JP6869942B2 - Water-in-oil emulsified cosmetics - Google Patents

Description

The present invention relates to a water-in-oil emulsified cosmetic, and more particularly to a water-in-oil emulsified cosmetic having an excellent effect of preventing secondary adhesion and an excellent usability.

Conventionally, water-in-oil emulsified cosmetics have been used as skin external preparations because oil-soluble active ingredients such as emollient oils, ultraviolet absorbers, and oil-soluble agents can be efficiently spread on the skin. It is a dosage form and is often used in make-up cosmetics because of its high water resistance. In recent years, due to the increasing demand for sports, there is a demand for cosmetics that can maintain a beautiful cosmetic film without being destroyed by a large amount of sweat or sebum. In addition, there is a rapidly increasing need for solving skin problems peculiar to menopause, and in particular, there is a demand for a cosmetic called "hot flash" that does not collapse even when suddenly a large amount of sweating occurs. In addition, since it is easy to feel the dryness of the skin after sweating, there is a demand for a cosmetic film having a long-lasting moisturizing feeling in these cosmetics having excellent water resistance and sebum resistance.
Conventionally, water-in-oil emulsified cosmetics have important functions such as water resistance and prevention of color transfer due to mixing with sebum (secondary adhesion prevention effect), and there are various methods for enhancing these functions. Consideration has been made. For example, by using a specific volatile organopolysiloxane, oil-soluble resin, water-repellent powder, and water in combination, a technology that improves lightness of elongation during application, non-stickiness, secondary adhesion prevention effect, and long-lasting makeup. (See Patent Document 1), contains (meth) acrylic acid / alkyl (meth) acrylic acid copolymer emulsion, partially crosslinked organopolysiloxane polymer, volatile silicone, and substantially no surfactant. Therefore, a technique for improving transparency, water resistance, skin oil resistance, smooth feel, and storage stability (see Patent Document 2), or a volatile oil agent, a resin that does not dissolve in the volatile oil agent, and a melting point of 75 ° C. or higher. Technology that improves the lightness of elongation at the time of application, smoothness, secondary adhesion prevention effect, water resistance, oil resistance, makeup retention, and uniformity of cosmetic film by using solid oil and dextrin fatty acid ester together. (See Patent Document 3) is known.

Japanese Unexamined Patent Publication No. 2006-290878 Japanese Unexamined Patent Publication No. 2006-008585 Japanese Unexamined Patent Publication No. 2008-255014

However, in the technique of improving the water resistance and the effect of preventing secondary adhesion by using an oil-soluble resin as in the technique of Patent Document 1, the decorative film becomes hard and gives a feeling of tension, and the solvent volatilizes and gives a feeling of dryness. There was a problem of feeling. Further, if the amount of the resin component is increased in order to enhance the effect, there is a drawback that the spread and spread at the time of application becomes heavy and the usability is impaired. Further, in the cosmetics obtained in Patent Document 2, the coating film is easily compatible with water, so that the water resistance is not sufficient, and the solvent tends to volatilize and a feeling of dryness is easily felt. Further, the cosmetic obtained in Patent Document 3 has a problem that the film formed by the high melting point wax gives a feeling of tension due to the hardness, and the solvent volatilizes and a feeling of dryness is felt.
Therefore, the spread and spread during application is light, and the cosmetic film after application has excellent water resistance and secondary adhesion prevention effect, but there is no feeling of tension and a feeling of moisturizing is also excellent. Providing cosmetics was an issue.

In such a situation, as a result of diligent research, the present inventors have conducted an alkyl-styrene copolymer dispersion using a volatile hydrocarbon oil as a dispersion medium, an oil-soluble resin, a polyhydric alcohol, and a partially crosslinked organopoly. By containing siloxane, the spread and spread during application is light, and the decorative film after application has excellent water resistance and secondary adhesion prevention effect, but there is no feeling of tension and a feeling of moisturization is also excellent. We have found that water-in-oil emulsified cosmetics can be obtained. The alkyl acrylate / styrene copolymer dispersion itself forms a film, but the partially crosslinked organopolysiloxane gives flexibility to the film with stronger bond points by combining with an oil-soluble resin. By adding it, the water resistance and the effect of preventing secondary adhesion are remarkably improved, and the cosmetic film, which has excellent followability to the skin and has an extremely low burden, blocks the polyhydric alcohol and suppresses the evaporation of water from the skin. Therefore, they have found that the sustainability of the moisturizing sensation is dramatically enhanced, and have completed the present invention.

That is, the present invention describes the following components (A) to (D);
(A) Alkyl acrylate / styrene copolymer dispersion using volatile hydrocarbon oil as a dispersion medium (B) Oil-soluble resin (C) Polyhydric alcohol (D) Partially crosslinked organopolysiloxane .
One or 2 in which the component (B) is selected from trimethylsiloxysilicic acid, polymethylsilsesquioxane, (Acrylate / dimethicone) copolymer, acrylic copolymer, dextrin fatty acid ester, and hydrogenated pentaerythrityl rosinate. More than a seed,
The component (C) is one or more selected from tripropylene glycol, dipropylene glycol, and glycerin .
The content of the component (A) is 0.1 to 10% by mass in the cosmetic in terms of solid content.
The content of the component (B) is 0.1 to 10% by mass in the cosmetic.
The content of the component (C) is 3 to 30% by mass in the cosmetic.
The content of the component (D) is 0.1 to 5% by mass in the cosmetic.
It is a water-in-oil emulsified cosmetic.

In the present invention, water in oil has a light spread and spread during application, and the decorative film after application has excellent water resistance and secondary adhesion prevention effect, but does not have a feeling of tension and a long-lasting moisturizing feeling. It is related to type emulsified cosmetics.

Hereinafter, the present invention will be described in detail.
The component (A) used in the present invention is a dispersion in which an alkyl acrylate / styrene copolymer is dispersed in a volatile hydrocarbon oil. The alkyl acrylate / styrene copolymer to be dispersed is listed as STYRENE / ACRYLATES COPOLYMER under the INCI name (International Nomenclature Cosmetic Ingredient labeling names), and is one or more of alkyl acrylate and alkyl methacrylate. It can be obtained by polymerizing styrene. These are in the form of dispersion without being dissolved in volatile hydrocarbon oil, and are generally referred to as non-aqueous dispersion (NAD = Non Aqua Dispersion, also synonymous with non-aqueous emulsion). The alkyl acrylate / styrene copolymer is not particularly limited, but one containing alkyl acrylate and alkyl methacrylate and styrene in a mass ratio of 70/30 to 90/10 is preferable, and the number average molecular weight is 50,000 to 300,000 (). The polystyrene-equivalent value obtained by gel permeation chromatography) is preferably used. Within this range, it does not dissolve in volatile hydrocarbon oil and a good dispersion state can be maintained. Further, when the average particle size of the resin particles by the centrifugal precipitation method is 0.1 to 2.0 μm, the change in the viscosity of the dispersion is small and the particles are less likely to precipitate, which is preferable.

The volatile hydrocarbon oil used as the dispersion medium of the component (A) is not particularly limited as long as it is generally used in cosmetics. For example, a hydrocarbon having a boiling point of 260 ° C. or lower at normal pressure, isooctane (2). , 2,4-trimethylpentane, 2,3-dimethylhexane, etc.), isododecane (2,2,4,6,6-pentamethylheptan, etc.), isohexadecane, isoeikosaene, and other hydrocarbons with side chains, isoparaffin, Alternatively, a mixture thereof, isobutene, n-butene, etc. may be polymerized or copolymerized (preferably having a degree of polymerization of 4 to 6) and then hydrogenated, etc., and one or more of them may be used as required. Can be used in combination. Among them, saturated hydrocarbon oil having a side chain having 4 to 18 carbon atoms is more preferable because it has good dispersibility of the alkyl acrylate / styrene copolymer, accelerates drying, and forms a strong coating film by volatilization. .. Commercially available products of these volatile hydrocarbon oils include IP Solvent 1620 MU, IP Solvent 2028 MU (all manufactured by Idemitsu Petrochemical Co., Ltd.), Isopar (manufactured by Esso Chemical Co., Ltd.), Marcazole R (manufactured by Maruzen Petrochemical Co., Ltd.), etc. Can be mentioned.

The component (A) is a dispersion obtained by dispersing an alkyl acrylate / styrene copolymer in a volatile hydrocarbon oil, and in the volatile hydrocarbon oil, it is mixed with alkyl acrylate or alkyl methacrylate. , In addition to being obtained by polymerizing styrene, the copolymer can be obtained by dispersing it in a volatile hydrocarbon oil. The alkyl acrylate / styrene copolymer is preferably contained in the component (A) in an amount of 30 to 60% by mass (hereinafter, simply referred to as “%”), more preferably 35 to 50%, still more preferably 40 to 40 to 50%. Contains 50%. Within this range, the component (A) is likely to be uniformly miscible in the cosmetic. As the component (A), a commercially available component (A) can be used, and examples thereof include Nisetsu U-3700A (manufactured by Nippon Carbide Co., Ltd.).

The content of the component (A) in the present invention is not particularly limited depending on the copolymer concentration, but is preferably 0.1 to 10% in the cosmetic in terms of solid content, and more preferably 0. It is 5 to 7.5%, particularly preferably 1 to 6%. This range is preferable in that it is superior in water resistance and no feeling of burden.

The oil-soluble resin of the component (B) used in the present invention is soluble in an oil agent such as volatile oil and forms a film. Anything normally used for cosmetics can be used without particular limitation. Since the component (B) has excellent sebum resistance and forms a hard and strong coating film, the component (B) is contained in combination with the component (A) to form a bonding point of the coating film formed by fusing the dispersion. By making it stronger, the effect of preventing secondary adhesion can be remarkably improved. Specific examples thereof include terpene-based resins, silicone resins, hydrocarbon resins, rosin-based resins, vinyl acetate-based resins, acrylic-based resins, etc., and one or a combination of two or more thereof may be used as necessary. Can be done.

Among them, silicone resins such as trimethylsiloxysilicic acid, polymethylsilsesquioxane, and (acrylate / dimethicone) copolymers are more preferable because they are more excellent in preventing secondary adhesion. Commercially available products include Silicon KF-7312J (solid content 50%, solvent: cyclopentasiloxane, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) and Silicon KF-9021 (solid content 50%, solvent: cyclopentasiloxane, manufactured by Shin-Etsu Chemical Industry Co., Ltd.). , BY11-018 (solid content 30%, solvent: cyclopentasiloxane, manufactured by Toray Dow Corning), Silicon KP-541 (solid content 60%, solvent: isopropanol, manufactured by Shin-Etsu Chemical Industry Co., Ltd.), SR-1000 (momentive) -Performance Materials Japan Co., Ltd.), Silicon KP-545 (solid content 30%, solvent: cyclopentasiloxane, manufactured by Shin-Etsu Chemical Industry Co., Ltd.), Silicon KP-575 (solid content 30%, solvent: cyclopentasiloxane, (Shinetsu Chemical Industry Co., Ltd.), SILFORM FLEXIBLE RESIN (manufactured by Momentive Performance Materials Japan), Opanol B-100 (manufactured by BASF) and the like.

Among them, as the component (B), the component (A): an acrylate and / or a methacrylate containing a cycloalkyl group, and the component (B): an acrylate containing a linear or branched alkyl group having 8 to 12 carbon atoms and / Or Methacrylate and / or (C): An acrylic copolymer obtained by polymerizing a monomer containing an organopolysiloxane macromonomer containing a radically polymerizable group at one end is also excellent in the effect of preventing secondary adhesion. Is preferable.
Specifically, the acrylic copolymer contains 50 to 90% by mass of the component (A) and 10 to 50% by mass of the components (B) and / or (C) in the total amount of the constituent monomers. More preferably, it is dissolved in light isoparaffin at 25 ° C. by at least 30% by mass.

Here, the light isoparaffin refers to a mixture of hydrocarbons mainly composed of isoparaffin, specifically a saturated hydrocarbon having a side chain and having 9 to 12 carbon atoms, and retained at 95% by volume in a distillation test of JIS-K2254. It means that the output temperature is 200 ° C or less.

The acrylic copolymer is preferably composed of a component (A) and a component (B), and is composed of a component (A) and a component (C), and is composed of a component (A), a component (B) and a component. It is composed of (C), and more preferably, it is composed of only the component (A) and the component (B), or only the component (A), the component (B) and the component (C).

Specifically, the acrylic copolymer requires a component (A), a component (B), a component (C), and an optional component as necessary, or a component (A) and a component (B). It can be obtained by polymerizing the optional component according to the above, or the component (A), the component (C) and, if necessary, the optional component in the presence of an organic solvent in the absence of water. ..

More specifically, the acrylic copolymer is composed of a component (A) and a component (B), and the component (B) is 10 to 50 parts by mass with respect to 50 to 90 parts by mass of the component (A). Is composed of an acrylic copolymer in which is polymerized, or a component (A) and a component (C), and 10 to 50 parts by mass of the component (C) is polymerized with respect to 50 to 90 parts by mass of the component (A). It is composed of the acrylic copolymer, the component (A), the component (B), and the component (C), and the total of the components (B) and (C) is 50 to 90 parts by mass of the component (A). An acrylic copolymer in which 10 to 50 parts by mass is polymerized can be preferably exemplified.

The cycloalkyl group-containing acrylate and / or methacrylate of the component (A) is a lipophilic polymerizable monomer and forms a skeleton having a water-resistant transparent and hard film-forming ability. Specific examples include cyclohexyl acrylate, cyclohexyl methacrylate, dicyclopentanyl acrylate, dicyclopentanyl methacrylate, tricyclodecyl acrylate, tricyclodecyl methacrylate, tricyclodecanyl acrylate, tricyclodecanyl methacrylate and the like. , These can be used alone or in combination of two or more. Among these, cyclohexyl methacrylate is particularly preferable because it has good radical polymerization property, high yield, and has a suitable glass transition point for forming a hard film.

The acrylate and / or methacrylate containing a linear or branched alkyl group having 8 to 12 carbon atoms of the component (B) is a lipophilic polymerizable monomer that imparts flexibility and adhesiveness to the film and becomes a light isoparaffin. Increases the solubility of. Specific examples include octyl acrylate, octyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, isononyl acrylate, isononyl methacrylate, lauryl acrylate, and lauryl methacrylate, which may be used alone or in combination of two. The above can be mixed and used. Among these, 2-ethylhexyl methacrylate and lauryl methacrylate are preferable, and 2-ethylhexyl methacrylate is particularly preferable.

式中、ｍは１〜１０、好ましくは１〜４、ｎは０〜２００の整数、Ｒ_１は、水素又はメチル基を示し、Ｒ_２〜Ｒ_８は、炭素数１〜５のアルキル基を示す。
これらは１種単独で又は２種以上混合して用いることができる。Examples of the organopolysiloxane macromonomer containing a radically polymerizable group at one end of the component (C) include an ester compound in which an organopolysiloxane is linked to acrylic acid or methacrylic acid via a divalent hydrocarbon group. Specifically, the 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 a hydrogen or methyl group, and R _{2 to} R ₈ represents an alkyl group having 1 to 5 carbon atoms. Shown.
These can be used alone or in combination of two or more.

ジメチルポリシロキサン基の繰返し単位を示す重合度ｎは０〜２００が好ましく、さらに好ましくは５〜１５０である。重合度ｎが５未満である場合には、充分な耐水性を得ることができないおそれがあり、１５０を超えると透明で均一な皮膜を得ることが困難になる場合がある。The organopolysiloxane macromonomer containing a radically polymerizable group at one end of the component (C) imparts water resistance to the film and enhances its solubility in light isoparaffin. More specifically, a dimethylpolysiloxane macromonomer represented by the general formula (1) can be mentioned.

The degree of polymerization n indicating the repeating unit of the dimethylpolysiloxane group is preferably 0 to 200, more preferably 5 to 150. If the degree of polymerization n is less than 5, sufficient water resistance may not be obtained, and if it exceeds 150, it may be difficult to obtain a transparent and uniform film.

The acrylic copolymer preferably contains only the component (A) and the component (B) in order to enhance the effect of the present invention, with cyclohexyl methacrylate as the component (A) and 2-ethylhexyl methacrylate as the component (B). A methacrylate / ethylhexyl methacrylate copolymer using the above is particularly preferable.
Here, the content ratio of cyclohexyl methacrylate to 2-ethylhexyl methacrylate in the methacrylohexyl / ethylhexyl methacrylate copolymer is preferably 0.5: 1 to 5: 1, preferably 2: 1 to 5: 1. More preferably, it is more preferably 2: 1 to 4: 1, and particularly preferably 2.5: 1 to 4: 1.
Examples of commercially available products include plastic size L-250 manufactured by GOO CHEMICAL CO., LTD.

Further, the acrylic copolymer of the component (B) can contain a polymerizable monomer other than the above components (A) to (C) as a constituent monomer as long as the effect of the present invention is not impaired. The polymerizable monomer other than the components (A) to (C) is not particularly limited, but styrene, substituted styrene, vinyl acetate, acrylic acid, methacrylic acid, acrylic acid esters and methacrylic acid esters other than the above, maleic anhydride, Maleic acid ester, fumaric acid ester, vinyl chloride, vinylidene chloride, ethylene, propylene, butadiene, acrylonitrile, fluorinated olefin, acrylamide, methacrylic acid, methyl acrylamide, methyl methacrylate, dimethyl methacrylate, N-isopropylacrylamide, N-vinyl Pyrrolidone, N-vinylacetamide, t-butyl acrylate, t-butyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, dimethylaminoethyl methacrylate, dimethylaminoethyl methacrylate, 2-acrylamide-2-dimethylpropane sulfonate, etc. be able to.

As for the compounding ratio of the components (A) to (C) and the optional components, the compounding amount of the component (A) is 50 to 90% by mass, preferably 50 to 80% by mass, based on the total amount of the constituent monomers. If it is less than 50% by mass, a film having sufficient hardness cannot be obtained, and if it exceeds 90% by mass, its solubility in light isoparaffin is deteriorated. The blending amount of the component (B) is 10 to 50% by mass, preferably 15 to 45% by mass, based on the total amount of the constituent monomers. If it is less than 10% by mass, the solubility in light isoparaffin is deteriorated, and if it exceeds 50% by mass, a film having sufficient hardness cannot be obtained, which has drawbacks such as stickiness, tackiness and non-uniformity of the film. Occurs. The blending amount of the component (C) is 10 to 50% by mass, preferably 15 to 45% by mass, based on the total amount of the constituent monomers. If it is less than 10% by mass, the solubility in light isoparaffin is deteriorated, and if it exceeds 50% by mass, a film having sufficient hardness cannot be obtained, and there are drawbacks such as stickiness, tackiness and non-uniformity of the film. Occurs. When the component (B) and the component (C) are used in combination, the total amount thereof is 10 to 50% by mass, preferably 15 to 45% by mass. If the total amount of the component (B) and the component (C) exceeds 50% by mass, a film having sufficient hardness cannot be obtained, and there are drawbacks such as stickiness, tackiness, and non-uniformity of the film. If the total amount is less than 10% by mass, the solubility in light isoparaffin is deteriorated. The blending amount of the optional component may be in the range of 30% by mass or less of the total amount of the constituent monomers, preferably 20% by mass or less, and for example, 0.01 to 10% by mass can be blended.

The weight average molecular weight of the acrylic copolymer is not particularly limited, preferably in the range of ^{1.0 × 10 4 ~2.0 × 10 5} . The weight average molecular weight is measured by liquid gel permeation chromatography (GPC) using tetrahydrofuran as the eluent and a calibration curve prepared with a linear polystyrene standard and a refractometer. Weight average molecular weight is slightly inferior to the film-forming at 1.0 × 10 ⁴ or less, 2.0 × slightly inferior undesirable uniformity of high coating solution viscosity in light isoparaffin in the 10 ⁵ or more.

The acrylic copolymer uses the above components (A) to (C) and, if necessary, other arbitrary components as constituent monomers, and is a known polymerization method in the presence of an organic solvent (in the absence of water). It can be obtained by random polymerization according to. Although not particularly limited, organic peroxides such as benzoyl peroxide and lauroyl peroxide, α, α'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 2, The polymerization may be carried out in the presence of a radical polymerization initiator such as an azo compound such as 2'-azobis (2-methylbutyronitrile), a persulfate-based polymerization initiator such as potassium persulfate and ammonium persulfate, and a solution. A polymerization method, a suspension polymerization method, a massive polymerization method, a precipitation polymerization method and the like can be used. Of these, the solution polymerization method is particularly preferable because it is easy to adjust the molecular weight of the obtained acrylic copolymer in the optimum range.

Examples of the organic solvent used in the polymerization of the acrylic copolymer include aromatic hydrocarbons such as benzene, toluene and xylene, ketones such as methyl ethyl ketone and methyl isobutyl ketone, esters such as ethyl acetate and butyl acetate, and isopropanol. Alcohols such as ethanol and methanol can be mentioned, and one or a combination of two or more of these can be used. It can also be polymerized in paraffinic solvents 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 a temperature range in which a normal radical polymerization initiator can be used, but it is usually carried out in the range of 40 to 120 ° C. The reaction temperature varies depending on the radical polymerization initiator used, the type of monomer, and the reaction temperature, but is usually carried out for 2 to 24 hours. If the polymerization time is too short, the amount of residual monomers is large and the yield is low, which is not preferable.

The acrylic copolymer can be dissolved in the paraffin solvent at the time of reaction, or if necessary, diluted with other oils such as hydrocarbons, esters, triglycerides, etc., or to other oils. Solvent substitution can also be performed. An acrylic copolymer composition containing such an oil-soluble cycloalkyl group is also included in the present invention. Further, the acrylic copolymer can be taken out as a solid by removing the solvent of the solution, and the obtained acrylic copolymer polymer can be used as an acrylic copolymer solution by dissolving it in light isoparaffin. You can also do it. The above acrylic copolymer and its solution can be used by mixing two or more kinds.

The component (B) is a fatty acid ester of dextrin having an average degree of polymerization of glucose of 3 to 150, and the branched saturated fatty acid having 4 to 26 carbon atoms is more than 50 mol% and 100 mol% or less based on the total fatty acid. One or two selected from the group consisting of linear saturated fatty acids having 2 to 22 carbon atoms, linear or branched unsaturated fatty acids having 6 to 30 carbon atoms, and cyclic saturated or unsaturated fatty acids having 6 to 30 carbon atoms. Dextrin fatty acid esters containing 0 mol% or more and less than 50 mol% of all fatty acids and having a fatty acid substitution degree of 1.0 to 3.0 per glucose unit are also preferably used.

A suitable dextrin fatty acid ester is an esterified product of dextrin and fatty acid, and the degree of substitution of fatty acid with dextrin is 1.0 to 3.0, preferably 1.2 to 2.8 per glucose unit. .. If the degree of substitution is less than 1.0, the dissolution temperature in liquid oil or the like becomes as high as 100 ° C. or higher, and coloring or a peculiar odor is generated, which is not preferable.

Suitable dextrin fatty acid esters have the following properties:
1) Suitable dextrin fatty acid esters do not gel when mixed with liquid oil.
“Liquid oil does not gel” means that when liquid paraffin having a kinematic viscosity at 40 ° C. of 8 mm ² / s according to the ASTM D445 measuring method is used as the liquid oil, the flow containing 5% by mass of a suitable dextrin fatty acid ester. When paraffin was melted at 100 ° C and the viscosity was measured at 25 ° C after 24 hours, the viscosity was below the detection limit of the Yamaco DIGITAL VISCOMATE viscometer VM-100A (vibration type) (manufactured by Yamaichi Denki Co., Ltd.). means. In the case of gelation, it can be confirmed by detecting the viscosity.
2) The film formed by a suitable dextrin fatty acid ester has a specific range of tackiness.
For "tackiness", the dextrin fatty acid ester is applied to the support, and the other supports are brought into surface contact with each other from a state of being separated from each other, and then retracted and separated, and then completely separated after the receding is started. When expressed by the load change (maximum stress value) applied to the contact point, a light fluid isoparaffin solution containing 40% by mass of the dextrin fatty acid ester was formed on a glass plate with a 400 μm-thick applicator, and the film was dried. , Texture Analyzer, eg Texture Analyzer TA. Using XTplus (manufactured by Table Micro Systems), a probe made of a 12.5 mm diameter columnar polyacetal resin (manufactured by Delrin (registered trademark) DuPont) was used as a probe, and a load of 100 g was applied and held for 10 seconds. The load change when separated at 5 mm / sec, that is, the tackiness is 30 to 1,000 g.

The dextrin used in a suitable dextrin fatty acid ester is preferably a dextrin having a glucose average degree of polymerization of 3 to 150, particularly 10 to 100. When the average degree of polymerization of glucose is 2 or less, the obtained dextrin ester becomes wax-like and the solubility in the oil agent is lowered. On the other hand, if the average degree of polymerization of glucose exceeds 150, problems such as an increase in the dissolution temperature of the dextrin ester in an oil agent or a decrease in solubility may occur. The sugar chain of dextrin may be linear, branched or cyclic.

The fatty acid used in a suitable dextrin fatty acid ester requires one or more branched saturated fatty acids having 4 to 26 carbon atoms, and further has a linear saturated fatty acid having 2 to 22 carbon atoms and 6 to 30 carbon atoms. One or more selected from the group consisting of linear or branched unsaturated fatty acids and cyclic saturated or unsaturated fatty acids having 6 to 30 carbon atoms (hereinafter, other than these branched saturated fatty acids having 4 to 26 carbon atoms). When fatty acids are collectively represented, they may contain (referred to as "other fatty acids").

In a preferred form, the composition ratio of the fatty acid is 100 mol% or less, preferably 55 mol% or more and 100 mol% or less, in which one or more of the branched saturated fatty acids having 4 to 26 carbon atoms are more than 50 mol% and 100 mol% or less with respect to the total fatty acids. Other fatty acids are 0 mol% or more and less than 50 mol%, preferably 0 mol% or more and 45 mol% or less.

Examples of the branched saturated fatty acids having 4 to 26 carbon atoms used in the preferred form include isobutyric acid, isovaleric acid, 2-ethylbutyric acid, ethylmethylacetic acid, isoheptanic acid, 2-ethylhexanoic acid, isononanoic acid and isodecanoic acid. Examples thereof include isotridecanoic acid, isomyristic acid, isopalmitic acid, isostearic acid, isoaraquinic acid, isohexacosanoic acid and the like, and one or more of these can be appropriately selected or used in combination. Of these, those having 12 to 22 carbon atoms are preferable, isostearic acid is particularly preferable, and there are no particular restrictions such as structural differences.

In a preferred form, isostearic acid means one or a mixture of two or more branched stearic acids. For example, 5,7,7-trimethyl-2- (1,3,3-trimethylbutyl) -octanoic acid is converted into a branched aldehyde having 9 carbon atoms by an oxo reaction of an isobutylene dimer, and then carbon is produced by aldol condensation of this aldehyde. It can be produced by preparing a branched unsaturated aldehyde of number 18 and then hydrogenating and oxidizing it (hereinafter abbreviated as "aldol condensation type"), which is commercially available from, for example, Nissan Chemical Industry Co., Ltd. 2-Heptylundecanoic acid can be produced by subjecting a nonyl alcohol to a Guerbet reaction and then oxidizing it, which is commercially available, for example, from Mitsubishi Kasei Corp. and is a similar mixture with slightly different branching positions. The type that is commercially available from Nissan Chemical Industries, Ltd., and the starting alcohol is not linearly saturated and has two methyl branches is also commercially available from Nissan Chemical Industries, Ltd. (hereinafter abbreviated as "Gervet reaction type"). .. Methyl-branched isostearic acid is obtained, for example, as a by-product of oleic acid during dimer production [for example, J. Amer. Oil Chem. Soc. , 51, 522 (1974)], for example, those commercially available from Emery, Inc. of the United States (hereinafter abbreviated as "emery type"). Further starting material of dimer acid, which is a starting material of emery-type isostearic acid, may include not only oleic acid but also linoleic acid, linolenic acid and the like. In the present invention, this emery type is particularly preferable.

Examples of the linear saturated fatty acid having 2 to 22 carbon atoms used in the preferred form include acetic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, araquinic acid, behenic acid and the like. One or more of these may be appropriately selected or used in combination. Of these, those having 8 to 22 carbon atoms are preferable, and those having 12 to 22 carbon atoms are particularly preferable.

As the linear or branched unsaturated fatty acid having 6 to 30 carbon atoms used in the preferred form, for example, as the monoene unsaturated fatty acid, cis-4-decene (obtusyl) acid, 9-decene (caproleine) acid, cis -4-dodecene (lindel) acid, cis-4-tetradecene (tsuzu) acid, cis-5-tetradecene (fiseterin) acid, cis-9-tetradecene (myristolene) acid, cis-6-hexadecenoic acid, cis- 9-Hexadecene (palmitoleic) acid, cis-9-octadecenoic acid (olein) acid, trans-9-octadecenoic acid (ellaic acid), cis-11-octadecenoic acid (asklepin) acid, cis-11-eicocenic acid (gondrain) acid, Examples include cis-17-hexacosene (ximene) acid, cis-21-triaconenic acid (lumecene) acid, and examples of polyene unsaturated fatty acids include sorbic acid, linoleic acid, hirago acid, punicic acid, linolenic acid, and γ-linolene. Examples thereof include acids, moroctic acid, stearidonic acid, arachidonic acid, EPA, sardine acid, DHA, heric acid, stearolic acid, crepenic acid, ximenic acid and the like.

The cyclic saturated or unsaturated fatty acid having 6 to 30 carbon atoms used in the preferred form means a saturated or unsaturated fatty acid having 6 to 30 carbon atoms having a cyclic structure in at least a part of the basic skeleton, for example, 9,10. -Methylene-9-octadecenoic acid; arepric acid, arepric acid, gorphosphate, α-cyclopentyl acid, α-cyclohexyl acid, α-cyclopentylethyl acid, α-cyclohexylmethyl acid, ω-cyclohexyl acid; Examples thereof include -4-hexyl-2-cyclohexene-1-octanoic acid, malvalic acid, sterclinic acid, hydnocarpine acid and shohlmuglycic acid.

In a preferred form, examples of the dextrin fatty acid ester when the branched saturated fatty acid is used alone as the fatty acid include the following.
Dextrin Isobutyric Acid Ester Dextrin Ethylmethyl Acetate Ester Dextrin Isoheptanic Acid Ester Dextrin 2-Ethylhexanoic Acid Ester Dextrin Isononanoic Acid Ester Dextrin Isodecanoic Acid Ester Dextrin Isopalmitic Acid Ester Dextrin Isostearic Acid Ester Dextrin Isoaraquinic Acid Ester Dextrin (isovaleric acid / isostearic acid) ester

In a preferred form, examples of the dextrin fatty acid ester when a mixed fatty acid of a branched saturated fatty acid and another fatty acid are used as the fatty acid include the following.
Dextrin (isobutyric acid / capric acid) ester Dextrin (2-ethylhexanoic acid / capric acid) ester Dextrin (isoarakinic acid / capric acid) ester Dextrin (isopalmitic acid / capric acid) ester Dextrin (ethylmethylacetic acid / 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 (isohexacosanoic 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 / caproic acid) Ester dextrin (2-ethylhexanoic acid / palmitic acid / stearer) Acid) Ester dextrin (isodecanoic acid / palmitic acid) Ester dextrin (isopalmitic acid / stearic acid) Ester dextrin (isostearic acid / araquinic acid) Ester dextrin (2-ethylhexanoic acid / araquinic acid) Ester dextrin (2-ethylbutyric acid / Behenic acid) Ester dextrin (isononanoic acid / linoleic acid) Ester dextrin (isopalmitic acid / arachidonic acid) Ester dextrin (isopalmitic acid / capric acid / linoleic acid) Ester dextrin (isostearic acid / stearic acid / oleic acid) Ester dextrin (isostearic acid / stearic acid / oleic acid) Isoaraquinic acid / palmitic acid / shoal muglic acid) ester

Next, a method for producing a suitable dextrin fatty acid ester will be described.
The production method is not particularly limited, and a known production method can be adopted, and for example, it can be produced as follows.

1) Dextrin having an average degree of polymerization of glucose of 3 to 150 and one or more branched saturated fatty acid derivatives having 4 to 26 carbon atoms are contained in an amount of more than 50 mol% and 100 mol% or less based on all fatty acid derivatives. One selected from the group consisting of linear saturated fatty acid derivatives having 2 to 22 carbon atoms, linear or branched unsaturated fatty acid derivatives having 6 to 30 carbon atoms, and cyclic saturated or unsaturated fatty acid derivatives having 6 to 30 carbon atoms. Alternatively, two or more kinds (hereinafter, referred to as "other fatty acid derivatives" when these fatty acid derivatives are collectively represented) are reacted with a fatty acid derivative containing 0 mol% or more and less than 50 mol% with respect to all fatty acid derivatives.

2) Dextrin having an average degree of polymerization of glucose of 3 to 150 is reacted with one or more branched saturated fatty acid derivatives having 4 to 26 carbon atoms, and then the product and other fatty acid derivatives are reacted. React.
In that case, one or more of the branched saturated fatty acid derivatives having 4 to 26 carbon atoms are more than 50 mol% and 100 mol% or less with respect to the total fatty acid derivatives, and 0 mol% of the other fatty acid derivatives with respect to the total fatty acid derivatives. Use more than 50 mol%.

In a preferred form, as the fatty acid derivative used in the esterification reaction with the dextrin, for example, a halide of the fatty acid, an acid anhydride or the like is used.
In both cases 1) and 2), first, dextrin is dispersed in a reaction solvent, and a catalyst is added if necessary. To this, a halide of the above fatty acid, an acid anhydride or the like is added and reacted. In the case of the production method of 1), these acids are mixed and subjected to simultaneous addition reaction, and in the case of the production method of 2), a branched saturated fatty acid derivative having low reactivity is first reacted, and then other fatty acid derivatives are reacted. Is added and reacted.

Of these, the preferred method can be adopted in the production. As the reaction solvent, a formamide type such as dimethylformamide or formamide; an acetamide type; a ketone type; an aromatic compound type such as benzene, toluene or xylene; or a solvent such as dioxane can be appropriately used. As the reaction catalyst, a tertiary amino compound such as pyridine or picoline can be used. The reaction temperature is appropriately selected depending on the raw material fatty acid and the like, but a temperature of 0 ° C. to 100 ° C. is preferable.

An example of production of an example of the present invention (example of production of dextrin isostearic acid (emery type) ester) is described below.
21.41 g (0.132 mol) of dextrin having an average glucose polymerization degree of 30 was dispersed at 70 ° C. in a mixed solvent consisting of 71 g of dimethylformamide and 62 g (0.666 mol) of 3-methylpyridine, and 120 g of isostearic acid chloride (emery type). (0.396 mol) is added dropwise over 30 minutes. After completion of the dropping, the reaction temperature is set to 80 ° C. and the reaction is carried out for 5 hours. After completion of the reaction, the reaction solution is dispersed in methanol and the upper layer is removed. The semi-solid content is washed with methanol several times and then dried to obtain 107 g of a pale yellow resinous substance.
For resinous materials obtained by the above example, derived dextrin from IR spectrum 1000 to 1200 ^-1, derived from ester 1742 cm ^-1, can see a peak derived from alkyl 2800 to 3000 cm ^-1, also after alkali decomposition From the amount of fatty acid and gas chromatography, it can be confirmed that the degree of substitution is 2.2, isostearic acid 60 mol%, and other fatty acids 40 mol% (including palmitic acid 10 mol%).

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

The content of the component (B) in the present invention is not particularly limited, but is preferably 0.1 to 10%, more preferably 0.3 to 8%, and particularly preferably 0.5 to 5% in the cosmetic. %. This range is preferable in that it is more excellent in the effect of preventing secondary adhesion.

The polyhydric alcohol of the component (C) used in the present invention can be used without particular limitation as long as it is usually used in cosmetics, and specifically, propylene glycol, dipropylene glycol, butylene glycol, or tri. Examples thereof include propylene glycol, caprylyl glycol, glycerin, diglycerin, ethylene glycol, polyethylene glycol, hexanediol and the like, and one or a combination of two or more can be used as required. When the component (C) is combined with the component (A), it acts as a lubricant to reduce the spread and spread during application, and by being blocked in the coating film, it suppresses the evaporation of water from the skin and gives a moisturizing feeling. Can dramatically increase the sustainability of. Among them, tripropylene glycol (INCI name, TRIPROPPYLENE GLYCOL or PPG-3) realizes light spread and spread without stickiness until the end, and also has excellent skin compatibility, so it stands out for its long-lasting moisturizing feeling. It is more preferable in that it is excellent. Examples of commercially available products include Nieuport PP-200 (manufactured by Sanyo Chemical Industries, Ltd.).

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%. This range is preferable in that it is more excellent in lightness of spreading and spreading and maintenance of moisturizing feeling.

In the embodiment of the present invention, it is particularly preferable to use a methacrylic acid / ethylhexyl methacrylate copolymer, which is a resin having a fast film formation, as the component (B) and tripropylene glycol as the component (C) in combination. ..

The partially crosslinked organopolysiloxane of the component (D) used in the present invention is an organopolysiloxane polymer having a three-dimensional crosslinked structure, and can be used without particular limitation as long as it is usually used for cosmetics. it can. Specifically, partially cross-linked methylpolysiloxanes such as (dimethicone / vinyldimethicone) crosspolymers, partially cross-linked methylphenylpolysiloxanes such as (dimethicone / phenyldimethicone) crosspolymers, (vinyldimethicone / lauryldimethicone) crosspolymers, Partially cross-linked alkyl-modified silicone such as (dimethicone / phenylvinyl dimethicone) cross-polymer, partially cross-linked silicone / alkyl co-modified silicone such as (laurylpolydimethylsiloxyethyl dimethicone / bisvinyl dimethicone) dimethicone / (PEG-10) / 15)) Partially crosslinked polyether-modified silicone such as crosspolymer, partially crosslinked alkyl-polyether co-modified silicone such as PEG-15 lauryl dimethicone crosspolymer, (PEG-15 / laurylpolydimethylsiloxyethyl dimethicone) crosspolymer Partially crosslinked silicone / alkyl / polyether co-modified silicone, (dimethicone / polyglycerin-3) partially crosslinked polyglycerin modified silicone such as crosspolymer, (lauryl / polyglycerin-3) partially crosslinked polymer, etc. Alkyl polyglycerin co-modified silicone, (polyglyceryl-3 / lauryl polydimethylsiloxyethyl dimethicone) cross-polymer, etc. Partially cross-linked silicone alkyl-polyglycerin co-modified silicone, trifluoropropyl dimethicone / trifluoropropyl divinyl dimethicone) cross polymer Such as partially crosslinked type fluorine-modified silicone and the like can be mentioned, and one type or a combination of two or more types can be used as required.
The partially crosslinked polymer means a cross-linked polymer.

By combining the component (D) with the components (A) and (B), it is possible to impart flexibility to the oil-soluble resin and realize a decorative film with extremely little burden. When the component (D) is swollen with an oil agent, it is uniformly dispersed, the effect of improving the hardness of the cosmetic film becomes more remarkable, and it is often marketed as a mixture with an oil agent. -15 (solid content 5%), KSG-16 (solid content 20-30%), KSG-18 (solid content 10-20%), KSG-41A (solid content 20-30%), KSG-042Z (solid content 20-30%) Minutes 15 to 25%), KSG-210 (solids 20 to 30%), KSG-310 (solids 25 to 35%), KSG-320Z (solids 20 to 30%), KSG-710 (solids 20) ~ 30%), KSG-810 (solid content 25-35%), KSG-820Z (solid content 20-30%), KSG-850Z (solid content 20-30%), KSG-1510 (solid content 5-10) %), KSG-1610 (solid content 15 to 20%), KSG-18A (solid content 10 to 20%), KSG-016F (solid content 20 to 30%), KSG-045Z (solid content 15 to 25%) , KSG-048Z (solid content 15-25%), KSG-240 (solid content 15-25%), KSG-320Z (solid content 20-30%), KSG-350Z (solid content 20-30%), KSG -360Z (solid content 30-40%), KSG-380Z (solid content 25-35%), KSG-41 (solid content 25-35%), KSG-42 (solid content 20-30%), KSG-43 (Solid content 25-35%), KSG-44 (Solid content 25-35%), KSG-310 (Solid content 25-35%), KSG-320 (Solid content 20-30%), KSG-330 (Solid content 20-30%) Minutes 15-25%), KSG-340 (solids 25-35%), KSG-340 (solids 25-35%), KSG-710 (solids 20-30%), KSG-51 (solids 15) ~ 25%) (above, manufactured by Shin-Etsu Chemical Co., Ltd.) and the like.

In the embodiment of the present invention, as the component (D), a partially crosslinked polyglycerin-modified silicone and a partially crosslinked silicone / alkyl / polyglycerin co-modified silicone are preferable, and specifically, KSG-710 and KSG-820Z. , KSG-850Z is preferable.
In the embodiment of the present invention, as the component (D), in particular, a partially crosslinked polyglycerin-modified silicone and / or a partially crosslinked silicone / alkyl / polyglycerin co-modified silicone, a partially crosslinked methylpolysiloxane, and / Alternatively, a combination with a partially crosslinked methylphenyl polysiloxane and / or a partially crosslinked silicone / alkyl co-modified silicone is preferable, and specifically, KSG-710, KSG-820Z, KSG-850Z, and KSG-15. , KSG-1510, KSG-16, KSG-1610, KSG-18A, KSG-19, KSG-016F, KSG-042Z, KSG-045Z, KSG-048Z.
In the embodiment of the present invention, as the component (D), in particular, a partially crosslinked polyglycerin-modified silicone and / or a partially crosslinked silicone / alkyl / polyglycerin co-modified silicone, a partially crosslinked polyether-modified silicone, and / Or, a combination with a partially crosslinked silicone / alkyl / polyether co-modified silicone is preferable, specifically, KSG-710, KSG-820Z, KSG-850Z, and KSG-210, KSG-240, KSG-320Z. , KSG-350Z, KSG-360Z, KSG-380Z in combination is preferable.

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%, and particularly preferably 0.5 to 3%. This range is preferable in that a cosmetic film with less burden can be obtained.

Further, when the water-in-oil emulsified cosmetic of the present invention contains the component (E) spherical silica, it is preferable because the lightness of spreading and spreading at the time of application can be remarkably enhanced. As the component (E), any one used in ordinary cosmetics can be used, but one having an average particle size of 1 to 30 μm, preferably 3 to 15 μm, has good spreadability. It is more preferable in that it is more excellent. The average particle size is determined by a Coulter counter. Examples of commercially available products include Sunsphere NP-100 (manufactured by AGC SI Tech Co., Ltd.) and the like.

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%. Within this range, a more satisfactory product can be obtained in that it is excellent in lightness of spread and spread.

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

In addition to the above components, the water-in-oil emulsified cosmetic of the present invention includes oils such as solid oils, semi-solid oils, and liquid oils, surfactants, gelling agents, polymers, and colorants that are usually used in cosmetics. , Powder, ultraviolet absorber, preservative, antibacterial agent, antioxidant, fragrance, beauty ingredient and the like can be appropriately contained within a range that does not interfere with the effects of the present invention.

Examples of oils include liquid paraffin, liquid oil such as squalane, solid oil such as paraffin wax, ceresin wax, microcrystallin wax, polyethylene wax, and Fishertropch wax, olive oil, castor oil, jojoba oil, mink oil, macadamian nut oil, etc. Esters such as fats and oils, cetyl isooctanate, isopropyl myristate, isopropyl myristate, octyldodecyl myristate, isotridecyl isononanoate, cholesterol fatty acid ester, di-lauroyl-L-glutamate (cholesteryl behenyl octyldodecyl) , 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, bechenic acid, isostearic acid, oleic acid, 12-hydroxystearic acid, poly-12-hydroxystearic acid, fatty acid soaps, acylglutamates, alkyl phosphates, etc. Anionic surfactants such as polyoxyalkylene-added alkyl phosphates, cationic surfactants such as alkylamine salts and alkyl quaternary ammonium salts, glycerin fatty acid esters and their alkylene glycol adducts, propylene glycol fatty acid esters And alkylene glycol adducts thereof, sorbitan fatty acid esters and alkylene glycol adducts thereof, sucrose fatty acid esters, polyoxyalkylene-modified organopolysiloxanes, glycerin-modified organopolysiloxanes and other nonionic surfactants.

As the gelling agent, as a polymer such as dextrin palmitate, (palmitic acid / ethylhexanoic acid) dextrin, inulin stearate, organically modified bentonite, fumigant anhydrous silicic acid, aluminum isostearate, zinc stearate, magnesium stearate, etc. Carrageenan, xanthan gum, methyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, carboxyvinyl polymer, alkyl-modified carboxyvinyl polymer, polyvinyl alcohol, polyvinyl pyrrolidone, etc. As UV absorbers, silicic acid derivatives, aminobenzoic acid derivatives, salicylic acid derivatives, etc. Examples include benzophenone derivatives, phenylbenzoimidazole derivatives, phenylbenzotriazole derivatives, and preservatives such as paraoxybenzoic acid derivatives, phenoxyethanol, and alkanediol, and beauty ingredients such as rosemary extract, chamomile extract, collagen, hyaluronic acid, and ceramide. Can be mentioned.

The colorant and powder are not particularly limited by the shape of a plate, a spindle, a needle, etc., the particle size of a fumes, fine particles, pigment grade, etc., and the particle structure of porous, non-porous, etc., and are inorganic. Examples thereof include powders, glittering powders, organic powders, pigment powders, and composite powders. Specifically, Conjo, 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 titanium nitride, bright powders such as bismuth oxychloride and aluminum powder, organic powders such as silicone powder and polyethylene powder, organic tar pigments, and dye powders such as rake pigments of organic pigments. , Titanium oxide coated mica, iron oxide treated mica, iron oxide coated mica titanium, organic pigment treated mica titanium, silicon dioxide / titanium oxide coated mica, titanium oxide coated glass powder, iron oxide titanium oxide coated glass powder, titanium oxide containing silicon dioxide , Composite powder such as barium sulfate-coated titanium dioxide, polyethylene terephthalate / aluminum / epoxy laminated powder, polyethylene terephthalate / polymethylmethacrylate laminated film powder, etc., and one or more of these can be used. May be treated with one or more of fluorine-based compounds, silicone-based compounds, metal soaps, lecithin, hydrocarbons, higher fatty acids, higher alcohols, esters, waxes, surfactants and the like.

The water-in-oil emulsified cosmetic of the present invention can be applied to foundations, foundations, beauty essences, sunscreen cosmetics, etc., and preferably, the foundations, foundations, BB creams, etc., which are expected to exhibit the effects of the present application. Makeup cosmetics, more preferably foundations. Examples of the method of use include a method of using with hands and fingers, a method of impregnating with a puff, a sponge, or the like. In addition, the properties can be implemented as cosmetics having various properties such as gel and liquid.

Hereinafter, the present invention will be described in detail with reference to examples. It should be noted that these do not limit the present invention in any way.
Examples 1 to 20 and Comparative Examples 1 to 5: Water-in-oil emulsified foundation (liquid)
The water-in-oil emulsified foundation of the formulation shown in Table 1 below was prepared, and the water resistance, the effect of preventing secondary adhesion, the lightness of spreading and spreading, the feeling of no burden, and the duration of the moisturizing feeling were evaluated by the following methods. The results are also shown in Table 1.

* 1: Ceramide 2 0.2%, (palmitate / ethylcaproic acid) dextrin 1.8% treatment * 2: Isostearate isopropyltitanium triisostearate 3%, hydrogen dimethicone 5% treatment * 3: SILFROM FLEXIBLE RESIN (momentive performance)・ Materials Japan)
* 4: Nissetu U-3700A (manufactured by Nippon Carbide Industry Co., Ltd.)
* 5: Silicon KSG-710 (solid content 25%, solvent: dimethicone, manufactured by Shin-Etsu Chemical Co., Ltd.)
* 6: Silicon KSG-16 (solid content 25%, solvent: dimethicone, manufactured by Shin-Etsu Chemical Co., Ltd.)
* 7: Sunsphere NP-100 (manufactured by AGC SI Tech)
* 8: Yodosol GH41F (manufactured by AkzoNobel)
* 9: Nieuport PP-200 (manufactured by Sanyo Chemical Industries, Ltd.)
* 30: Prepared as follows.
Nitrogen gas was introduced by adding 22.5 g of cyclohexyl methacrylate, 7.5 g of 2-ethylhexyl methacrylate and 70 g of toluene to a four-port separable flask equipped with a reflux condenser, a thermometer, a nitrogen introduction tube and a stirrer. After the nitrogen atmosphere was sufficiently adjusted, the mixture was heated to 100 ° C., 0.15 g of AIBN was added, and the mixture was refluxed for 3 hours for polymerization. Methanol was injected into the obtained reaction product to precipitate and precipitate an acrylic copolymer, and the precipitate was filtered off and then vacuum dried to obtain 27.4 g of a cycloalkyl group-containing acrylic copolymer solid content. The weight average molecular weight terms of polystyrene was 5.0 × 10 ^4.
* 31: Ester gum HP (manufactured by Arakawa Chemical Industry Co., Ltd.)

(Production method)
A. The components (1) to (9) are uniformly dispersed.
B. The components (10) to (16) and (32) to (36) are heated and uniformly dissolved, and then added to A and uniformly mixed.
C. Ingredients (17) to (24) are added to B and mixed uniformly.
D. The components (25) to (31) are uniformly mixed.
E. D is gradually added to C for dispersion emulsification.
F: E is defoamed and filled in a container.

(Evaluation method)
The following evaluation items a to e were evaluated by the following methods.
(Evaluation item)
I. Water resistance b. Secondary adhesion prevention effect After 3 hours have passed, 20 specialist panels were asked to apply the sample, and for evaluation item A, the cotton moistened with water was pressed against the skin for 10 seconds, and the color of the cotton after peeling off was changed. The degree of transfer was evaluated, and for the evaluation item b, the degree of color transfer to the tissue after being lightly pressed with a tissue was evaluated. Each person in the panel evaluated in 5 stages by the following absolute evaluation, calculated the average value for each sample, and judged according to the following judgment criteria.
<Absolute evaluation criteria>
(Score): (Evaluation)
4: Very good 3: Good 2: Normal 1: Bad 0: Very bad <Criteria>
(Judgment): (Average score)
◎: More than 3.5 points: Very good ○: More than 2.5 points and less than 3.5 points: Good △: More than 1 point and less than 2.5 points: Slightly bad ×: More than 1 point: Less than

(Evaluation item)
C. Lightness of expansion and spread d. No sense of burden e. Sustaining a moisturizing feeling We asked 20 specialized panels to apply the sample, and for C, do you feel a burden that makes your skin feel taut immediately after application, for C, and for E, live a normal life after application? The moisturizing sensation 6 hours after the treatment was evaluated on a 7-point scale according to the following absolute evaluation criteria, and a score was given. The average value was calculated from the total score of all the panels of each sample, and the judgment was made according to the following criteria.
<Absolute evaluation criteria>
(Score): (Evaluation)
6: Very good 5: Good 4: Somewhat good 3: Normal 2: Somewhat bad 1: Bad 0: Very bad <Judgment criteria>
(Judgment): (Average score)
◎: More than 5 points: Very good ○: More than 3.5 points 5 points or less: Good △: More than 1 point 3.5 points or less: Slightly defective ×: 1 point or less: Defective

As is clear from the results in Table 1, the water-in-oil emulsified foundations of Examples 1 to 20 of the present invention have water resistance and secondary adhesion prevention effect as compared with the oil-in-oil emulsified foundations of Comparative Examples 1 to 5. It was excellent in terms of lightness of spread, no burden, and long-lasting moisturizing feeling.
On the other hand, in Comparative Example 1 in which the component (A) is not contained, the strength of the cosmetic film is weak, so that it easily collapses, and further, it is not possible to suppress the evaporation of water from the skin over time. No satisfactory result was obtained in terms of the next adhesion prevention effect and the maintenance of moisturizing feeling.
In Comparative Example 2 in which the alkyl-styrene copolymer acrylate dispersion using water as a dispersion medium was used instead of the component (A), the decorative film was inferior in water resistance because it was easily compatible with water, and the coating film became flexible. Since it is lacking, it cannot follow the movement of the skin, and it is not possible to suppress the evaporation of water from the skin over time. Therefore, it was not possible to obtain satisfactory results in terms of water resistance, no feeling of burden, and maintenance of moisturizing feeling. ..
In Comparative Example 3 in which the component (B) is not contained, since the bonding point of the coating film formed by fusing the component (A) is weak, it easily blends with sebum and is inferior in the effect of preventing secondary adhesion. It was.
In Comparative Example 4 in which the component (C) is not contained, the weight of the spread and spread due to the components (A) and (B) is easily felt, and the moisture evaporation of the skin over time cannot be suppressed. It was not enough in terms of lightness and long-lasting moisturizing feeling.
In Comparative Example 5 in which the component (D) was not contained, the hardness of the cosmetic film due to the oil-soluble resin was easily felt, and a satisfactory one was not obtained in terms of no feeling of burden.
In Example 14 in which trimethylsiloxysilicic acid, which is a hard resin, was used as the component (B), all of water resistance, secondary adhesion prevention effect, light spread and spread, no burden feeling, and maintenance of moisturizing feeling. Not only was it excellent in, but it was also excellent in the effect of giving a feeling of firmness to the skin.
In Example 15 in which a highly flexible (Acrylate / Dimethicone) copolymer was used as the component (B), water resistance, secondary adhesion prevention effect, light spread and spread, no burden feeling, and maintenance of moisturizing feeling were all all. Not only was it excellent in the above, but it was also excellent in the effect of preventing the cosmetic film from twisting in areas such as around the eyes and around the mouth where movements associated with facial expressions were large.
In Example 16 using dextrin isostearate, which is rich in luster, as the component (B), it is only excellent in water resistance, secondary adhesion prevention effect, light spread and spread, no burden feeling, and maintenance of moisturizing feeling. There was no such thing, and the gloss of the cosmetic film was excellent.
In Examples 17 and 18 in which methacrylic acid / ethylhexyl methacrylate copolymer, which is a resin having a fast film formation, was used as the component (B), water resistance, secondary adhesion prevention effect, light spread and spread, and a feeling of burden were exhibited. Not only was it excellent in terms of the lack of moisture and the sustainability of the moisturizing sensation, but it was also excellent in that a uniform cosmetic film was produced without uneven coating.
Even in Example 19 in which hydrogenated pentaerythrityl rosinate was used as the component (B), effects were obtained in all of water resistance, secondary adhesion prevention effect, light spread and spread, no burden feeling, and maintenance of moisturizing feeling. It turned out to be.

Example 21: Water-in-oil emulsified base (creamy)
(Ingredient) (%)
(1) Dimethylpolysiloxane 3% treated titanium oxide 1.5
(2) Dimethylpolysiloxane 2% treated iron oxide 0.1
(3) Dimethylpolysiloxane 2% treated Gunjo 0.1
(4) Dimethylpolysiloxane 3% zinc oxide 10.0
(5) Dimethylpolysiloxane 3% treated talc 1.0
(6) Dimethylpolysiloxane 2% treated mica titanium 2.0
(7) PEG-9 Dimethicone * 10 2.0
(8) Decamethylcyclopentasiloxane 15.0
(9) 2-Ethylhexyl paramethoxycinnamate 8.0
(10) 2- (4-Diethylamino-2-hydroxybenzoyl)
Benzoic acid hexyl ester 1.0
(11) Alkyl acrylate / styrene copolymer dispersion * 4 0.5
(12) (Acrylate / Dimethicone) Copolymer * 11 1.0
(13) (Dimethicone / (PEG-10 / 15)) Crosspolymer * 12 4.0
(14) Sorbitan sesquiisostearate 0.3
(15) Isotridecyl isononanoate 2.0
(16) Tri (capryl capric acid) glyceryl 3.0
(17) Dimethicone 3.0
(18) Lavender oil 0.1
(19) Spherical silica (hollow, average particle size 18 μm) * 13 0.3
(20) Boron Nitride 3.0
(21) Methyl methacrylate crosspolymer / polyisoprene composite powder * 14 1.0
(22) Remaining amount of purified water (23) Tripropylene glycol 15.0
(24) Propylene glycol 10.0
(25) Glycerin 5.0
(26) Ethyl alcohol 5.0
(27) Water-soluble collagen 0.5
* 10: KF-6019 (manufactured by Shin-Etsu Chemical Co., Ltd.)
* 11: Silicon KP-545 (solid content 30%, manufactured by Shin-Etsu Chemical Co., Ltd.)
* 12: Silicon KSG-210 (solid content 25%, manufactured by Shin-Etsu Chemical Co., Ltd.)
* 13: SILICA MICRO BEAD BA-1 (manufactured by JGC Catalysts and Chemicals Co., Ltd.)
* 14: Ganzpar GMI-0804 (manufactured by Ganz Kasei Co., Ltd.)

(Production method)
A. The components (1) to (8) are uniformly dispersed.
B. After the components (9) to (10) are heated and uniformly dissolved, they are added to A and uniformly mixed.
C. Ingredients (11) to (21) are added to B and mixed uniformly.
D. The components (22) to (27) are uniformly mixed.
E. D is gradually added to C for dispersion emulsification.
F: E is defoamed and filled in a container.

The water-in-oil emulsified base (cream-like) of the present invention spreads and spreads lightly at the time of application, and the decorative film after application has excellent water resistance and secondary adhesion prevention effect, but does not have a feeling of tension. Furthermore, it was also excellent in maintaining a moisturizing feeling.

Example 22: Water-in-oil emulsified sunscreen cosmetic (liquid)
(Ingredient) (%)
(1) Decamethylcyclopentasiloxane 10.0
(2) PEG-3 Dimethicone * 15 4.0
(3) Zinc oxide * 2 15.0
(4) 2-Ethylhexyl paramethoxycinnamate 3.0
(5) 4-tert-Butyl-4'-methoxy-dibenzoylmethane 1.0
(6) Polysilicone-15 3.0
(7) Hydrogenated polyisobutene * 16 5.0
(8) Trimethylsiloxysilicic acid * 17 8.0
(9) Neopentyl glycol diethylcaproate 1.0
(10) Cetyl 2-ethylhexanoate 1.0
(11) Propylene glycol dicaprate 1.0
(12) 2-decyltetradecanol 8.0
(13) Alkyl acrylate / styrene copolymer dispersion * 4 16.0
(14) (Dimethicone / Phenylvinyl Dimethicone) Cross Polymer * 18 0.3
(15) Spherical silica (average particle size 3 to 5 μm) * 19 5.0
(16) Methyl methacrylate crosspolymer (average particle size 15 μm) 1.0
(17) Remaining amount of purified water (18) Sodium chloride 0.2
(19) Tripropylene glycol 1.0
(20) 1,3-butylene glycol 0.5
(21) Glucosyltrehalose 2.0
(22) Polyvinylpyrrolidone 0.5
(23) Ethanol 5.0
(24) Methylparaben 0.1
* 15: Silicon KF-6015 (manufactured by Shin-Etsu Chemical Co., Ltd.)
* 16: IP Solvent 2028 MU (manufactured by Idemitsu Petrochemical Co., Ltd.)
* 17: Silicon KF-7312J (solid content 50%, solvent: cyclopentasiloxane, manufactured by Shin-Etsu Chemical Co., Ltd.)
* 18: KSG-18 (solid content 15%, solvent: diphenylsiloxyphenyl trimeticone, manufactured by Shin-Etsu Chemical Co., Ltd.)
* 19: Sunsphere NP-30 (manufactured by AGC SI Tech)

(Production method)
A. The components (1) to (3) are uniformly dispersed.
B. After the components (4) to (8) are heated and uniformly dissolved, they are added to A and uniformly mixed.
C. Ingredients (9) to (16) are added to B and mixed uniformly.
D. The components (17) to (24) are uniformly mixed.
E. D is gradually added to C for dispersion emulsification.
F: E is defoamed and filled in a container.

The water-in-oil emulsified sunscreen cosmetic (liquid) of the present invention spreads and spreads lightly at the time of application, and the cosmetic film after application has excellent water resistance and secondary adhesion prevention effect, but gives a feeling of tension. It was also excellent in maintaining a moisturizing feeling.

Example 23: Water-in-oil emulsified blusher (gel)
(Ingredient) (%)
(1) Triethoxycaprylylsilane 3% treated titanium oxide 3.0
(2) Triethoxycaprylylsilane 3% treated red 226 0.5
(3) Triethoxycaprylylsilane 3% treated yellow 4 0.2
(4) Triethoxycaprylylsilane 3% treated black iron oxide 0.1
(5) Methyltrimethicone 5.0
(6) Isododecane 10.0
(7) Trimethylsiloxysilicic acid * 20 7.5
(8) Dextrin isostearate * 21 0.5
(9) Alkyl acrylate / styrene copolymer dispersion * 22 8.0
(10) Lauryl PEG-9 Polydimethylsiloxyethyl Dimethicone 1.5
(11) PEG / PPG-10 / 3 Oleyl Ether Dimethicone * 23 1.0
(12) (Dimethicone / Polyglycerin-3) Crosspolymer * 5 3.0
(13) Glyceryl tri2-ethylhexanoate 2.0
(14) Diisostearyl malate 0.5
(15) Dextrin palmitate * 24 5.0
(16) Squalene 1.0
(17) Mica Titanium 10.0
(18) Titanium oxide coated glass powder * 25 3.0
(19) Organically modified bentonite * 26 3.0
(20) Mica 2.0
(21) Spherical silica * 7 10.0
(22) Remaining amount of purified water (23) Tripropylene glycol 5.0
(24) Ethanol 3.0
(25) Methyl paraoxybenzoate 0.1
(26) Fragrance 0.2
* 20: SR-1000 (manufactured by Momentive Performance Materials Japan)
* 21: Unifilma HVY (manufactured by Chiba Flour Milling Co., Ltd.)
* 22: Dispersion with 50% solid content of the same alkyl acrylate / styrene copolymer as * 4, and dispersion medium: isododecane. Prepared as follows.
The (meth) acrylate monomer, styrene, and the polymerization initiator were added to the dispersion medium isododecane and stirred to carry out the polymerization. The polymerization solution was filtered and the monomer was removed from the filter under reduced pressure to obtain a dispersion of isododecane as the dispersion medium.
* 23: Silicon KF-6026 ((manufactured by Shin-Etsu Chemical Co., Ltd.))
* 24: Leopard TL-2 (manufactured by Chiba Flour Milling Co., Ltd.)
* 25: Metashine 1080RC-R (manufactured by Nippon Sheet Glass), perfluorooctyltriethoxysilane 3% treatment * 26: BENTONE 27V (manufactured by ELEMENTIS)

(Production method)
A. The components (1) to (5) are uniformly dispersed.
B. After the components (6) to (8) are uniformly dissolved, they are added to A and mixed uniformly.
C. Ingredients (9) to (21) are added to B and mixed uniformly.
D. The components (22) to (26) are uniformly mixed.
E. D is gradually added to C for dispersion emulsification.
F: E is defoamed and filled in a container.

The water-in-oil emulsified blusher (gel) of the present invention spreads and spreads lightly at the time of application, and while the cosmetic film after application has excellent water resistance and secondary adhesion prevention effect, there is no feeling of tension. Furthermore, it was also excellent in maintaining a moisturizing feeling.

Example 24: Water-in-oil emulsified sunscreen cosmetic (liquid)
(Ingredient) (%)
(1) Zinc oxide * 2 10.0
(2) Dimethylsilylated silica 5.0
(3) Polyhydroxystearic acid 1.0
(4) 2-Ethylhexyl paramethoxycinnamate 10.0
(5) Diethylaminohydroxybenzoyl hexyl benzoate 2.0
(6) Bisethylhexyloxyphenol methoxyphenyl triazine 1.0
(7) Polysilicone-15 3.0
(8) PEG-9 Polydimethylsiloxyethyl Dimethicone 0.5
(9) Decamethylcyclopentasiloxane 5.0
(10) Dimethicone 3.0
(11) Propylene Glycol Dicaprate 20.0
(12) (Dimethicone / (PEG-10 / 15)) Crosspolymer * 27 1.0
(13) (Vinyl Dimethicone / Lauryl Dimethicone) Cross Polymer * 28 2.0
(14) Alkyl acrylate / styrene copolymer dispersion * 4 10.0
(15) (Acrylate / Dimethicone) Copolymer * 11 8.0
(16) Remaining amount of purified water (17) Disodium edetate 0.05
(18) 1,2-Hexanediol 0.5
(19) Caprylyl glycol 2.0
(20) Ethanol 13.0
(21) Methylparaben 0.1
* 27: KSG-210 (solid content 25%, solvent: dimethicone, manufactured by Shin-Etsu Chemical Co., Ltd.)
* 28: KSG-43 (solid content 30%, solvent: glyceryl tri2-ethylhexanoate, manufactured by Shin-Etsu Chemical Co., Ltd.)

(Production method)
A. The components (1) to (3) are uniformly dispersed.
B. After the components (4) to (11) are heated and uniformly dissolved, they are added to A and uniformly mixed.
C. Ingredients (12) to (15) are added to B and mixed uniformly.
D. The components (16) to (21) are uniformly mixed.
E. D is gradually added to C for dispersion emulsification.
F: E is defoamed and filled in a container.

The water-in-oil emulsified sunscreen cosmetic (liquid) of the present invention spreads and spreads lightly at the time of application, and the cosmetic film after application has excellent water resistance and secondary adhesion prevention effect, but gives a feeling of tension. It was also excellent in maintaining a moisturizing feeling.

Example 26: Water-in-oil emulsified sunscreen cosmetic (solid)
(Ingredient) (%)
(1) Decamethylcyclopentasiloxane 20.0
(2) Zinc oxide * 2 15.0
(3) Dimethylsilylated silica 3.0
(4) PEG-9 Polydimethylsiloxyethyl Dimethicone 1.0
(5) Triethylhexanoin 10.0
(6) Cetyl 2-ethylhexanoate 5.0
(7) 2-Ethylhexyl paramethoxycinnamate 5.0
(8) 4-tert-Butyl-4'-methoxy-dibenzoylmethane 1.0
(9) Polysilicone-15 3.0
(10) Neopentyl glycol diethylcaproate 3.0
(11) Propylene glycol dicaprate 3.0
(12) Alkyl acrylate / styrene copolymer dispersion * 4 1.5
(13) Dipropylene glycol 1.0
(14) Polymethylsilsesquioxane * 3 5.0
(15) Spherical silica (average particle size 3 to 5 μm) * 19 5.0
(16) Remaining amount of purified water (17) Sodium chloride 0.2
(18) Polyethylene 10.0
(19) Microcrystalline wax 2.0

(Production method)
A. The components (1) to (6) are uniformly dispersed.
B. After the components (7) to (13) are uniformly dissolved, they are added to A and mixed uniformly.
C. Ingredients (14) and (15) are added to B and mixed uniformly.
D. The components (16) and (17) are uniformly mixed.
E. D is gradually added to C for dispersion emulsification.
F: Add (18) and (19) to E, heat to 100 ° C. to mix and dissolve, and then fill the container.

The water-in-oil emulsified sunscreen cosmetic (solid) of the present invention spreads and spreads lightly at the time of application, and the cosmetic film after application has excellent water resistance and secondary adhesion prevention effect, but has a feeling of tension. It was also excellent in maintaining a moisturizing feeling.

Example 26: Water-in-oil emulsified sunscreen cosmetic (spray)
(Ingredient) (%)
(Stock solution)
(1) 2-Ethylhexyl paramethoxycinnamate 8.0
(2) Diethylaminohydroxybenzoyl hexyl benzoate 0.5
(3) Bisethylhexyloxyphenol methoxyphenyl triazine 2.0
(4) Propylene glycol dicaprate 30.0
(5) Alkylate benzoate 1.0
(6) Isododecane 5.0
(7) Alkyl acrylate / styrene copolymer dispersion * 22 5.0
(8) (Vinyl dimethicone / methicone silsesquioxane) Cross polymer * 29 3.0
(9) (Dimethicone / Phenylvinyl Dimethicone) Cross Polymer * 18 1.0
(10) Polymethylsilsesquioxane * 3 2.0
(11) Spherical silica * 32 0.5
(12) Purified water 5.0
(13) 1,2-Hexanediol 0.5
(14) Caprylyl glycol 0.5
(15) Remaining amount of ethanol (propellant)
(16) LPG 100.0
* 29: KSP-100 (manufactured by Shin-Etsu Chemical Co., Ltd.)
* 32: God Ball E-90C (manufactured by Suzuki Yushi Kogyo Co., Ltd.)

(Production method)
A. The components (1) to (5) are uniformly dispersed.
B. After the components (6) to (11) are uniformly dissolved, they are added to A and mixed uniformly.
C. The components (12) to (15) are uniformly mixed.
D. C is gradually added to B for dispersion emulsification.
E: (stock solution): (propellant) = 30:70 The container is filled.

The water-in-oil emulsified sunscreen cosmetic (spray) of the present invention spreads and spreads lightly at the time of application, and the cosmetic film after application has excellent water resistance and secondary adhesion prevention effect, but has a feeling of tension. It was also excellent in maintaining a moisturizing feeling.

Claims (3)

The following components (A) to (D);
(A) Alkyl acrylate / styrene copolymer dispersion using volatile hydrocarbon oil as a dispersion medium (B) Oil-soluble resin (C) Polyhydric alcohol (D) Partially crosslinked organopolysiloxane .
One or 2 in which the component (B) is selected from trimethylsiloxysilicic acid, polymethylsilsesquioxane, (Acrylate / dimethicone) copolymer, acrylic copolymer, dextrin fatty acid ester, and hydrogenated pentaerythrityl rosinate. More than a seed,
The component (C) is one or more selected from tripropylene glycol, dipropylene glycol, and glycerin .
The content of the component (A) is 0.1 to 10% by mass in the cosmetic in terms of solid content.
The content of the component (B) is 0.1 to 10% by mass in the cosmetic.
The content of the component (C) is 3 to 30% by mass in the cosmetic.
The content of the component (D) is 0.1 to 5% by mass in the cosmetic.
Water-in-oil emulsified cosmetics. It said components (C) contains tripropylene glycol, water-in-oil emulsion cosmetic according to claim 1. Further contains a component (E) spherical silica according to claim 1 or 2, water-in-oil emulsified cosmetic according to.