TWI698257B - Water-in-oil emulsified cosmetics - Google Patents

Abstract

A water-in-oil type emulsified cosmetic material, which comprises an alkyl acrylate/styrene copolymer dispersion using a volatile hydrocarbon oil as a dispersing medium, an oil-soluble resin, a polyol, and a partially crosslinked organopolysiloxane.

Description

Water-in-oil emulsion cosmetics

The present invention relates to a water-in-oil type emulsified cosmetic. More specifically, the present invention relates to a water-in-oil type emulsified cosmetic with excellent secondary adhesion prevention effect and excellent use feeling.

Since the past, water-in-oil emulsified cosmetics can effectively spread oil-soluble active ingredients, such as emollient oils, ultraviolet absorbers, oil-soluble drugs, etc., on the skin, so they are used as external skin agents Because of its high water resistance, it is especially commonly used in cosmetics. In recent years, due to the increasing demand for exercise, there is a demand for a cosmetic that can maintain a beautiful makeup mask without losing the appearance even with a large amount of sweat or sebum. In addition, the demand for the elimination of skin troubles peculiar to menopause is rapidly increasing, and among them, there is an urgent desire for a cosmetic that does not deviate even if it is called a "hotflash" (hotflash), even with sudden large amounts of sweating. In addition, since it is easy to feel the dryness of the skin after sweating, these cosmetics that are excellent in water resistance and sebum resistance require a durable cosmetic film that also has a moisturizing feeling.

In the past, water-in-oil emulsified cosmetics have important functions such as water resistance and prevention of color shift caused by mixing with sebum (secondary adhesion prevention effect). Methods for improving these functions have been implemented. Various studies have been conducted. For example, the following technologies are known: by combining specific volatile organic polysiloxanes, oil-soluble resins, water-repellent powders, and water, the lightness, non-stickiness, and secondary adhesion of the spread during application are improved. Technology for preventing effects and cosmetic durability (refer to Patent Document 1); or by containing (meth)acrylic acid‧(meth)acrylic acid alkyl ester copolymer emulsion, partially crosslinked organopolysiloxane polymer, Volatile silicone, which does not substantially contain surfactants, and improves transparency, water resistance, sebum resistance, lubricating touch, and storage stability (refer to Patent Document 2); or by using volatile oil in combination Resin that does not dissolve in volatile oils, solid oil with a melting point of 75°C or higher, and dextrin fatty acid esters, improve the lightness of spreading, lubricity, secondary adhesion prevention effect, water resistance, Technology for oil resistance, cosmetic durability, and uniformity of cosmetic film (see Patent Document 3).

Prior art literature

Patent literature

Patent Document 1: Japanese Patent Laid-Open No. 2006-290878

Patent Document 2: Japanese Patent Laid-Open No. 2006-008585

Patent Document 3: Japanese Patent Laid-Open No. 2008-255014

However, in the technique of improving water resistance and preventing secondary adhesion by using oil-soluble resin like the technique of Patent Document 1, there are the following problems: the cosmetic film becomes hard, giving a burden such as stiffness, In addition, a dry feeling was felt along with the volatilization of the solvent. Furthermore, if the resin component is added in order to improve the effect, there is a disadvantage that spreading during application becomes thick and the feeling of use is impaired. In addition, the cosmetic material obtained in Patent Document 2 has insufficient water resistance because the coating film easily fuses with water, and furthermore, it is easy to feel a dry feeling accompanying the volatilization of the solvent. Furthermore, as obtained in Patent Document 3 The cosmetics have the following problems: because the film formed by the high melting point wax is hard, it gives a sense of burden such as stiffness, and it feels dry with the volatilization of the solvent.

Therefore, the subject of the present invention is to provide an oil pack that spreads lightly during application, has excellent water resistance and secondary adhesion prevention effects of the applied cosmetic film, and has no burden of stiffness or the like, and furthermore has an excellent moisturizing feeling. Water-based emulsifying cosmetics.

Under the above-mentioned actual conditions, the inventors of the present invention have repeatedly studied hard and found that by containing a volatile hydrocarbon oil as a dispersing medium, a dispersion of an alkyl acrylate·styrene copolymer, an oil-soluble resin, a polyol, and some The cross-linked organopolysiloxane can provide light spreading during application, and the applied cosmetic film has excellent water resistance and secondary adhesion prevention effects, and there is no burden such as stiffness, and the moisturizing feeling is also excellent. Water-in-oil emulsion cosmetics. It was found that although the alkyl acrylate and styrene copolymer dispersion itself forms a film, the partially cross-linked organopolysiloxane imparts flexibility to the film whose bonding point becomes stronger due to the combination of oil-soluble resins. The water resistance and secondary adhesion prevention effect are significantly improved, and the cosmetic film with excellent followability to the skin and minimal burden is clogged by polyols, suppressing the evaporation of skin moisture, and drastically improving the durability of the moisturizing feeling. this invention.

That is, the present invention is a water-in-oil type emulsified cosmetic, which includes the following components (A) to (D):

(A) Alkyl acrylate·styrene copolymer dispersion using volatile hydrocarbon oil as the dispersing medium

(B) Oil-soluble resin

(C) Polyol

(D) Partially cross-linked organopolysiloxane.

The present invention relates to a water-in-oil type emulsification that has light spreading during application, excellent water resistance and secondary adhesion prevention effects of the applied cosmetic film, and no burden of stiffness or the like, and furthermore has excellent moisturizing feeling. Cosmetics.

Hereinafter, the present invention will be described in detail.

The component (A) used in the present invention is a dispersion obtained by dispersing alkyl acrylate·styrene copolymer in volatile hydrocarbon oil. The dispersed alkyl acrylate and styrene copolymer is in INCI name (International Nomenclature Cosmetic Ingredient labeling names), as styrene and acrylate copolymer (STYRENE/ACRYLATES COPOLYMER) It can be obtained by polymerizing at least one of alkyl acrylate and alkyl methacrylate with styrene. These are insoluble in volatile hydrocarbon oils and have the form of dispersions, and are usually called non-aqueous dispersions (NAD=Non Aqua Dispersion, and non-aqueous emulsions also have the same meaning). The alkyl acrylate·styrene copolymer is not particularly limited, but it is preferably one containing alkyl acrylate and alkyl methacrylate and styrene in a mass ratio of 70/30 to 90/10. The number average molecular weight is 50,000~300,000 (the polymer obtained by gel permeation chromatography) Styrene conversion value). If it is in this range, it will not dissolve in volatile hydrocarbon oil and can maintain a good dispersion state. In addition, if the average particle diameter of the resin particles obtained by the centrifugal precipitation method is 0.1 μm to 2.0 μm, the viscosity of the dispersion is less changed, and precipitation of the particles is also difficult to occur, which is preferable.

The volatile hydrocarbon oil used as the dispersing medium of component (A) is not particularly limited as long as it is generally used in cosmetics. For example, hydrocarbons with a boiling point of 260°C or less under normal pressure, isooctane (2 , 2,4-trimethylpentane, 2,3-dimethylhexane, etc.), isododecane (2,2,4,6,6-pentamethylheptane, etc.), isohexadecane , Isoeicosane and other side chain hydrocarbons, isoparaffin, or a mixture of these, after polymerization or copolymerization of isobutylene, n-butene, etc. (polymerization degree is preferably 4~6), then hydrogenation If necessary, one type may be used, or two or more types may be used in combination. Among them, saturated hydrocarbon oils with side chains with 4 to 18 carbons are those that have good dispersibility, quick drying, and volatilization to form a firm coating film, which is better. Commercial products of these volatile hydrocarbon oils include: IP Solvent 1620 MU, IP Solvent 2028 MU (all manufactured by Idemitsu Petrochemical Co., Ltd.), Isoper (manufactured by Esso Chemical Co., Ltd.), and Maru Marukasol R (manufactured by Marukasol Petrochemical Company), etc.

Component (A) is made by dispersing alkyl acrylate ‧ styrene copolymer in volatile hydrocarbon oil to make a dispersion, but except by volatilizing alkyl acrylate or alkyl methacrylate and styrene In addition to polymerizing in a volatile hydrocarbon oil, it can be obtained by dispersing the copolymer in a volatile hydrocarbon oil. In the component (A), it is preferable to contain 80% by mass to 60% by mass (hereinafter, only referred to as "%") of alkyl acrylate‧benzene The ethylene copolymer more preferably contains 35% to 50%, and even more preferably 40% to 50%. If it is this range, the component (A) will be easily mixed uniformly in a cosmetic. As the component (A), a commercially available dispersion liquid can be used, and examples thereof include Nissetsu U-3700A (manufactured by Nippon Carbide).

The content of the component (A) in the present invention also depends on the concentration of the copolymer and is not particularly limited, but in terms of solid content, it is preferably 0.1% to 10% in cosmetics, more preferably 0.5% to 7.5% , Especially preferred is 1%~6%. If it is this range, it is preferable from a viewpoint of more excellent water resistance and unburdened feeling.

The oil-soluble resin of the component (B) used in the present invention is one that is soluble in oil agents such as volatile oil, and that forms a film. As long as it is usually used in cosmetics, it can be used without particular limitation. Component (B) has excellent sebum resistance and forms a hard and strong coating film, so it is contained in combination with component (A) to make the bonding points of the coating film formed by fusion of the dispersion stronger, thereby Significantly improve the effect of preventing secondary adhesion. Specifically, terpene-based resins, silicone resins, hydrocarbon resins, rosin acid-based resins, vinyl acetate-based resins, acrylic resins, etc. can be cited, and one type or two or more types may be used in combination as necessary.

Among them, from the viewpoint that the secondary adhesion prevention effect is more excellent, more preferred are trimethylsilyloxysilicate, polymethylsilsesquioxane, (acrylate/simethicone) as silicone resin Copolymer etc. Commercially available products include: silicon KF-7312J (50% solid content, solvent: cyclopentasiloxane, manufactured by Shin-Etsu Chemical Co., Ltd.), silicon KF-9021 (solid content 50%, solvent: cyclopentasiloxane Oxyane, manufactured by Shin-Etsu Chemical Industry Co., Ltd.), BY11-018 (30% solid content, solvent: cyclopentasiloxane, Toray Dow Corning Corporation), Silicon KP-541 (60% solid content, solvent: isopropanol, Shin-Etsu Chemical Co., Ltd.), SR-1000 (Made in Japan Momentive Advanced Materials), Silicon KP-545 ( Solid content is 30%, solvent: cyclopentasiloxane, manufactured by Shin-Etsu Chemical Co., Ltd., silicon KP-575 (solid content is 30%, solvent: cyclopentasiloxane, manufactured by Shin-Etsu Chemical Co., Ltd.), Silfer SILFORM FLEXIBLE RESIN (manufactured by Momentive Advanced Materials Co., Ltd.), Oppanol B-100 (manufactured by BASF), etc.

In addition, from the viewpoint that the secondary adhesion prevention effect is more excellent, as the component (B), the component (A): cycloalkyl-containing acrylate and/or methacrylate and the component (B): Acrylate and/or methacrylate of a linear or branched alkyl group with 8 to 12 carbon atoms, and/or (C): an organopolysiloxane macromonomer containing a radical polymerizable group at one end Acrylic copolymers obtained by polymerizing the monomers of are also preferred.

Specifically, the acrylic copolymer is more preferably in the total amount of constituent monomers, the blending amount of component (A) is 50% to 90% by mass, and the blending amount of component (B) and/or (C) It is 10% by mass to 50% by mass, and at least 30% by mass is dissolved in light isoparaffins at 25°C.

Here, the so-called light isoparaffin refers to a mixture of hydrocarbons mainly containing isoparaffin, specifically refers to a saturated hydrocarbon having a side chain of 9 to 12 carbon atoms, and refers to 95 in the distillation test of JIS-K2254 The volume% distillation temperature is below 200°C.

The acrylic copolymer preferably includes component (A) and component (B), component (A) and component (C), component (A) and component (B), and component (C) It is more preferable to include only component (A) and component (B), or only component (A), component (B), and component (C).

Specifically, the acrylic copolymer can be prepared by combining component (A), component (B), component (C), and optional components, or component (A), component (B), and optional components. Component, or component (A) and component (C), and optional components, respectively, are obtained by polymerization in the presence of an organic solvent and in the absence of water.

More specifically, as the acrylic copolymer, it is possible to suitably exemplify the component (A) and the component (B), and the component (A) is 50 to 90 parts by mass and 10 to 50 parts by mass. Parts of component (B) are polymerized acrylic copolymer, or containing component (A) and component (C), and 50 to 90 parts by mass of component (A) and 10 to 50 parts by mass Component (C) polymerized acrylic copolymer, or contains component (A), component (B) and component (C), and makes 50 to 90 parts by mass of component (A) and a total of 10 mass An acrylic copolymer obtained by polymerizing the component (B) and the component (C) from parts to 50 parts by mass.

The cycloalkyl-containing acrylate and/or methacrylate of the component (A) is a lipophilic polymerizable monomer, and constitutes a skeleton having the ability to form a transparent and hard film having water resistance. Specific examples include cyclohexyl acrylate, cyclohexyl methacrylate, dicyclopentyl acrylate, dicyclopentyl methacrylate, tricyclodecyl acrylate, tricyclodecyl methacrylate, tricyclodecyl acrylate Alkyl ester, tricyclodecyl methacrylate, etc., these can be used alone or in combination of two or more. Among these, cyclohexyl methacrylate has good radical polymerizability, high yield, and has a suitable glass transition point for forming a hard film, so it is particularly preferable.

The acrylate and/or methacrylate of component (B) containing a linear or branched alkyl group with 8 to 12 carbon atoms is a lipophilic polymerizable monomer that imparts flexibility or adhesion to the film and improves The solubility of light isoparaffins. Specific examples include octyl acrylate, octyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, isononyl acrylate, isononyl methacrylate, lauryl acrylate, Lauryl methacrylate, etc., these can be used alone or in combination of two or more. Among these, 2-ethylhexyl methacrylate and lauryl methacrylate are preferred, and 2-ethylhexyl methacrylate is particularly preferred.

As the component (C), the organopolysiloxane macromonomer containing a radical polymerizable group at one end includes an ester in which the organopolysiloxane is linked to acrylic acid or methacrylic acid via a divalent hydrocarbon group. As the compound, specifically, an organopolysiloxane macromonomer of the following formula (2) can be exemplified.

In the formula, m is 1 to 10, preferably 1 to 4, n is an integer of 0 to 200, R ₁ represents hydrogen or methyl, and R ₂ to R ₈ represent an alkyl group having 1 to 5 carbon atoms.

These can be used alone or in combination of two or more.

Component (C) Organopolysilicon containing a radical polymerizable group at one end The oxane macromonomer imparts water resistance to the film and improves the solubility to light isoparaffins. More specifically, the dimethylpolysiloxane macromonomer shown in the general formula (1) can be cited.

The polymerization degree n of the repeating unit representing the dimethylpolysiloxane group is preferably 0 to 200, more preferably 5 to 150. When the degree of polymerization n is less than 5, there is a possibility that sufficient water resistance cannot be obtained, and when it exceeds 150, it may be difficult to obtain a transparent and uniform film.

As an acrylic copolymer, in the sense of enhancing the effect of the present invention, it is preferably one containing only the (A) component and (B) component, and it is particularly preferable to use cyclohexyl methacrylate as the (A) component and (B) The (cyclohexyl methacrylate/ethylhexyl methacrylate) copolymer of 2-ethylhexyl methacrylate as the component.

Here, the content ratio of cyclohexyl methacrylate and 2-ethylhexyl methacrylate in the (cyclohexyl methacrylate/ethylhexyl methacrylate) copolymer is preferably 0.5:1~5: 1. More preferably 2:1~5:1, even more preferably 2:1~4:1, particularly preferably 2.5:1~4:1.

As a commercially available product, Plascize L-250 manufactured by Inter-Chemical Industry Co., Ltd. can be cited.

In addition, as long as it is in a range that does not impair the effect of the present invention, the acrylic copolymer of the component (B) may contain polymerization other than the component (A) to the component (C). Monomers are used as constituent monomers. The polymerizable monomers other than component (A) to component (C) are not particularly limited, and examples include styrene, substituted styrene, vinyl acetate, acrylic acid, methacrylic acid, acrylates other than the above, and methacrylic acid. Base acrylate, maleic anhydride, maleate, fumarate, vinyl chloride, vinylidene chloride, ethylene, propylene, butadiene, acrylonitrile, fluorinated olefin, acrylamide , Methacrylamide, methylacrylamide, methyl methacrylamide, dimethyl methacrylamide, N-isopropyl acrylamide, N-vinylpyrrolidone, N-vinylacetamide, tertiary butyl acrylate, tertiary butyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, dimethylaminoethyl methacrylate, dimethyl Aminoethylmethacrylamide, 2-acrylamide-2-dimethylpropanesulfonate, etc.

As the blending ratio of the components (A) to (C) or optional components, the blending amount of the component (A) is 50% to 90% by mass of the total monomers, preferably 50% to 80% by mass %. If it is less than 50% by mass, a film with sufficient hardness cannot be obtained, and if it exceeds 90% by mass, the solubility to light isoparaffins deteriorates. The compounding amount of the component (B) is 10% by mass to 50% by mass of the total monomers, preferably 15% by mass to 45% by mass. If it is less than 10% by mass, the solubility to light isoparaffins will deteriorate. If it exceeds 50% by mass, a film with sufficient hardness will not be obtained, and stickiness or adhesion, film unevenness, etc. will occur. Disadvantages. The compounding amount of the component (C) is 10% by mass to 50% by mass of the total monomers, preferably 15% by mass to 45% by mass. If it is less than 10% by mass, the solubility for light isoparaffins will become poor, and if it exceeds 50% by mass, the hardness cannot be obtained. Divided film, and produce stickiness or adhesion, film unevenness and other shortcomings. In addition, when the component (B) and the component (C) are used in combination, the total blending amount is 10% by mass to 50% by mass, preferably 15% by mass to 45% by mass. If the combined amount of component (B) and component (C) exceeds 50% by mass, a film with sufficient hardness cannot be obtained, and defects such as stickiness, adhesion, and film unevenness may be seen. If the total is less than 10% by mass, the solubility to light isoparaffins deteriorates. The blending amount of the optional component may be in the range of 30% by mass or less of the total monomers, preferably 20% by mass or less, for example, 0.01% by mass to 10% by mass can be adjusted.

The weight average molecular weight of the acrylic copolymer is not particularly limited, but is preferably in the range of 1.0×10 ⁴ to 2.0×10 ⁵ . The weight average molecular weight is measured by using tetrahydrofuran as the eluent, and by using a calibration curve made of linear polystyrene standards and a refractive index detector using Gel Permeation Chromatography (GPC). If the weight average molecular weight is 1.0×10 ⁴ or less, the film formation is slightly inferior, and if it is 2.0×10 ⁵ or more, the solubility viscosity in the light isoparaffin is high and the uniformity of the film is slightly poor.

The components (A) to (C) or other optional components as needed can be used as constituent monomers in the presence of an organic solvent (in the absence of water), by using a known polymerization method. Regular polymerization to obtain the acrylic copolymer. Although it is not particularly limited, as long as it is organic peroxide such as benzyl peroxide and lauryl peroxide, α,α'-azobisisobutyronitrile, 2,2'-azobis(2 ,4-dimethylvaleronitrile), 2,2'-azobis(2-methylbutyronitrile) and other azo compounds, potassium persulfate, persulfate The polymerization may be carried out in the presence of a radical polymerization initiator such as a persulfuric acid polymerization initiator such as ammonium, and a solution polymerization method, a suspension polymerization method, a bulk polymerization method, a precipitation polymerization method, etc. can be used. Among these, the solution polymerization method is particularly preferable because it is easy to adjust the molecular weight of the obtained acrylic copolymer to the optimum range.

The organic solvent used in the polymerization of the acrylic copolymer includes, for example, aromatic hydrocarbons such as benzene, toluene, and xylene, ketones such as methyl ethyl ketone and methyl isobutyl ketone, ethyl acetate, Esters such as butyl acetate and alcohols such as isopropanol, ethanol, methanol, etc., can be used alone or in combination of two or more. In addition, it can also be polymerized in a paraffinic solvent such as light isoparaffin, isododecane, and isohexadecane.

The polymerization reaction temperature of the acrylic copolymer is not particularly limited as long as it is within the usable temperature range of a general radical polymerization initiator, but it is usually carried out in the range of 40°C to 120°C. The reaction time varies depending on the radical polymerization initiator used, the type of monomer, and the reaction temperature, but it is usually carried out for 2 hours to 24 hours. If the polymerization time is too short, the amount of residual monomers will be large and the yield will be low and unfavorable.

The acrylic copolymer may maintain the state of being dissolved in the paraffinic solvent during the reaction, or may be diluted with oils such as other hydrocarbons, esters, and triglycerides as necessary, or may be replaced with other oils. Such an oil-soluble form of acrylic copolymer composition containing a cycloalkyl group is also included in the present invention. In addition, the solvent of the solution can be removed and the acrylic copolymer can be taken out as a solid, and the obtained acrylic copolymer polymer can also be used as an acrylic copolymer solution by dissolving the obtained acrylic copolymer polymer in a light isoparaffin. The acrylic copolymer and its solution can also be mixed with two Use more than one species.

In addition, as the component (B), the following fatty acid ester of dextrin can also be preferably used. The fatty acid ester of dextrin is a fatty acid ester of dextrin with an average degree of polymerization of glucose of 3 to 150, and contains relative to All fatty acids are more than 50mol%, 100mol% or less branched saturated fatty acids with carbon numbers 4 to 26, and 0 mol% or more and less than 50mol% of all fatty acids are selected from straight chain saturated fatty acids with carbon numbers 2 to 22, One or two or more of the group consisting of straight or branched unsaturated fatty acids with 6 to 30 carbons and cyclic saturated or unsaturated fatty acids with 6 to 30 carbons, substitution of fatty acids per unit of glucose The degree is 1.0~3.0.

Suitable fatty acid esters of dextrin are esters of dextrin and fatty acids, and the degree of substitution of fatty acids for dextrin is 1.0 to 3.0 per unit of glucose, preferably 1.2 to 2.8. If the degree of substitution is less than 1.0, the dissolution temperature for liquid oil or the like will be as high as 100°C or higher, and coloration or abnormal odor will occur, which is not preferable.

Suitable dextrin fatty acid esters have the following characteristics.

1) When a suitable dextrin fatty acid ester is mixed with liquid oil, the liquid oil will not gel.

The so-called "liquid oil will not gel" means that when a liquid paraffin with a dynamic viscosity of 8 mm ² /s at 40°C obtained by the ASTM D445 measurement method is used as a liquid oil, it contains 5 mass% The liquid paraffin of suitable dextrin fatty acid ester is dissolved at 100°C, and when the viscosity is measured at 25°C after 24 hours, the viscosity is Yamco DIGITAL VISCOMATE viscometer VM-100A (vibration type) (manufactured by Yamaichi Electric Co.) Below the detection limit. Furthermore, in the case of gelation, it can be confirmed by measuring the viscosity.

2) The film formed by the appropriate dextrin fatty acid ester has a specific range of adhesion Sex.

When the dextrin fatty acid ester is applied to the support body, the other support body is brought into surface contact from the state of being separated from each other, the support body is retreated and separated, and the contact point from the beginning of the retreat to the complete separation When the load change (maximum stress value) is used to express the "adhesiveness", a 400μm thick applicator is used to form a light liquid isoparaffin solution containing 40% by mass of the dextrin fatty acid ester on a glass plate , And using a texture analyzer, such as the texture analyzer TA.XTplus (manufactured by Stable Micro Systems), a cylindrical polyacetal resin (Delrin) (registered) with a diameter of 12.5 mm Trademark) The probe made by DuPont Co., Ltd. was used as the probe. After applying a load of 100g to the dried film and keeping it for 10 seconds, the load change at 0.5mm/sec separation, that is, the adhesiveness was 30g~1,000g.

The dextrin used in the suitable dextrin fatty acid ester is preferably dextrin with an average degree of glucose polymerization of 3 to 150, especially 10 to 100. If the average degree of glucose polymerization is 2 or less, the obtained dextrin ester becomes waxy and the solubility to the oil agent decreases. In addition, if the average degree of glucose polymerization exceeds 150, problems such as a high dissolution temperature of the dextrin ester with respect to an oil agent and poor solubility may occur. The sugar chain of dextrin may be linear, branched, or cyclic.

The fatty acid used in the suitable dextrin fatty acid ester means that one or two or more of the branched saturated fatty acids having 4 to 26 carbons are used as essential components, and the fatty acids may be selected from straight chain saturated fatty acids having 2 to 22 carbons. One or two or more of the group consisting of straight-chain or branched unsaturated fatty acids with 6 to 30 carbons and cyclic saturated or unsaturated fatty acids with 6 to 30 carbons (hereinafter, collectively refer to these Carbon number 4 Fatty acids other than ~26 branched saturated fatty acids are called "other fatty acids").

In a suitable form, the composition ratio of fatty acids is relative to all fatty acids. One or two or more of branched saturated fatty acids with carbon numbers of 4 to 26 are more than 50mol% and 100mol% or less, preferably 55mol% or more and 100mol% or less , Other fatty acids are 0 mol% or more but less than 50 mol%, preferably 0 mol% or more and 45 mol% or less.

Examples of branched saturated fatty acids with 4 to 26 carbon atoms used in suitable forms include isobutyric acid, isovaleric acid, 2-ethylbutanoic acid, ethyl methyl acetic acid, isoheptanoic acid, and 2-ethylhexyl Acid, isononanoic acid, isodecanoic acid, isotridecanoic acid, isomyristic acid, isopalmitic acid, isostearic acid, isoarachidic acid, isohexadecanoic acid, etc., one of these can be appropriately selected Use, or appropriately select two or more and use them in combination. Among these, those with 12 to 22 carbon atoms are preferred, and isostearic acid is particularly preferred, and there are no particular limitations such as structural differences.

In a suitable form, the so-called isostearic acid refers to one or a mixture of two or more branched stearic acids. For example, 5,7,7-trimethyl-2-(1,3,3-trimethylbutyl)-octanoic acid can be produced by the following method: Carbon is produced by the carbonylation reaction of isobutylene dimer The branched aldehyde of number 9 is then produced by the aldol condensation of the aldehyde to form a branched unsaturated aldehyde of carbon number 18, followed by hydrogenation and oxidation (hereinafter, abbreviated as "aldol condensation type"), for example by Nissan Chemical Industrial Co., Ltd. is commercially available. 2-heptylundecanoic acid can be produced by supplying nonanol to the Guerhet reaction and then oxidizing it. For example, it is commercially available from Mitsubishi Chemical Co., Ltd. and has slightly different branch positions. Similar mixtures, manufactured by Nissan Chemical Industry Co., Ltd. Nissan Chemical Industry Co., Ltd. is also commercially available. Furthermore, the two-position methyl branched type whose starting alcohol is not linearly saturated is also commercially available from Nissan Chemical Industry Co., Ltd. (hereinafter, collectively abbreviated as "Guerbert reaction type") . In addition, methyl branched isostearic acid is obtained, for example, as a by-product in the production of dimers of oleic acid [for example, in "J. Amer. Oil Chem. Soc.", It is described in 51,522 (1974)], for example, a commercially available product from Emery, Inc., USA (hereinafter, abbreviated as "Emory type"). The further starting material of the dimer acid which is the starting material of Emory-type isostearic acid may include not only oleic acid but also linoleic acid, hypolinoleic acid, and the like. In the present invention, the Emory type is particularly preferable.

Examples of straight-chain saturated fatty acids with 2 to 22 carbon atoms used in suitable forms include acetic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, and behenic acid. , One of these may be appropriately selected and used, or two or more may be appropriately selected and used in combination. Among these, those with 8 to 22 carbon atoms are preferred, and those with 12 to 22 carbon atoms are particularly preferred.

As the straight-chain or branched unsaturated fatty acid with 6 to 30 carbon atoms used in the suitable form, for example, as monoethylenically unsaturated fatty acid, cis-4-decenoic acid (obtusilic acid, trisonic acid), 9- Decenoic acid (caproleic acid), cis-4-dodecenoic acid (linderic acid, ursolic acid), cis-4-tetradecenoic acid (tsuzuic acid, crude acid), cis-5-decanoic acid Tetraenoic acid (physeteric acid, sperm cetic acid), cis-9-tetradecenoic acid (myristoleic acid, myristoleic acid), cis-6-hexadecenoic acid, cis-9-hexadecenoic acid ( palmitoleic acid, palmitoleic acid), cis-9-octadecenoic acid (oleic acid, oleic acid), trans-9-octadecenoic acid (elaidic acid), cis-11-octadecanoic acid Asclepic acid (asclepic acid), cis-11-eicosenoic acid (gadoleic acid, codoleic acid), cis-17- hexadecenoic acid (ximenic acid), cis-21- Lumequeic acid and the like. Examples of polyethylenically unsaturated fatty acids include sorbic acid, linoleic acid, hiragoic acid, punicic acid, linolenic acid, and γ-linolenic acid. Acid, stearidonic acid, stearidonic acid, arachidonic acid, eicosapentaenoic acid (Eicosapntemacnioc Acid, EPA), catfish acid, docosahexaenoic acid (DHA) , Niacinic acid (nisinic acid, herring acid), stearinic acid, yangshen oleic acid, ximenynic acid, etc.

The cyclic saturated or unsaturated fatty acids with 6 to 30 carbons used in suitable forms refer to saturated or unsaturated fatty acids with 6 to 30 carbons that have a cyclic structure in at least a part of the basic skeleton, for example: 9,10-methylene-9-octadecenoic acid; cyclopentenheptanoic acid, cyclopentenonanoic acid, cyclopentene tridecenoic acid, α-cyclopentyl acid, α-cyclohexyl acid, α- Cyclopentyl ethyl acid, α-cyclohexyl methyl acid, ω-cyclohexyl acid; 5(6)-carboxy-4-hexyl-2-cyclohexene-1-octanoic acid, malvacic acid, malabolic acid, Cyclopentene undecanoic acid, dafengzi acid, etc.

In a suitable form, as a dextrin fatty acid ester when only a branched saturated fatty acid is used as a fatty acid, the following etc. are mentioned, for example.

Dextrin isobutyrate

Dextrin ethyl methyl acetate

Dextrin Isoheptanoate

Dextrin 2-ethylhexanoate

Dextrin isononanoate

Dextrin isodecanoate

Dextrin isopalmitate

Dextrin Isostearate

Dextrin Isarachidate

Dextrin isohexadecanoate

Dextrin (Isovaleric Acid/Isostearic Acid) Ester

In a suitable form, as a fatty acid ester of dextrin when a mixed fatty acid of a branched saturated fatty acid and another fatty acid is used as a fatty acid, the following are mentioned, for example.

Dextrin (isobutyric acid/caprylic acid) ester

Dextrin (2-ethylhexanoic acid/caprylic acid) ester

Dextrin (isoarachidic acid/caprylic acid) ester

Dextrin (isopalmitic acid/caprylic acid) ester

Dextrin (ethyl methyl acetate/lauric acid) ester

Dextrin (2-ethylhexanoic acid/lauric acid) ester

Dextrin (isoheptanoic acid/lauric acid/behenic acid) ester

Dextrin (isostearic acid/myristic acid) ester

Dextrin (isohexadecanoic acid/myristic acid) ester

Dextrin (2-ethylhexanoic acid/palmitic acid) ester

Dextrin (isostearic acid/palmitic acid) ester

Dextrin (isostearic acid/isovaleric acid/palmitic acid) ester

Dextrin (isononanoic acid/palmitic acid/hexanoic acid) ester

Dextrin (2-ethylhexanoic acid/palmitic acid/stearic acid) ester

Dextrin (isodecanoic acid/palmitic acid) ester

Dextrin (isopalmitic acid/stearic acid) ester

Dextrin (isostearic acid/arachidic acid) ester

Dextrin (2-ethylhexanoic acid/arachidic acid) ester

Dextrin (2-ethylbutyric acid/behenic acid) ester

Dextrin (isononanoic acid/linoleic acid) ester

Dextrin (isopalmitic acid/arachidonic acid) ester

Dextrin (isopalmitic acid/caprylic acid/linoleic acid) ester

Dextrin (isostearic acid/stearic acid/oleic acid) ester

Dextrin (isoarachidic acid/palmitic acid/galactic acid) ester

Next, the manufacturing method of a suitable dextrin fatty acid ester is demonstrated.

It does not specifically limit as a manufacturing method, A well-known manufacturing method can be used, for example, it can manufacture as follows.

1) A dextrin having an average degree of polymerization of glucose of 3 to 150 is reacted with a fatty acid derivative containing more than 50 mol% and 100 mol% or less carbon number 4 to 4 to all fatty acid derivatives. One or two or more of 26 branched saturated fatty acid derivatives, and 0 mol% or more and less than 50 mol% of all fatty acid derivatives selected from straight-chain saturated fatty acid derivatives with carbon numbers 2 to 22, carbon numbers 6 to One or two or more of the group consisting of 30 straight-chain or branched unsaturated fatty acid derivatives and carbon 6-30 cyclic saturated or unsaturated fatty acid derivatives (hereinafter, collectively refer to these Fatty acid derivatives are called As "other fatty acid derivatives").

2) Reacting dextrin with an average degree of polymerization of glucose of 3 to 150 and one or more of branched saturated fatty acid derivatives with 4 to 26 carbon atoms, and then reacting the product with other fatty acid derivatives.

In this case, one or two or more of the branched saturated fatty acid derivatives with 4 to 26 carbons that are more than 50 mol% and 100 mol% or less relative to all fatty acid derivatives are used, and 0 mol% relative to all fatty acid derivatives Above and less than 50mol% of other fatty acid derivatives.

In a suitable form, as the fatty acid derivative used in the esterification reaction with the dextrin, for example, the halide and acid anhydride of the fatty acid can be used.

In either case of 1) and 2), first, dextrin is dispersed in a reaction solvent, and a catalyst is added as necessary. The halide of the fatty acid, acid anhydride, etc. are added thereto to perform the reaction. In the case of the production method of 1), these acids are mixed and added at the same time. In the case of the production method of 2), the branched saturated fatty acid derivative with low reactivity is first reacted, and then other fatty acids The derivative undergoes an addition reaction.

In manufacturing, the better method among these methods can be used. As the reaction solvent, a formamide series such as dimethylformamide and formamide; an acetamide series; a ketone series; aromatic compound series such as benzene, toluene, and xylene; solvents such as dioxane can be suitably used as the reaction solvent. As the reaction catalyst, tertiary amino compounds such as pyridine and picoline can be used. The reaction temperature is appropriately selected according to the raw material fatty acid, etc., but is preferably a temperature of 0°C to 100°C.

The following describes a production example of an example of the present invention (a production example of dextrin isostearic acid (Emory type) ester).

Disperse 21.41g (0.132mol) of dextrin with an average glucose polymerization degree of 30 in a mixed solvent containing 71g of dimethylformamide and 62g (0.666mol) of 3-methylpyridine at 70°C for 30 120 g (0.396 mol) of isostearyl chloride (Emory type) was added dropwise every minute. After the dropwise addition, the reaction temperature was set to 80°C and the reaction was performed for 5 hours. After the reaction, the reaction liquid was dispersed in methanol, and the upper layer was removed. After washing the semisolid content several times with methanol, it dried to obtain 107 g of a light yellow resin-like substance.

Examples regarding the obtained resinous substance, the infrared (Infrared, IR) spectroscopy, it was confirmed from the peak dextrin 1000cm ^-1 ~ 1200cm ^-1, the peak at 1742cm ^-1 is derived from ester, The peak derived from the alkyl group at 2800cm ^-1 ~ 3000cm ^-1 . In addition, according to the amount of fatty acid after alkali decomposition and gas chromatography, it can be confirmed that the degree of substitution is 2.2, isostearic acid is 60 mol%, and other fatty acids are 40mol% (of which palmitic acid is 10mol%).

Examples of commercially available products of dextrin fatty acid esters include Unifilma HVY (manufactured by Chiba Flour Mills) and the like.

The content of the component (B) in the present invention is not particularly limited, but is preferably 0.1% to 10% in the cosmetics, more preferably 0.3% to 8%, and particularly preferably 0.5% to 5%. If it is this range, it is preferable from a viewpoint that the secondary adhesion prevention effect is more excellent.

The polyol of the component (C) used in the present invention can be used without particular limitation as long as it is generally used in cosmetics. Specifically, propylene glycol, dipropylene glycol, butylene glycol, tripropylene glycol, and octane can be used. Glycol, glycerin, diglycerin, ethylene glycol, polyethylene glycol, hexylene glycol, etc., if necessary, one kind or a combination of two or more can be used use. When ingredient (C) is combined with ingredient (A), it acts as a lubricant, spreads lightly when applied, and it is blocked in the coating film to inhibit the evaporation of moisture from the skin, which can dramatically improve the continuity of moisturizing feeling Sex. Among them, tripropylene glycol (TRIPROPYLENE GLYCOL or PPG-3 in the INCI name) realizes easy spreading without stickiness until it stops, and has excellent skin fusion properties. Therefore, from the viewpoint of the persistence of moisturizing feeling Better. As a commercially available product, Newpol PP-200 (manufactured by Sanyo Chemical Industry Co., Ltd.) and the like can be cited.

The content of the component (C) in the present invention is not particularly limited, but is preferably 1% to 30%, more preferably 3% to 25%, and particularly preferably 5% to 20%. If it is this range, it is preferable from a viewpoint that the lightness of spreading and the continuation of a moisturizing feeling are more excellent.

In the embodiment of the present invention, it is particularly preferable to combine the (cyclohexyl methacrylate/ethylhexyl methacrylate) copolymer as the component (B) as a fast film-forming resin and the component (C) Tripropylene glycol is used in combination.

The partially cross-linked organopolysiloxane of component (D) used in the present invention is an organopolysiloxane polymer having a three-dimensional cross-linked structure, and it is not particularly limited as long as it is generally used in cosmetics. To use. Specifically, it can include (Dimethicone/Vinyl Dimethicone) cross-linked polymer and other partially cross-linked methyl polysiloxane, (Dimethicone/Phenyl dimethicone) cross-linked polymer and other parts Cross-linked methyl phenyl polysiloxane, (vinyl dimethicone/lauryl dimethicone) cross-linked polymer, (dimethicone/phenyl vinyl dimethicone) cross-linked polymer and other partially cross-linked Alkyl-modified silicone, (lauryl polydimethylsiloxyethyl simethicone / divinyl simethicone) cross-linked polymer and other partially cross-linked silicone ‧ alkyl co-modified silicone Ketone, (Simethicone/(PEG-10/15)) Partially cross-linked polyether modified silicone such as cross-linked polymer, PEG-15 lauryl simethicone cross-linked polymer and other partially cross-linked alkyl‧polyether co-modified silicone, (PEG-15/laurel (Dimethicone/Polyglycerol-3) cross-linked silicone ‧ alkyl ‧ polyether co-modified silicone, cross-linked polymer Partially cross-linked polyglycerol-modified silicone, (lauryl/polyglycerol-3) cross-linked polymer and other partially cross-linked alkyl ‧ polyglycerol co-modified silicone, (polyglyceryl-3/laurel Base polydimethylsilyloxyethyl simethicone) cross-linked polymer and other partially cross-linked silicone ‧ alkyl ‧ polyglycerin co-modified silicone, (trifluoropropyl dimethyl siloxane/trifluoropropyl Partially cross-linked fluorine-modified silicones such as divinyl dimethicone cross-linked polymers, etc., can be used in one kind or in combination of two or more kinds if necessary.

In addition, the so-called partially cross-linked polymer refers to a cross-linked polymer.

By combining the component (D) with the components (A) and (B), softness can be imparted to the oil-soluble resin, and a cosmetic film with minimal burden can be realized. If component (D) swells in an oil agent, it will be uniformly dispersed, and the effect of improving the hardness of the cosmetic film becomes more remarkable. It is often marketed as a mixture with an oil agent. As such a commercial product, KSG -15 (solid content is 5%), KSG-16 (solid content is 20% to 30%), KSG-18 (solid content is 10% to 20%), KSG-41A (solid content is 20% to 30%) ), KSG-042Z (solid content is 15% to 25%), KSG-210 (solid content is 20% to 30%), KSG-310 (solid content is 25% to 35%), KSG-320Z (solid content 20% to 30%), KSG-710 (solid content of 20% to 30%), KSG-810 (solid content of 25% to 35%), KSG-820Z (solid content of 20% to 30%), KSG-850Z (solid content is 20% to 30%), KSG-1510 (solid Composition is 5%~10%), KSG-1610 (solid content is 15%~20%), KSG-18A (solid content is 10%~20%), KSG-016F (solid content is 20%~30%) , KSG-045Z (solid content is 15% to 25%), KSG-048Z (solid content is 15% to 25%), KSG-240 (solid content is 15% to 25%), KSG-320Z (solid content is 20%~30%), KSG-350Z (solid content is 20%~30%), KSG-360Z (solid content is 30%~40%), KSG-380Z (solid content is 25%~35%), KSG -41 (solid content is 25% to 35%), KSG-42 (solid content is 20% to 30%), KSG-43 (solid content is 25% to 35%), KSG-44 (solid content is 25% ~35%), KSG-310 (solid content of 25% to 35%), KSG-320 (solid content of 20% to 30%), KSG-330 (solid content of 15% to 25%), KSG-340 (Solid content is 25% to 35%), KSG-340 (Solid content is 25% to 35%), KSG-710 (Solid content is 20% to 30%), KSG-51 (Solid content is 15 to 25%) ) (Above, manufactured by Shin-Etsu Chemical Co., Ltd.) etc.

In the embodiment of the present invention, the component (D) is particularly preferably partially cross-linked polyglycerin-modified silicone, partially cross-linked silicone‧alkyl‧polyglycerol co-modified silicone, specifically, Preferably it is KSG-710, KSG-820Z, KSG-850Z.

In the embodiment of the present invention, as component (D), it is particularly preferred to be partially cross-linked polyglycerin-modified silicone, and/or partially cross-linked silicone‧alkyl‧polyglycerol co-modified silicone and part Cross-linked methyl polysiloxane, and/or partially cross-linked methyl phenyl polysiloxane, and/or a combination of partially cross-linked silicone and alkyl co-modified silicone, specifically, Preferably KSG-710, KSG-820Z, KSG-850Z and KSG-15, KSG-1510, KSG-16, KSG-1610, KSG-18A, KSG-19, KSG-016F, KSG-042Z, A combination of KSG-045Z and KSG-048Z.

In the embodiment of the present invention, as component (D), it is particularly preferred to be partially cross-linked polyglycerin-modified silicone, and/or partially cross-linked silicone‧alkyl‧polyglycerol co-modified silicone and part Cross-linked polyether-modified silicone, and/or a combination of partially cross-linked silicone‧alkyl‧polyether co-modified silicone, specifically, preferably KSG-710, KSG-820Z, KSG- The combination of 850Z and KSG-210, KSG-240, KSG-320Z, KSG-350Z, KSG-360Z, KSG-380Z.

The content of the component (D) in the present invention is not particularly limited, but is preferably 0.1% to 5%, more preferably 0.2% to 4%, particularly preferably 0.5% to 3%. If it is this range, it is preferable from the viewpoint of obtaining a cosmetic film with less burden.

Furthermore, if the water-in-oil type emulsified cosmetic of the present invention contains the component (E) spherical silica, the degree of spreading at the time of application can be significantly increased, which is preferable. As long as the component (E) is usually used in cosmetics, any one can be used, but the average particle diameter is 1 μm to 30 μm, preferably 3 μm to 15 μm, from the viewpoint of better spreading good. The average particle size is calculated by a coulter counter. As a commercially available product, Sunsphere NP-100 (manufactured by AGC Si-Tech) and the like can be cited.

The content of the component (E) in the present invention is not particularly limited, but is preferably 0.1% to 10%, more preferably 0.5% to 7%, and particularly preferably 1% to 5%. If it is this range, a more satisfactory one can be obtained from the viewpoint that the degree of spreading is excellent.

The water-in-oil type emulsified cosmetic of the present invention has an oil phase as a continuous phase and water as a dispersed phase. The content of water is not particularly limited, but it is more Preferably, it is 5%~60%, more preferably is 10%~50%, and particularly preferably is 15%~40%.

In addition to the above-mentioned ingredients, the water-in-oil emulsified cosmetic of the present invention may suitably contain oil agents such as solid oil, semi-solid oil, and liquid oil that are generally used in cosmetics within a range that does not hinder the effects of the present invention. Surfactants, gelling agents, polymers, colorants, powders, UV absorbers, preservatives, antibacterial agents, antioxidants, fragrances, beauty ingredients, etc.

As the oil agent, liquid oils such as liquid paraffins and squalane, solid oils such as paraffin wax, ozokerite wax, microcrystalline wax, polyethylene wax, and Fischer-Tropsch wax, olive oil, Castor oil, jojoba oil, mink oil, Australian walnut oil and other fats, cetyl isooctanoate, isopropyl myristate, isopropyl palmitate, octyl dodecyl myristate, isononanoate Triesters, cholesterol fatty acid esters, N-laurinyl-L-glutamic acid di(cholesteryl‧docosyl‧octyldodecyl) esters and other esters, dimethylpolysiloxane, cyclic Silicone, phenyl modified polysiloxane, fluorine modified polysiloxane, amino modified polysiloxane, alkyl modified polysiloxane and other silicone oils.

Surfactants include: stearic acid, lauric acid, myristic acid, behenic acid, isostearic acid, oleic acid, 12-hydroxystearic acid, poly12-hydroxystearic acid, fatty acid soaps , Anionic surfactants such as glutamine salts, alkyl phosphates, polyoxyalkylene addition alkyl phosphates, cationic surfactants such as alkyl amine salts and alkyl quaternary ammonium salts, Glycerin fatty acid ester and its alkylene glycol adduct, propylene glycol fatty acid ester and its alkylene glycol adduct, sorbitan fatty acid ester and its alkylene glycol adduct, sucrose fatty acid ester, polyoxyethylene Non-ionic surfactants such as alkyl-modified organopolysiloxane and glycerin-modified organopolysiloxane.

Examples of gelling agents include dextrin palmitate, (palmitic acid/ethylhexanoic acid) dextrin, inulin stearate, organically modified bentonite, smoked silicic anhydride, aluminum isostearate, and stearic acid Zinc, magnesium stearate, etc., as the polymer, carrageenan, trixian gum, methyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, carboxyvinyl polymer, alkyl-modified carboxyvinyl Base polymers, polyvinyl alcohol, polyvinylpyrrolidone, etc. As ultraviolet absorbers, cinnamic acid derivatives, aminobenzoic acid derivatives, salicylic acid derivatives, benzophenone derivatives, phenylbenzene Bisimidazole derivatives, phenylbenzotriazole derivatives, etc., and preservatives such as para-hydroxybenzoic acid derivatives, phenoxyethanol, alkanediol, Rosemary extract, chamomile extract, collagen, Beauty ingredients such as hyaluronic acid and ceramide.

Colorants or powders are not particularly limited according to shapes such as plate, spindle, and needle shapes, particle sizes such as smoke, fine particles, and pigment grades, and particle structures such as porous and non-porous. Examples include inorganic powders. Type, bright powder type, organic powder type, pigment powder type, composite powder type, etc. Specifically, cyan, ultramarine, carbon black, magnesium carbonate, calcium carbonate, aluminum silicate, magnesium silicate, titanium oxide, zinc oxide, cerium oxide, mica, sericite, talc, kaolin, silicon carbide, barium sulfate Inorganic powders such as, boron nitride, bright powders such as bismuth oxychloride and aluminum powder, organic powders such as silicone powder, polyethylene powder, organic tar pigments, lake pigments of organic pigments, etc. Body type, titanium oxide coated mica, iron oxide treated mica, iron oxide coated titanium mica, organic pigment treated titanium mica, silicon dioxide‧titanium oxide coated mica, titanium oxide coated glass powder, iron oxide coated with titanium oxide Glass powder, silicon dioxide containing titanium oxide, barium sulfate coated titanium mica and other composite powders, polyethylene terephthalate‧ Aluminum‧Epoxy resin laminated powder, polyethylene terephthalate‧Polymethyl methacrylate laminated film powder, etc. One or two or more of these can be used, as well as fluorine-based compounds and silicone-based compounds , Metal soaps, lecithin, hydrocarbons, higher fatty acids, higher alcohols, esters, waxes, surfactants and other one or two or more of these are treated.

The water-in-oil type emulsified cosmetics of the present invention can be applied to makeup primers, foundations, beauty liquids, sunscreen cosmetics, etc., and are preferably makeup primers, foundations, BB creams, etc., which are expected to exert the effects of the application Material, more preferably a foundation. In addition, the method of use includes a method of using with hands or fingers, a method of using it by impregnation in a puff, sponge, or the like. In addition, its properties can be implemented as cosmetics of various properties such as gel and liquid.

Example

Examples are listed below to illustrate the present invention in detail. Furthermore, these do not limit the present invention in any way.

Example 1 to Example 20 and Comparative Example 1 to Comparative Example 5: Water-in-oil emulsified foundation (liquid)

The water-in-oil emulsified foundation of the formula shown in Table 1 below was prepared, and the water resistance, the effect of preventing secondary adhesion, the lightness of spreading, the unburdened feeling, and the continuation of the moisturizing feeling were evaluated by the following methods. The results are also shown in Table 1.

*1: Ceramide 20.2%, (palmitic acid/ethylhexanoic acid) dextrin 1.8% treatment

*2: 3% isopropyl titanium triisostearate, 5% hydrogen simethicone treatment

*3: SILFORM FLEXIBLE RESIN (manufactured by Momentive Advanced Materials, Japan)

*4: Nissetsu U-3700A (manufactured by Nippon Carbon & Chemical Corporation)

*5: Silicon KSG-710 (25% solid content, solvent: simethicone, manufactured by Shin-Etsu Chemical Co., Ltd.)

*6: Silicon KSG-16 (25% solid content, solvent: simethicone, manufactured by Shin-Etsu Chemical Co., Ltd.)

*7: Sunsphere NP-100 (manufactured by AGC Si-Tech)

*8: Yodosol GH41F (manufactured by Akzo Nobel)

*9: Newpol PP-200 (manufactured by Sanyo Chemical Co., Ltd.)

*30: Prepared as follows.

Add 22.5 g of cyclohexyl methacrylate, 7.5 g of 2-ethylhexyl methacrylate and 70 g of toluene to a four-neck separable flask equipped with a reflux cooler, thermometer, nitrogen introduction tube and stirring device, and introduce nitrogen After fully forming a nitrogen environment, the temperature was increased to 100°C, 0.15 g of AIBN was added, and refluxing was performed for 3 hours to perform polymerization. Methanol was poured into the obtained reactant to precipitate the acrylic copolymer, and after filtering the precipitate, vacuum drying was performed to obtain 27.4 g of a cycloalkyl group-containing acrylic copolymer solid content. The weight average molecular weight obtained by conversion from polystyrene is 5.0×10 ⁴ .

*31: Ester glue HP (manufactured by Arakawa Chemical Industry Co., Ltd.)

(Manufacturing method)

A. Disperse ingredient (1) to ingredient (9) uniformly.

B. After warming the ingredients (10) to (16), and from the ingredients (32) to (36) to uniformly dissolve them, they are added to A and mixed uniformly.

C. Add ingredient (17) to ingredient (24) to B and mix them uniformly.

D. Mix ingredients (25) to (31) uniformly.

E. Slowly add D to C, and disperse and emulsify.

F: Degas E and fill it into the container.

(Evaluation method)

Regarding the following evaluation items of i to v, they were evaluated by the following methods.

(Evaluation item)

i. Water resistance

ii. Secondary adhesion prevention effect

The sample was applied to a panel of 20 people. After 3 hours, the cotton moistened with water was pressed onto the skin for evaluation item i for 10 seconds, and the color shift to the cotton after peeling was evaluated. About the evaluation item ii. Evaluate the color shift on the tissue after lightly pressing with tissue. In the following absolute evaluation, each panelist evaluated in five levels, calculated an average value for each sample, and judged by the following judgment criteria.

<Absolute evaluation criteria>

(Rating): (evaluation)

4: Very good

3: good

2: Normal

1: Poor

0: very bad

<Judgment Criteria>

(Judgment): (Average score of score)

◎: More than 3.5 points: very good

○: More than 2.5 points and less than 3.5 points: Good

△: more than 1 point, less than 2.5 points: slightly bad

×: 1 point or less: bad

(Evaluation item)

iii. Mild spread

iv. No burden

v. Continuous moisturizing

The sample was applied to a panel of 20 people, iii for the use, iv for whether the skin feels stiff or burdened immediately after application, v for the moisturizing feeling after 6 hours of normal life after application, based on the following absolute evaluation criteria , Evaluate and score in 7 levels, calculate the average value based on the scores of all the members of the group of each sample, and judge by the following criteria.

<Absolute evaluation criteria>

(Rating): (evaluation)

6: Very good

5: good

4: Slightly good

3: Normal

2: slightly worse

1: Poor

0: very bad

<Judgment Criteria>

(Judgment): (Average score of score)

◎: More than 5 points: very good

○: More than 3.5 points and less than 5 points: Good

△: more than 1 point, less than 3.5 points: slightly bad

×: 1 point or less: bad

As is clear from the results of Table 1, compared with the water-in-oil emulsified foundations of Comparative Examples 1 to 5, the water-in-oil emulsified foundations of Examples 1 to 20 of the present invention are more resistant to water The secondary adhesion prevention effect, the lightness of spreading, the unburdened feeling, and the continuation of the moisturizing feeling are excellent in all aspects.

On the other hand, in Comparative Example 1 which does not contain the component (A), the cosmetic film is weak in strength, so it is easy to lose its appearance. Furthermore, the skin cannot be prevented from evaporating moisture over time, so it has water resistance and secondary adhesion prevention effects. From the viewpoint of the continuation of the moisturizing feeling, no satisfactory ones can be obtained.

In Comparative Example 2 using an alkyl acrylate-styrene copolymer dispersion with water as a dispersion medium instead of component (A), the cosmetic film is easily fused with water, so it is resistant The water is not good, and the flexibility of the coating film is insufficient, so it cannot follow the movement of the skin, and furthermore, because the skin's time-dependent moisture evaporation cannot be suppressed, it is not possible in terms of water resistance, unburdened feeling, and continuation of moisturizing feeling. Get a satisfactory one.

In Comparative Example 3 that does not contain the component (B), the coating film formed by the fusion of the component (A) has weak bonding points, so it easily fuses with sebum, and the effect of preventing secondary adhesion is not good.

In Comparative Example 4 that does not contain component (C), it is easy to feel the spreading weight of component (A) and component (B), and the skin's moisture evaporation over time cannot be suppressed, so the spreading is light The viewpoints of the degree and the continuation of the moisturizing feeling are not sufficient.

In Comparative Example 5 that does not contain the component (D), the hardness of the cosmetic film due to the oil-soluble resin is easily felt, and it is not satisfactory from the viewpoint of no burden.

In Example 14 using trimethylsilyloxysilicate, which is a hard resin, as the component (B), it is not only excellent in water resistance, secondary adhesion prevention effect, light spreading, no burden, and moisture retention It is excellent in all aspects of continuation, and the effect of imparting tension to the skin is excellent.

In Example 15 using a flexible (acrylate/simethicone) copolymer as component (B), it is not only good for water resistance, secondary adhesion prevention effect, light spreading, no burden, and moisture retention It is excellent in all aspects of continuity, and the effect of preventing wrinkles of the cosmetic film in areas with large movements accompanying expressions, such as around the eyes or around the mouth, is excellent.

For Example 16 using dextrin isostearate with rich gloss as ingredient (B) Among them, it is not only excellent in all aspects of water resistance, secondary adhesion prevention effect, lightness of spreading, unburdened feeling, and continuation of moisturizing feeling, but also excellent gloss of the cosmetic film.

In Example 17 and Example 18 using (cyclohexyl methacrylate/ethylhexyl methacrylate) copolymer as the component (B) as a resin with fast film formation, it is not only good for water resistance and secondary adhesion It is excellent in all aspects of the prevention effect, the lightness of spreading, the feeling of no burden, and the continuation of the moisturizing feeling, and it is excellent in terms of producing a uniform cosmetic film without uneven application.

In Example 19 using hydrogenated rosin acid pentaerythritol as the component (B), it can be seen that all aspects of water resistance, secondary adhesion prevention effect, mildness of spreading, unburdened feeling, and continuation of moisturizing feeling are also obtained.

Example 21: Water-in-oil emulsion type makeup primer (cream)

*10: KF-6019 (manufactured by Shin-Etsu Chemical Co., Ltd.)

*11: Silicon KP-545 (30% solid content, manufactured by Shin-Etsu Chemical Co., Ltd.)

*12: Silicon KSG-210 (25% solid content, manufactured by Shin-Etsu Chemical Co., Ltd.)

*13: SILICA MICRO BEAD BA-1 (manufactured by Nikkei Catalyzer Kasei)

*14: Ganzpearl GMI-0804 (manufactured by Ganz Chemical)

(Manufacturing method)

A. Disperse ingredient (1) to ingredient (8) evenly.

B. After warming component (9) to component (10) to uniformly dissolve, add to A and mix uniformly.

C. Add component (11) to component (21) to B and mix them uniformly.

D. Mix the ingredients (22) to (27) uniformly.

E. Slowly add D to C, and disperse and emulsify.

F: Degas E and fill it into the container.

The water-in-oil emulsion type makeup primer (cream-like) of the present invention spreads lightly when applied, and the applied makeup film has excellent water resistance and secondary adhesion prevention effects, and does not have a burden such as stiffness, thereby providing a moisturizing feeling The continuity is also excellent.

Example 22: Water-in-oil emulsified sunscreen cosmetics (liquid)

*15: Silicon KF-6015 (manufactured by Shin-Etsu Chemical Co., Ltd.)

* 16: IP Solvent 2028 MU (manufactured by Idemitsu Petrochemical Corporation)

*17: Silicon KF-7312J (solid content is 50%, solvent: cyclopentasiloxane, Shin-Etsu Chemical Industry Co., Ltd.)

*18: KSG-18 (15% solid content, solvent: diphenylsilanoxy phenyl trimethicone, manufactured by Shin-Etsu Chemical Co., Ltd.)

*19: Sunsphere NP-30 (manufactured by AGC Si-Tech) (manufacturing method)

A. Disperse ingredients (1) to (3) uniformly.

B. After warming component (4) to component (8) to dissolve it uniformly, add to A and mix it uniformly.

C. Add component (9) to component (16) to B and mix them uniformly.

D. Mix component (17)~component (24) evenly.

E. Slowly add D to C, and disperse and emulsify.

F: Degas E and fill it into the container.

The water-in-oil emulsified sunscreen cosmetic (liquid) of the present invention spreads lightly when applied, and the applied cosmetic film has excellent water resistance and secondary adhesion prevention effects, and has no burden such as stiffness, thereby providing a moisturizing feeling The continuity is also excellent.

Example 23: Water-in-oil emulsified blush (gel)

*20: SR-1000 (manufactured by Momentive Advanced Materials, Japan)

*21: Unifilma HVY (manufactured by Chiba Flour Mills)

*22: The same alkyl acrylate and styrene copolymer as *4, with 50% solid content and dispersion medium: isododecane. Prepare as follows.

The (meth)acrylate monomer, styrene, and polymerization initiator are added to the isododecane of the dispersing medium, and the mixture is stirred to perform polymerization. The polymerization solution is filtered, and the filtrate is subjected to the removal of monomers under reduced pressure to obtain a dispersion in which isododecane is the dispersion medium.

*23: Silicon KF-6026 (manufactured by Shin-Etsu Chemical Co., Ltd.)

*24: Rheopearl TL-2 (manufactured by Chiba Flour Milling Company)

*25: Metashine 1080RC-R (manufactured by Nippon Sheet Glass), 3% perfluorooctyl triethoxysilane treatment

*26: Bentonite (BENTONE) 27V (manufactured by ELEMENTIS)

(Manufacturing method)

A. Disperse ingredient (1) to ingredient (5) uniformly.

B. After dissolving component (6) to component (8) uniformly, add to A and mix uniformly.

C. Add component (9) to component (21) to B and mix them uniformly.

D. Mix the ingredients (22) to (26) uniformly.

E. Slowly add D to C, and disperse and emulsify.

F: Degas E and fill it into the container.

The water-in-oil emulsified blush (gel-like) of the present invention spreads lightly during application, and has excellent water resistance and secondary adhesion prevention effects of the cosmetic film after application, and no Stiffness and other burdens, and the continuation of moisturizing feeling is also excellent.

Example 24: Water-in-oil emulsified sunscreen cosmetics (liquid)

*27: KSG-210 (25% solid content, solvent: simethicone, manufactured by Shin-Etsu Chemical Co., Ltd.)

*28: KSG-43 (30% solid content, solvent: triglyceride 2-ethylhexanoate, manufactured by Shin-Etsu Chemical Co., Ltd.)

(Manufacturing method)

A. Disperse ingredients (1) to (3) uniformly.

B. After warming component (4) to component (11) to uniformly dissolve, add to A and mix uniformly.

C. Add component (12) to component (15) to B and mix them uniformly.

D. Mix component (16)~component (21) uniformly.

E. Slowly add D to C, and disperse and emulsify.

F: Degas E and fill it into the container.

The water-in-oil emulsified sunscreen cosmetic (liquid) of the present invention spreads lightly during application, and the applied cosmetic film has excellent water resistance and secondary adhesion prevention effects, and has no burden such as stiffness, and thus provides a moisturizing feeling The continuity is also excellent.

Example 26: Water-in-oil emulsified sunscreen cosmetic (solid)

(Manufacturing method)

A. Disperse ingredient (1) to ingredient (6) evenly.

B. After dissolving component (7) to component (13) uniformly, add to A and mix uniformly.

C. Add component (14) and component (15) to B and mix them uniformly.

D. Mix component (16) and component (17) uniformly.

E. Slowly add D to C, and disperse and emulsify.

F: After adding (18) and (19) to E, heating to 100°C and mixing and dissolving, the container is filled.

The water-in-oil emulsified sunscreen cosmetic (solid) of the present invention spreads lightly when applied, and the applied cosmetic film has excellent water resistance and secondary adhesion prevention effects, and has no burden such as stiffness, and thus provides a moisturizing feeling The continuity is also excellent.

Example 26: Water-in-oil emulsified sunscreen cosmetics (spray)

*29: KSP-100 (manufactured by Shin-Etsu Chemical Co., Ltd.)

*32: Godd Ball E-90C (manufactured by Suzuki Oil Industry Co.)

(Manufacturing method)

A. Disperse ingredient (1) to ingredient (5) uniformly.

B. After dissolving component (6) to component (11) uniformly, add to A and mix uniformly.

C. Mix component (12)~component (15) uniformly.

D. Slowly add C to B, and disperse and emulsify.

E: Fill the container so as to become (stock solution): (propellant)=30:70.

The water-in-oil emulsified sunscreen cosmetic (spray form) of the present invention spreads lightly when applied, and the applied cosmetic film has excellent water resistance and secondary adhesion prevention effects, and does not have a burden such as stiffness, thereby providing a moisturizing feeling The continuity is also excellent.

Claims (7)

A water-in-oil type emulsified cosmetic material, comprising the following components (A) to (D): (A) Alkyl acrylate·styrene copolymer dispersion with volatile hydrocarbon oil as a dispersion medium (B) Oil Soluble resin (C) polyol (D) partially cross-linked organopolysiloxane, the component (B) is selected from trimethylsilyloxysilicate, polymethylsilsesquioxane, (acrylic acid) (Ester/Dimethicone) copolymer, acrylic copolymer, dextrin fatty acid ester and hydrogenated rosin acid pentaerythritol one or more, the component (C) is selected from tripropylene glycol, dipropylene glycol and glycerin One or more than two. The water-in-oil type emulsified cosmetic according to the first item of the patent application, wherein the component (C) contains tripropylene glycol. The water-in-oil emulsified cosmetics described in item 1 or item 2 of the scope of patent application further includes ingredient (E) spherical silica. The water-in-oil emulsified cosmetics according to item 1 or item 2 of the scope of patent application, wherein the component (B) is selected from polymethylsilsesquioxane, (acrylate/dimethicone) copolymer One or more of pentaerythritol, dextrin fatty acid ester, acrylic copolymer, and hydrogenated rosin acid. Water-in-oil type emulsification as described in item 1 or item 2 of the scope of patent application Cosmetics, wherein the content of the component (C) is 3% by mass to 25% by mass of the water-in-oil emulsified cosmetics. The water-in-oil type emulsified cosmetic material described in item 1 or item 2 of the scope of patent application, wherein the content of the ingredient (A) is 0.1% by mass of the water-in-oil type emulsified cosmetic material in terms of solid content ~3% by mass. The water-in-oil emulsified cosmetic according to item 1 or 2 of the scope of patent application, wherein the content of the component (B) is 0.1% by mass to 10% by mass of the water-in-oil emulsified cosmetic.