) copolymer was used instead of component (B), satisfactory results were not obtained in terms of water resistance, long-term stability, and secondary adhesion reduction effect. In Comparative Example 6, where a salt-resistant, water-soluble polymer (sodium acrylate / sodium acryloyldimethyl taurate) copolymer was used instead of component (A), satisfactory water resistance was not obtained. In Comparative Example 7, where polyacrylamide, a salt-resistant water-soluble polymer, was used instead of component (B), satisfactory results were not obtained in terms of water resistance, long-term stability, and secondary adhesion reduction effect. In Comparative Example 8, where polyacrylamide, a salt-resistant, water-soluble polymer, was used instead of component (A), satisfactory water resistance could not be obtained. In Comparative Example 9, where the content of component (B) exceeded 1%, satisfactory results were not obtained in terms of water resistance and a fresh, non-sticky feel. In Comparative Example 10, where the content of component (B) was less than 0.05%, satisfactory results were not obtained in terms of long-term stability and secondary adhesion reduction effect. In Comparative Example 11, where the content of component (C) exceeded 20%, satisfactory results were not obtained in terms of water resistance, long-term stability, a fresh and non-sticky feel, and a secondary adhesion-free effect. In Comparative Example 12, where the content of component (D) exceeded 20%, satisfactory results were not obtained in terms of a fresh, non-sticky feel and a secondary adhesion-free effect. In Comparative Example 13, where the content of component (D) was less than 5%, satisfactory results were not obtained in terms of UV protection and water resistance. In Comparative Example 14, where the surfactant content exceeded 0.1%, satisfactory results were not obtained in terms of water resistance and secondary adhesion prevention.

[0062] Example 21: Sunscreen gel (oil-in-water type) (components) (mass%) 1. (Acrylates / Beheneth-25 Methacrylate) Copolymer Component (A) Note 1 0.5 2. (PEG-240 / Decyltetradeceth-20 / HDI) Copolymer Component (B) Note 2 0.1 3. Sodium hydroxide 0.05 4. Ethylhexyl Methoxycinnamate (C) Note 4 5.0 5. Diethylamino hydroxybenzoyl hexyl benzoate Component (C) Note 5 1.0 6.2,4-Bis{[4-(2-ethylhexyloxy)-2 -hydroxy]-phenyl}-6-(4-methoxyphenyl) -1,3,5-triazine component (C) Note 6 1.0 7. Ethylhexyltriazone Component (C) Note 14 1.0 8,2-Cetyl ethylhexanoate, component (C) 1.0 9. Polymethylsilsesquioxane 3.0 10. Triethoxyoctylsilane-treated zinc oxide Component (D) Note 10 10 11. Polyhydroxystearic acid Note 15 0.2 12. Silica 1.0 13. Olive oil, component (C) 0.1 14. Di-2-ethylhexyl succinate Component (C) Note 16 1.0 15. Purified water remaining amount 16. Ethanol 10 17. Hyaluronic acid 0.15 18. Trehalose 0.05 19. Artemisia capillaris extract 0.01 20. Niacinamide 5.0 21. Tranexamic acid 2.0 (Note 14) UVINUL T150 (manufactured by Nikko Chemicals Co., Ltd.) (Note 15) Saracos HS-6C (manufactured by Nisshin Oillio Co., Ltd.) (Note 16) CRODAMOL OSU (manufactured by Croda)

[0063] (Manufacturing method) A: Disperse components 1-2 and a portion of component 15 uniformly, then add component 3 to neutralize. B: Mix components 10, 11, and 14 and disperse them using a three-roll mill. C: Dissolve components 4-8 uniformly at 70°C. Add components 9, 12, 13 and B to D:C and disperse them uniformly. E: Add D to A and emulsify. F:E was cooled to room temperature, and the remaining component 15 and components 16-21 were added and dispersed to obtain a sunscreen gel (oil-in-water type).

[0064] The sunscreen gel (oil-in-water type) of Example 21 had high UV protection and water resistance, as well as a refreshing, non-sticky feel, excellent stability over time, and a secondary adhesion-free effect. The mass ratio of component (A) to component (B) (A) / (B) was 5.

[0065] Example 22: Cream (oil-in-water type) (components) (mass%) 1. (Acrylates / Beheneth-25 Methacrylate) Copolymer Component (A) Note 1 0.7 2. (PEG-240 / Decyltetradeceth-20 / HDI) Copolymer Component (B) Note 2 0.15 3. Xanthan gum Note 17 0.1 4. Sodium hydroxide 0.06 5. Ethylhexyl Methoxycinnamate Component (C) Note 4 6.0 6. Diethylamino hydroxybenzoyl hexyl benzoate Component (C) Note 5 0.5 7.2,4-Bis{[4-(2-ethylhexyloxy)-2 -hydroxy]-phenyl}-6-(4-methoxyphenyl) -1,3,5-triazine component (C) Note 6 0.5 8. Ethylhexyltriazone Component (C) Note 14 0.5 9. Isononyl isononanoate Component (C) Note 18 1.0 10. Methylhydrogen dimethicone-treated zinc oxide Component (D) Note 11 10 11. Polyhydroxystearic acid Note 15 0.2 12. Silica 1.0 13. Isododecane Component (C) 0.5 14. Alkyl benzoate (C12-15) Component (C) 2.0 15. Purified water remaining amount 16. Ethanol 10 17. Tremella fuciformis extract (Note 19) 0.15 (Note 17) Nomucoat ZZ (manufactured by Nisshin Oillio Co., Ltd.) (Note 18) Saracos 99 (manufactured by Nisshin Oillio Co., Ltd.) (Note 19) TREMOIST-TP (manufactured by Nippon Seika Co., Ltd.)

[0066] (Manufacturing method) A: Disperse components 1-3 and a portion of component 15 uniformly, then add component 4 to neutralize. B: Mix components 10, 11, and 14 and disperse them using a three-roll mill. C: Dissolve components 5-9 uniformly at 70°C. Add components 12, 13, and B to D:C and disperse them uniformly. E: Add D to A and emulsify. F:E was cooled to room temperature, and the remaining portion of component 15 and components 16 and 17 were added and dispersed to obtain a cream (oil-in-water type).

[0067] The cream (oil-in-water type) of Example 22 had high UV protection and water resistance, as well as a refreshing, non-sticky feel, excellent stability over time, and a secondary adhesion-free effect. The mass ratio of component (A) to component (B) (A) / (B) was 4.7.

Claims

1. The following components (A) to (E): (A) (Acrylates / Beheneth-25 Methacrylate) Copolymer 0.15-1% by mass (B) (PEG-240 / decyltetradeceth-20 / HDI) copolymer 0.05-1% by mass (C) Liquid oil containing an oil-soluble UV absorber: 8-20% by mass (D) Hydrophobized metal oxide 5-20% by mass (E) Water An oil-in-water emulsion cosmetic containing the above, wherein the mass ratio of component (A) and component (B) (A) / (B) is 0.15 to 20, and substantially free of surfactants in an amount of 0% by mass or 0.1% by mass or less.

2. The oil-in-water emulsion cosmetic composition according to claim 1, wherein the content of the oil-soluble ultraviolet absorber relative to the total amount of component (C) is 30% by mass or more.

3. The oil-in-water emulsion cosmetic composition according to claim 1 or 2, wherein component (C) contains ethylhexyl methoxycinnamate, and the content of ethylhexyl methoxycinnamate relative to the total amount of component (C) is 30 to 80% by mass.

4. The oil-in-water emulsion cosmetic composition according to any one of claims 1 to 3, wherein the hydrophobic treatment agent for component (D) is one or more treatment agents selected from the group consisting of trialkoxyalkylsilane, alkyl titanate, dimethylpolysiloxane, and methylhydrogenpolysiloxane.

5. Furthermore, the oil-in-water emulsion cosmetic composition according to any one of claims 1 to 4, further comprising component (F) inulin fatty acid ester.

6. The oil-in-water emulsion cosmetic composition according to any one of claims 1 to 5, wherein the mass ratio of component (C) / {(A) + (B)} to the total content of component (A) and component (B) is 5 to 50.

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