Water-in-oil emulsion cosmetic

Abstract

To provide a water-in-oil emulsion cosmetic that is less tend to slip on the skin during application, exhibits excellent skin adherence, and is less prone to causing makeup smudging when layered on liquid foundation.SOLUTION: A water-in-oil emulsion cosmetic contains following components (A), (B), (C) and (D): (A) a polymer with a norbornane structure and / or a silicone-modified pullulan, (B) a phenyl-modified silicone oil, (C) a polyether-modified silicone, and (D) an oil-based gelator.SELECTED DRAWING: None

Description

[Technical field]

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

[0002] 2. Description of the Related Art Cosmetics containing film-forming polymers for the purpose of improving the uniformity of the cosmetic film and the durability of the cosmetic are known. For example, Patent Document 1 describes that a cosmetic containing a film-forming polymer in which a specific functional group has been introduced into the backbone of a polycycloolefin polymer has good cosmetic staying power and texture. Furthermore, Patent Document 2 describes that a skin topical composition that combines a specific film-forming polymer with a cationically modified clay mineral in a specific ratio improves skin wrinkles and also produces a uniform, bright finish with no unevenness in the thickness of the coating film immediately after application. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2012-17317 A [Patent Document 2] JP 2021-165262 A Summary of the Invention [Problem to be solved by the invention]

[0004] However, conventional cosmetics containing film-forming polymers have the problem that they slide over the skin during application, have poor adhesion to the skin, and are prone to smudging when applied over a liquid foundation. [Means for solving the problem]

[0005] The present inventors have discovered that a water-in-oil emulsion cosmetic, which combines a specific film-forming polymer with a phenyl-modified silicone oil, a polyether-modified silicone, and an oil-based gelling agent, does not slide easily over the skin during application, has excellent adhesion to the skin, and is less likely to cause makeup smudging when applied over a liquid foundation.

[0006] The present invention comprises the following components (A), (B), (C) and (D): (A) a polymer containing a norbornane structure and / or silicone-modified pullulan, (B) phenyl-modified silicone oil, (C) polyether-modified silicone, (D) Oil-based gelling agent The present invention relates to a water-in-oil emulsion cosmetic comprising the above-mentioned compound. Effect of the Invention

[0007] The water-in-oil emulsion cosmetic of the present invention maintains good spreadability when applied, does not slide easily over the skin during application, has excellent adhesion to the skin, and is less likely to cause makeup smudging when applied over a liquid foundation. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] The component (A) used in the present invention is (A1) a polymer containing a norbornane structure and / or (A2) a silicone-modified pullulan. In the component (A), the norbornane structure in the polymer (A1) containing a norbornane structure means a structure represented by the following formula: The polymer (A1) may have the structure represented by this formula at any site.

[0009] [ka]

[0010] There are no particular limitations on component (A1) so long as it is a polymer having the above-mentioned norbornane structure in the molecule, but from the viewpoint of improving the shrinkage of the coating film and adhesion to the skin due to the above-mentioned mechanism of action, it is more preferable that component (A1) is a silicone-modified polymer containing a norbornane structure.

[0011] Examples of the norbornane structure-containing silicone modified polymer include polymers having a repeating unit represented by the following general formula (1) or (2).

[0012] [ka]

[0013] In the formula, R 1 are each independently an alkyl group having 1 to 12 carbon atoms, and X is a group represented by the following formula (i): a is an integer of 1 to 3, and b is an integer of 0 to 2.

[0014] [ka]

[0015] In the formula, R 2 are each independently a hydrocarbon group having 1 to 12 carbon atoms, and c is an integer of 1 to 5.

[0016] [ka]

[0017] In the formula, R 1 , R 2 and b are the same as above, and d is an integer of 2 or more and 5 or less.

[0018] In the general formula (1), R 1 each independently represents an alkyl group having 1 to 12 carbon atoms, and from the viewpoint of controlling the shape of the skin, a methyl group, an ethyl group, an n-propyl group, a butyl group, or a pentyl group is preferable, and a methyl group is more preferable. X is a group represented by the formula (i), and in the formula (i), R 2 are each independently a hydrocarbon group having 1 to 12 carbon atoms. From the viewpoint of forming a uniform coating film on the skin and controlling the shape of the skin, R 2 is preferably an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms, more preferably an alkyl group having 1 to 12 carbon atoms or a phenyl group, further preferably an alkyl group having 1 to 3 carbon atoms, and even more preferably a methyl group. c is an integer of 1 to 5, and from the viewpoint of versatility, c=1 is preferable. That is, X is preferably a trimethylsiloxy group. a is an integer of 1 or more and 3 or less, and may be, for example, a polymer in which a repeating unit of a=2 and a repeating unit of a=3 are present in a mixture. From the viewpoint of versatility, a is preferably 3. b is an integer of 0 or more and 2 or less, and from the same viewpoint, is preferably 0, 1 or a combination thereof, and more preferably 0.

[0019] In the general formula (2), R 1 , R 2 and b are the same as above. d is an integer of 2 to 5, and from the viewpoint of versatility, d=2 is preferable. From the same viewpoint, the cyclic silicone structure in the general formula (2) is 1 and R 2 is preferably a methyl group, and d is preferably 2 or 3. That is, the cyclic silicone structure in general formula (2) is preferably a structure represented by the following formula (4) or (5).

[0020] [ka]

[0021] From the viewpoint of forming a uniform coating film on the skin and controlling the shape of the skin, the proportion of the repeating units represented by the general formula (1) or (2) in the norbornane structure-containing silicone modified polymer is preferably 10% or more, more preferably 30% or more, and even more preferably 50% or more of the total number of repeating units in the polymer. The upper limit is 100%, and is preferably 95% or less, more preferably 90% or less, and even more preferably 70% or less. The specific range of the number of repeating units represented by the general formula (1) or (2) in the norbornane structure-containing silicone modified polymer is preferably 10 to 100%, more preferably 10 to 95%, even more preferably 30 to 90%, and even more preferably 50 to 70% of the total number of repeating units in the polymer.

[0022] The norbornane structure-containing silicone modified polymer may have a repeating unit represented by the following general formula (3) in addition to the repeating unit represented by the general formula (1) or (2).

[0023] [ka]

[0024] In the formula, R 3 ~R 6 R are each independently a hydrogen atom, a halogen atom, a substituent selected from an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, and a halogenated hydrocarbon group having 1 to 10 carbon atoms, or an oxetanyl group, an alkoxycarbonyl group, a polyoxyalkylene group, a polyglyceryl group, or an alkoxysilyl group. 3 ~R 6 Two groups selected from the group may be bonded to each other to form an alicyclic structure, an aromatic ring structure, a carboimide group, or an acid anhydride group. b is the same as defined above.

[0025] The proportion of the repeating unit represented by the above general formula (3) in the norbornane structure-containing silicone modified polymer is preferably 90% or less, more preferably 70% or less, and even more preferably 50% or less of the total number of repeating units in the polymer, from the viewpoint of forming a uniform coating film on the skin and controlling the shape of the skin. When the repeating unit represented by the above general formula (3) is contained, the proportion is preferably 5% or more, more preferably 10% or more, and even more preferably 30% or more of the total number of repeating units in the polymer. The specific range of the number of repeating units represented by the above general formula (3) in the norbornane structure-containing silicone modified polymer is preferably 5 to 90%, more preferably 10 to 70%, and even more preferably 30 to 50% of the total number of repeating units in the polymer. The proportion of the repeating units represented by the above general formulas (1) to (3) in the norbornane structure-containing silicone modified polymer is 1 It can be determined by H-NMR measurement.

[0026] The norbornane structure-containing silicone modified polymer is preferably a silicone modified polynorbornene, more preferably a silicone modified polynorbornene represented by the following formula (6).

[0027] [ka]

[0028] In the formula, e and f are the numbers of repeating units and each is independently an integer of 1 or more. From the viewpoint of controlling the shape of the skin, the ratio of e and f in general formula (6) is preferably e / f=20 / 80 to 90 / 10 (mol / mol), more preferably 30 / 70 to 80 / 20 (mol / mol), and even more preferably 50 / 50 to 70 / 30 (mol / mol).

[0029] From the viewpoint of forming a uniform coating film on the skin and controlling the shape of the skin, the number average molecular weight Mn of the norbornane structure-containing silicone modified polymer is preferably 50,000 or more, more preferably 100,000 or more, and even more preferably 200,000 or more, and is preferably 2,000,000 or less, more preferably 1,500,000 or less, even more preferably 800,000 or less, and even more preferably 600,000 or less. The specific range of the number average molecular weight Mn of the norbornane structure-containing silicone modified polymer is preferably 50,000 to 2,000,000, more preferably 100,000 to 1,500,000, even more preferably 200,000 to 800,000, and even more preferably 200,000 to 600,000. The number average molecular weight Mn of the polymer can be measured by gel permeation chromatography (GPC) using polystyrene as a standard substance, specifically, by the method described in the Examples.

[0030] The component (A1) can be obtained, for example, by addition polymerization of a cyclic olefin monomer that contains a norbornane structure or is capable of forming a norbornane structure, by a known method. For example, if component (A1) is a norbornane structure-containing silicone modified polymer having a repeating unit represented by the above general formula (1) or (2), it can be obtained by addition polymerization of a cyclic olefin monomer represented by the following general formula (1a) or (2a). Furthermore, a cyclic olefin monomer represented by the following general formula (1a) may be copolymerized.

[0031] [ka]

[0032] In the formula, R 1 are each independently an alkyl group having 1 to 12 carbon atoms, and X is a group represented by the following formula (i): a is an integer of 1 to 3, and b is an integer of 0 to 2.

[0033] [ka]

[0034] In the formula, R 2are each independently a hydrocarbon group having 1 to 12 carbon atoms, and c is an integer of 1 to 5.

[0035] [ka]

[0036] In the formula, R 1 , R 2 and b are the same as above, and d is an integer of 2 or more and 5 or less.

[0037] [ka]

[0038] In the formula, R 3 ~R 6 R are each independently a hydrogen atom, a halogen atom, a substituent selected from an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, and a halogenated hydrocarbon group having 1 to 10 carbon atoms, or an oxetanyl group, an alkoxycarbonyl group, a polyoxyalkylene group, a polyglyceryl group, or an alkoxysilyl group. 3 ~R 6 Two groups selected from the group may be bonded to each other to form an alicyclic structure, an aromatic ring structure, a carboimide group, or an acid anhydride group. b is the same as defined above.

[0039] When the cyclic olefin monomer represented by the above general formula (3a) is copolymerized, the amount used, from the viewpoint of forming a uniform coating film on the skin and controlling the shape of the skin, is preferably 90 mol % or less, more preferably 70 mol % or less, and even more preferably 50 mol % or less, and is also preferably 5 mol % or more, more preferably 10 mol % or more, and even more preferably 30 mol % or more, based on 100 mol % of all monomers used in the polymerization.

[0040] The silicone-modified polynorbornene represented by the formula (6) can be obtained by addition polymerization of tris(trimethylsiloxy)silylnorbornene represented by the following formula (6a) and norbornene.

[0041] [ka]

[0042] From the viewpoint of forming a uniform coating film on the skin and controlling the shape of the skin, the copolymerization ratio of tris(trimethylsiloxy)silylnorbornene to norbornene is preferably 20 / 80 to 90 / 10 (mol / mol), more preferably 30 / 70 to 80 / 20 (mol / mol), and even more preferably 50 / 50 to 70 / 30 (mol / mol).

[0043] The repeating units shown in the general formulas (1) to (3) and the formula (6) all represent 2,3-addition structural units of the cyclic olefin monomers that are raw material monomers, but may also include 2,7-addition structural units formed by addition polymerization of the cyclic olefin monomers.

[0044] As the norbornane structure-containing silicone modified polymer, norbornene / tris(trimethylsiloxy)silylnorbornene copolymer is preferred, which is a compound represented by the INCI name (International Cosmetic Ingredient Dictionary and Handbook, 16th Edition, Vol. 2, 2016, p. 2274): NORBORNENE / TRIS(TRIMETHYLSILOXY)SILYLNORBORNENE COPOLYMER. An example of a commercially available silicone modified polymer containing a norbornane structure is "NBN-30-ID" (a solution of norbornene / tris(trimethylsiloxy)silylnorbornene) copolymer in isododecane, manufactured by Shin-Etsu Chemical Co., Ltd.

[0045] Of the components (A), (A2) the silicone-modified pullulan includes pullulan having a silicone structure in the side chain. Specifically, from the viewpoint of improving the shrinkage of the coating film and adhesion to the skin, silicone-modified pullulan in which at least a portion of the hydrogen atoms of the OH groups in the pullulan have been substituted with a group represented by the following general formula (7) is preferred.

[0046] [ka]

[0047] In the formula, Z 1 R is a single bond or a divalent organic group. 1 , X and a are the same as above, and from the same viewpoint, X is preferably a trimethylsiloxy group, and a is preferably 3.

[0048] In the general formula (7), from the same viewpoint, Z 1 is preferably a divalent organic group, more preferably a divalent group represented by the following general formula (8) or (9), and even more preferably a divalent group represented by the following general formula (9).

[0049] [ka]

[0050] In the formula, R 11 is an alkylene group having 1 to 10 carbon atoms, and examples thereof include a methylene group, an ethylene group, a trimethylene group, a propylene group, a butylene group, etc. From the same viewpoint, among these, an ethylene group, a trimethylene group, and a propylene group are preferable, and a trimethylene group or a propylene group is more preferable.

[0051] Commercially available silicone-modified pullulan includes "TSPL-30-ID" (a solution of tri(trimethylsiloxy)silylpropylcarbamic acid pullulan in isododecane) and "TSPL-30-D5" (a solution of tri(trimethylsiloxy)silylpropylcarbamic acid pullulan in cyclopentasiloxane) manufactured by Shin-Etsu Chemical Co., Ltd.

[0052] As component (A), from the viewpoints of forming a uniform coating film on the skin and controlling the shape of the skin, (A1) a polymer containing a norbornane structure is preferred, and a silicone-modified polymer containing a norbornane structure is more preferred.

[0053] Component (A) may be a polymer containing a norbornane structure, silicone modified pullulan, or a combination of two or more thereof, and the content is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more, as solid content, in the total composition, from the viewpoint of forming a uniform coating film on the skin and controlling the shape of the skin. The content of component (A) is preferably 0.1 to 30% by mass, more preferably 0.5 to 20% by mass, and even more preferably 1 to 15% by mass, as solid content, in the total composition.

[0054] The phenyl-modified silicone oil of component (B) is preferably a phenyl-modified silicone that is liquid at 25° C. Liquid means that the viscosity at 25° C. is 4000 mPa·s or less. The viscosity at 25°C of the phenyl-modified silicone that is liquid at 25°C is preferably 600 mPa·s or less, more preferably 200 mPa·s or less, and even more preferably 50 mPa·s or less. Here, the viscosity is measured at 25° C. using a B-type viscometer (TVB-10 model, manufactured by Toki Sangyo Co., Ltd.), rotor No. 4, 60 rpm, and 60 seconds.

[0055] Examples of phenyl-modified silicones that are liquid at 25° C. include phenyl trimethicone, diphenylsiloxyphenyl trimethicone, methylphenyl polysiloxane, diphenyl dimethicone, trimethylsiloxyphenyl dimethicone, and trimethylpentaphenyl trisiloxane. Among these, from the viewpoints of suppressing slippage on the skin during application and excellent adhesion to the skin, it is preferable to contain at least one or more selected from diphenylsiloxyphenyl trimethicone, methylphenyl polysiloxane, diphenyl dimethicone, and trimethylpentaphenyl trisiloxane, and among these, it is more preferable to contain diphenylsiloxyphenyl trimethicone.

[0056] Examples of commercially available products that can be used as component (B) include phenyl trimethicone such as DOWSIL SH-556 (manufactured by Dow Toray Co., Ltd.); diphenylsiloxyphenyl trimethicone such as KF-56A (manufactured by Shin-Etsu Chemical Co., Ltd.) and DOWSIL FZ-209 (manufactured by Dow Toray Co., Ltd.); diphenyl dimethicone such as KF-50 (manufactured by Shin-Etsu Chemical Co., Ltd.), KF-53 (manufactured by Shin-Etsu Chemical Co., Ltd.), and KF-54P (manufactured by Shin-Etsu Chemical Co., Ltd.); trimethylsiloxyphenyl dimethicone such as PDM-1000 (manufactured by Wacker Asahi Kasei Silicones Co., Ltd.); and trimethylpentaphenyl trisiloxiane such as PH-1555 HRI Cosmetic Fluid (manufactured by Dow Toray Co., Ltd.).

[0057] Component (B) can be used alone or in combination of two or more, and the content is preferably 0.1% by mass or more in the total composition, more preferably 0.3% by mass or more, even more preferably 1% by mass or more, and preferably 30% by mass or less, more preferably 15% by mass or less, and even more preferably 8% by mass or less, from the viewpoints of suppressing slippage on the skin during application, excellent adhesion to the skin, and suppressing makeup smudging when applied over a liquid foundation. The content of component (B) is preferably 0.1 to 30% by mass in the total composition, more preferably 0.3 to 15% by mass, and even more preferably 1 to 8% by mass.

[0058] In the present invention, from the viewpoints of excellent adhesion to the skin, forming a uniform coating film on the skin, and controlling the shape of the skin, the mass ratio (A) / (B) of component (A) to component (B) is preferably 0.2 or more, more preferably 0.3 or more, and even more preferably 0.5 or more, and is preferably 30 or less, more preferably 10 or less, and even more preferably 5 or less. Moreover, the mass ratio (A) / (B) of component (A) to component (B) is preferably 0.2 to 30, more preferably 0.3 to 10, and even more preferably 0.5 to 5.

[0059] The polyether-modified silicone of component (C) may be any of those used in ordinary cosmetics, such as polyoxyethylene-methylpolysiloxane copolymer, poly(oxyethylene-oxypropylene)methylpolysiloxane copolymer, and alkyl-modified polyether-modified silicone such as cetyl PEG / PPG-10 / 1 dimethicone, lauryl PEG-9 polydimethylsiloxyethyl dimethicone, and lauryl PEG / PPG-18 / 18 methicone.

[0060] The modified silicone of component (C) preferably has an HLB of 2 to 7, and more preferably 2 to 5, from the viewpoints of preventing the silicone from sliding on the skin during application and of excellent adhesion to the skin. In the present invention, HLB (Hydrophilic-Lipophilic Balance) indicates the molecular weight of the hydrophilic group portion in the total molecular weight of a surfactant, and is calculated by the following Griffin formula. HLB = 20 x (molecular weight of hydrophilic group / total molecular weight)

[0061] Component (C) may be used alone or in combination of two or more, and the content is preferably 0.1% by mass or more in the total composition, more preferably 0.3% by mass or more, even more preferably 0.5% by mass or more, and preferably 15% by mass or less, more preferably 10% by mass or less, and even more preferably 7% by mass or less, from the viewpoint of suppressing slippage on the skin during application and excellent adhesion to the skin. The content of component (C) is preferably 0.1 to 15% by mass in the total composition, more preferably 0.3 to 10% by mass, and even more preferably 0.5 to 7% by mass.

[0062] In the present invention, the mass ratio (A) / (C) of component (A) to component (C) is preferably 0.3 or more, more preferably 0.5 or more, even more preferably 1 or more, and is preferably 30 or less, more preferably 14 or less, and even more preferably 8 or less, from the viewpoints of suppressing slippage on the skin during application, excellent adhesion to the skin, and suppressing makeup smudging when applied over a liquid foundation. In addition, the mass ratio (A) / (C) of component (A) to component (C) is preferably 0.3 to 30, more preferably 0.5 to 14, and even more preferably 1 to 8.

[0063] The oil-based gelling agent of component (D) is one that is commonly used in cosmetics, and examples thereof include (D1) organopolysiloxanes formed by bonding poly(N-acylalkyleneimine) segments, (D2) styrene copolymers, (D3) glycerin fatty acid esters that are solid at 25°C, (D4) dextrin fatty acid esters, and (D5) organically modified clay minerals.

[0064] (D1) The organopolysiloxane obtained by bonding poly(N-acylalkyleneimine) segments is an organopolysiloxane having at least two silicon atoms of the organopolysiloxane segments constituting the main chain, which are bonded via an alkylene group containing a heteroatom to at least two silicon atoms of the organopolysiloxane segments constituting the main chain, and which is represented by the following general formula (11):

[0065] [ka]

[0066] (In the formula, R 21 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and t represents 2 or 3. An organopolysiloxane comprising poly(N-acylalkyleneimine) segments each having a repeating unit represented by the formula: The number average molecular weight of the poly(N-acylalkyleneimine) segment is 500 to 4000; the mass ratio (a / b) of the organopolysiloxane segment (a) constituting the main chain to the poly(N-acylalkyleneimine) segment (b) is 70 / 30 to 99 / 1; the weight average molecular weight of the organopolysiloxane segment between adjacent poly(N-acylalkyleneimine) segments is 5,000 to 40,000; An organopolysiloxane in which the organopolysiloxane segment constituting the main chain has a weight average molecular weight of 15,000 to 200,000 is preferred, and by using this component, better stability can be obtained.

[0067] At least two poly(N-acylalkyleneimine) segments are bonded to any silicon atom constituting the organopolysiloxane segment via an alkylene group containing a heteroatom.Furthermore, it is preferable that the poly(N-acylalkyleneimine) segments are bonded to one or more silicon atoms excluding both ends of the organopolysiloxane segment via the alkylene group, and it is more preferable that the poly(N-acylalkyleneimine) segments are bonded to two or more silicon atoms excluding both ends via the alkylene group.That is, the organopolysiloxane of component (D1) is a graft polymer having at least two poly(N-acylalkyleneimine) segments consisting of repeating units represented by the general formula (11) as side chains.

[0068] The alkylene group containing a heteroatom functions as a linking group for the poly(N-acylalkyleneimine) segment. Examples of such alkylene groups include alkylene groups having 2 to 20 carbon atoms and containing 1 to 3 nitrogen atoms, oxygen atoms, or sulfur atoms. Among these, a group represented by any one of the following formulae (i) to (vii) is preferred, a group represented by the following formulae (i) or (ii) is more preferred, and a group represented by the following formula (i) is even more preferred. In the formulae, An - represents a counter ion of a quaternary ammonium salt, and examples thereof include an ethyl sulfate ion, a methyl sulfate ion, a chloride ion, an iodide ion, a sulfate ion, a p-toluenesulfonate ion, and a perchlorate ion.

[0069] [ka]

[0070] In the N-acylalkyleneimine unit constituting the poly(N-acylalkyleneimine) segment, R 21 In the formula, examples of the alkyl group having 1 to 3 carbon atoms include linear alkyl groups having 1 to 3 carbon atoms, and branched alkyl groups having 3 carbon atoms. Specific examples include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.

[0071] In the general formula (11), t is the number 2 or 3, and is preferably 2 from the viewpoint of availability of raw materials in the production of organopolysiloxane.

[0072] The mass ratio (a / b) is in the range of 70 / 30 to 99 / 1, and from the viewpoints of excellent adhesion to the skin and uniformity of the finish, is preferably 75 / 25 to 98 / 2, and more preferably 83 / 17 to 97 / 3. In this specification, the mass ratio (a / b) is determined by dissolving 5% by mass of the organopolysiloxane of component (D1) in deuterated chloroform and measuring the mass ratio by nuclear magnetic resonance ( 1This refers to the value determined from the integral ratio of alkyl or phenyl groups in the organopolysiloxane segment to methylene groups in the poly(N-acylalkyleneimine) segment by H-NMR analysis.

[0073] In the organopolysiloxane, the weight average molecular weight (hereinafter also simply referred to as "MWg") of the organopolysiloxane segment between adjacent poly(N-acylalkyleneimine) segments is in the range of 5,000 to 40,000, and from the viewpoint of the flexibility of the cosmetic film, it is preferably 10,000 to 35,000, and more preferably 15,000 to 32,000.

[0074] In this specification, the term "organopolysiloxane segment between adjacent poly(N-acylalkyleneimine) segments" refers to a portion surrounded by a dashed line between the two points from the bonding point (bonding point A) of the poly(N-acylalkyleneimine) segment to the organopolysiloxane segment to the bonding point (bonding point B) of the adjacent poly(N-acylalkyleneimine) segment, as shown in the following formula (12), and is a region in which one R 22 SiO unit and one R 23 And y+1 (R 22 The term "poly(N-acylalkyleneimine) segment" refers to a segment composed of the above R 23 -ZR binds to 24 This refers to.

[0075] [ka]

[0076] In the above general formula (12), R 22 each independently represents an alkyl group having 1 to 22 carbon atoms or a phenyl group; R 23 represents an alkylene group containing a heteroatom, -ZR 24 indicates a poly(N-acylalkyleneimine) segment, and R 24 represents a residue of a polymerization initiator, and y represents a positive number.

[0077] MWg is the molecular weight of the portion enclosed by the dashed line in the above general formula (12), and can be interpreted as the mass (g / mol) of the organopolysiloxane segment per mole of the poly(N-acylalkyleneimine) segment. When the functional groups of the modified organopolysiloxane, which is the raw material compound, are 100% substituted with poly(N-acylalkyleneimine), it coincides with the functional group equivalent (g / mol) of the modified organopolysiloxane.

[0078] The molecular weight of the poly(N-acylalkyleneimine) segment can be calculated from the molecular weight and degree of polymerization of the N-acylalkyleneimine unit, or can be measured by gel permeation chromatography (hereinafter, also simply referred to as "GPC") measurement. In the present invention, it refers to the polystyrene-equivalent number average molecular weight (hereinafter, also simply referred to as "MNox") measured by GPC measurement performed under the measurement conditions described below. MNox is preferably in the range of 500 to 4000, more preferably 800 to 3500, and even more preferably 1000 to 3000, from the viewpoint of increasing the flexibility of the film of the cosmetic and the solubility in the solvent.

[0079] The MWg can be calculated from the content (mass %) of organopolysiloxane segments constituting the main chain (hereinafter, simply referred to as "Csi") according to the following formula (I). MWg=Csi×MNox / (100-Csi) (I)

[0080] The weight average molecular weight (hereinafter, simply referred to as "MWsi") of the organopolysiloxane segment constituting the main chain is 15,000 to 200,000, and preferably 50,000 to 170,000, more preferably 70,000 to 150,000, from the viewpoint of the flexibility of the cosmetic and the adhesion to the skin. In addition, the organopolysiloxane of the component (D1) can be easily blended into various products by dissolving it in a polar solvent such as water. Since the organopolysiloxane segment constituting the main chain has a common skeleton with the modified organopolysiloxane, which is the raw material compound, the MWsi is approximately the same as the weight average molecular weight of the modified organopolysiloxane, which is the raw material compound. The weight average molecular weight of the modified organopolysiloxane, which is the raw material compound, is measured by GPC under the measurement conditions described below and converted into polystyrene.

[0081] From the viewpoint of excellent adhesion to skin, the weight average molecular weight (hereinafter also simply referred to as "MWt") of the organopolysiloxane of component (D1) is preferably 15,000 to 200,000, more preferably 50,000 to 170,000, and even more preferably 70,000 to 150,000. MWt is a value measured by gel permeation chromatography (GPC) under the measurement conditions described below, and converted into polystyrene equivalent.

[0082] The organopolysiloxane of component (D1) has a high elastic modulus and a large amount of deformability, and in addition, when heated to a temperature range of 50 to 220°C, its plasticity improves significantly and it becomes soft, and when heating is stopped and the temperature returns to room temperature, it quickly regains its elasticity, which is a characteristic thermoplastic property.

[0083] The organopolysiloxane of component (D1) is, for example, a compound represented by the following general formula (13):

[0084] [ka]

[0085] (In the formula, R 22 has the same meaning as above, R 25 and R 26are R 22 or the following formulae (viii) to (xiii):

[0086] [ka]

[0087] R represents a monovalent group represented by any one of the following: 27 represents a monovalent group represented by the above formulas (viii) to (xiii), g represents a number from 91.5 to 1255.0, and h represents a number from 2.0 to 62.5. and a modified organopolysiloxane represented by the following general formula (14):

[0088] [ka]

[0089] (In the formula, R 21 and t have the same meaning as above) It is produced by reacting a cyclic imino ether represented by the following formula (1) with a terminally reactive poly(N-acylalkyleneimine) obtained by ring-opening polymerization of the cyclic imino ether represented by the following formula (1):

[0090] A polymerization initiator can be used for the ring-opening polymerization of the cyclic imino ether represented by general formula (14) (hereinafter, simply referred to as "cyclic imino ether (14)"). As the polymerization initiator, a compound having strong electrophilic reactivity, for example, an alkyl ester of a strong acid such as an alkyl ester of benzenesulfonate, an alkyl ester of p-toluenesulfonate, an alkyl ester of trifluoromethanesulfonate, an alkyl ester of trifluoroacetate, or a dialkyl sulfate can be used, and among them, a dialkyl sulfate is preferably used.

[0091] Examples of the polymerization solvent that can be used include acetates such as ethyl acetate and propyl acetate, ethers such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran, ketones such as acetone and methyl ethyl ketone, halogenated solvents such as chloroform and methylene chloride, nitrile solvents such as acetonitrile and benzonitrile, and aprotic polar solvents such as N,N-dimethylformamide, N,N-dimethylacetamide and dimethylsulfoxide, among which acetates are preferably used. The amount of the solvent used is usually 20 to 2000 parts by mass relative to 100 parts by mass of the cyclic iminoether (14).

[0092] The polymerization temperature is usually 30 to 170° C., preferably 40 to 150° C., and the polymerization time varies depending on the polymerization temperature etc., but is usually 1 to 60 hours.

[0093] For example, when 2-substituted-2-oxazoline is used as the cyclic iminoether (14), poly(N-acylethyleneimine) in which t=2 in the above general formula (11) is obtained, and when 2-substituted-dihydro-2-oxazine is used, poly(N-acylpropyleneimine) in which t=3 in the above general formula (11) is obtained.

[0094] The poly(N-acylalkyleneimine) obtained by living polymerization of the cyclic iminoether (14) has a reactive group at the end. Therefore, the organopolysiloxane of component (D1) can be obtained by reacting the reactive group at the end of this poly(N-acylalkyleneimine) with the reactive groups (viii) to (xiii) of the modified organopolysiloxane represented by general formula (13).

[0095] The above-mentioned production method by living polymerization is effective in that the degree of polymerization can be easily controlled by the amounts of cyclic iminoether (14) and polymerization initiator used, as shown in the theoretical formula (II) below, and that a substantially monodisperse poly(N-acylalkyleneimine) having a narrower molecular weight distribution than that obtained by conventional radical polymerization can be obtained.

[0096]

number

[0097] The amount of the cyclic iminoether (14) and the amount of the polymerization initiator used are preferably such that MNi in formula (II) is 500 to 4,000, more preferably 800 to 3,500, and even more preferably 1,000 to 3,000.

[0098] The weight average molecular weight of the modified organopolysiloxane represented by general formula (13) is preferably 15,000 to 220,000, more preferably 50,000 to 190,000, and even more preferably 70,000 to 170,000, from the viewpoints of the solubility of the resulting organopolysiloxane in polar solvents such as water and ease of handling after dissolution.

[0099] Furthermore, the functional group equivalent of the modified organopolysiloxane represented by general formula (13) has an upper limit in order to satisfy the mass ratio (a / b) and MWg of the organopolysiloxane of component (D1). From this viewpoint and from the viewpoint of imparting appropriate hydrophobicity to the main chain, the functional group equivalent is preferably 50,000 to 40,000, more preferably 10,000 to 35,000, and even more preferably 15,000 to 32,000. Here, the functional group equivalent of the modified organopolysiloxane represented by general formula (13) is the weight average molecular weight of the modified organopolysiloxane represented by general formula (13) divided by the number of R groups that the modified organopolysiloxane has per molecule. 27 This is the value obtained by dividing the number of

[0100] The usage amounts of the modified organopolysiloxane represented by the general formula (13) and the terminal-reactive poly(N-acylalkyleneimine) are preferably such that the mass ratio (modified organopolysiloxane / terminal-reactive poly(N-acylalkyleneimine)) is in the range of 70 / 30 to 99 / 1, more preferably 75 / 25 to 98 / 2, and even more preferably 83 / 17 to 97 / 3, from the viewpoints of the elastic modulus and the deformable amount of the resulting organopolysiloxane, and from the viewpoint of excellent adhesion to the skin and obtaining a uniform finish.

[0101] In the present invention, in the synthesis of each organopolysiloxane, various molecular weights were measured according to the following measurement conditions.

[0102] <Measurement conditions for the weight-average molecular weight of the modified organopolysiloxane> Column: Super HZ4000 + Super HZ2000 (manufactured by Tosoh Corporation) Eluent: 1 mM triethylamine / THF Flow rate: 0.35 mL / min Column temperature: 40°C Detector: UV Sample: 50 μL

[0103] <Measurement conditions for MNox and MWt> Column: Two K-804L (manufactured by Tosoh Corporation) columns connected in series were used. Eluent: 1 mM dimethyldodecylamine / chloroform Flow rate: 1.0 mL / min Column temperature: 40°C Detector: RI Sample: 50 μL

[0104] Also, for the calculation of the mass ratio (a / b) 1 1H-NMR measurement was performed under the following conditions. < 1 1H-NMR measurement conditions> The composition of the obtained polymer was 1 confirmed by 1H-NMR (400 MHz, manufactured by Varian). A sample of 0.5 g was dissolved in 2 g of measurement solvent (deuterated chloroform) and then measured. PULSE SEQUENCE Relax.delay: 30 seconds Pulse: 45 degrees Number of times: 8 Confirmation peaks around 0 ppm: Methyl groups of polydimethylsiloxane, Around 3.4 ppm: Methylene part of ethyleneimine. The ratio of silicone to poly(N-propionylethyleneimine) was calculated from each integral value.

[0105] As the organopolysiloxane of component (D1), from the viewpoints of excellent adhesion to the skin and obtaining a uniform finish, poly(N-formylethyleneimine)organosiloxane, poly(N-acetylethyleneimine)organosiloxane, poly(N-propionylethyleneimine)organosiloxane, etc. are preferred, and poly(N-propionylethyleneimine)organosiloxane (POLYSILICONE-9) is more preferred.

[0106] Examples of the (D2) styrene copolymer include copolymers such as styrene-isoprene, styrene-ethylene propylene, styrene-butadiene, styrene-ethylene butylene, styrene-propylene butylene, styrene-butylene, hydrogenated styrene-isoprene, etc. Among these, hydrogenated styrene-isoprene copolymers are preferred from the viewpoints of excellent adhesion to the skin and achieving a uniform finish. These diblock copolymers preferably have a number average molecular weight of 100,000 to 3,000,000, more preferably 150,000 to 1,500,000. The number average molecular weight (Mn) is determined by gel permeation liquid chromatography (THF solvent, calibration curve determined using linear polystyrene as standard, refractive index detector). The mass ratio of styrene to isoprene, ethylene propylene, butadiene, ethylene butylene, propylene butylene or butylene is preferably from 10 / 90 to 50 / 50, and more preferably from 20 / 80 to 40 / 60, in terms of smooth feel.

[0107] Examples of such styrene copolymers that can be used include commercially available products such as Kraton G1701, Kraton G1702 (Kraton), Viscup P (Arch), Versagel ME1600 (Penreco) dispersed in oil, and PIONIER GEL 12PAO (Hansen & Rosenthal KG).

[0108] (D3) In the glycerin fatty acid ester that is solid at 25°C, being solid at 25°C means that the glycerin fatty acid ester exhibits properties of a semi-solid to solid at 25°C. As the glycerin fatty acid ester that is solid at 25°C, a triester is preferred, and from the viewpoints of excellent adhesion to the skin and achieving a uniform finish, a triglyceride of a fatty acid having 20 to 28 carbon atoms is more preferred, a triglyceride of a fatty acid having 20 to 24 carbon atoms is even more preferred, and tribehenin is even more preferred.

[0109] The dextrin fatty acid ester (D4) is not limited as long as it is one that is commonly used in cosmetics, and is preferably an ester of dextrin with a fatty acid having 8 to 24 carbon atoms, more preferably an ester of dextrin with a fatty acid having 14 to 20 carbon atoms. In addition, the average degree of polymerization of the dextrin is preferably 3 to 150. Specific examples include dextrin palmitate, dextrin stearate, dextrin palmitate-stearate, dextrin oleate, dextrin isopalmitate, dextrin isostearate, dextrin myristate, and dextrin palmitate-2-ethylhexanoate. Of these, from the viewpoints of excellent adhesion to the skin and achieving a uniform finish, dextrin palmitate, dextrin myristate, and dextrin palmitate / 2-ethylhexanoate are preferred, and it is more preferred to include dextrin palmitate.

[0110] As the (D5) organically modified clay mineral, any one that is used in ordinary cosmetics can be used without any limitation. For example, a cationic modified clay mineral obtained by treating a layered clay mineral such as bentonite, laponite, hectorite, montmorillonite, or magnesium aluminum silicate with a quaternary ammonium salt type cationic surfactant is preferred. Here, the quaternary ammonium salt type cationic surfactant is represented by the following formula (15):

[0111] [ka]

[0112] (In the formula, R 31 represents an alkyl group having 10 to 22 carbon atoms or a benzyl group, R 32 represents a methyl group or an alkyl group having 10 to 22 carbon atoms; R 33 and R 34 represents an alkyl group or a hydroxyalkyl group having 1 to 3 carbon atoms, and X represents a halogen atom or a methyl sulfate residue. It is expressed as follows.

[0113] Specifically, dodecyl trimethyl ammonium chloride, myristyl trimethyl ammonium chloride, cetyl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, behenyl trimethyl ammonium chloride, myristyl dimethyl ethyl ammonium chloride, cetyl dimethyl ethyl ammonium chloride, stearyl dimethyl ethyl ammonium chloride, behenyl dimethyl ethyl ammonium chloride, myristyl diethyl methyl ammonium chloride, cetyl diethyl methyl ammonium chloride, stearyl diethyl methyl ammonium chloride, behenyl diethyl methyl ammonium chloride, Examples of the above-mentioned compounds include benzyl dimethyl myristyl ammonium chloride, benzyl dimethyl cetyl ammonium chloride, benzyl dimethyl stearyl ammonium chloride, benzyl dimethyl behenyl ammonium chloride, benzyl methyl ethyl cetyl ammonium chloride, benzyl methyl ethyl stearyl ammonium chloride, distearyl dimethyl ammonium chloride, dibehenyl dihydroxyethyl ammonium chloride, and compounds in which the chloride of each of the above-mentioned compounds is replaced with a bromide compound, and further examples thereof include dipalmityl propyl ethyl ammonium methyl sulfate. Of these, from the viewpoints of excellent adhesion to the skin and achieving a uniform finish, benzyl dimethylstearyl ammonium chloride and dimethyl distearyl ammonium chloride are preferred, and it is preferable to contain at least dimethyl distearyl ammonium chloride.

[0114] As the cationic modified clay mineral obtained by treating the layered clay mineral with a quaternary ammonium salt type cationic surfactant, dimethyl distearyl ammonium hectorite, dimethyl distearyl ammonium bentonite, benzyl dimethyl stearyl ammonium hectorite, etc. are preferable, and dimethyl distearyl ammonium hectorite is more preferable. In addition, examples of commercially available products include Benton 38, Benton 38VCG, Benton 27 (all manufactured by Elementis Japan Co., Ltd.), etc.

[0115] The organically modified clay mineral can also be used as a dispersion diluted with a solvent, because it improves workability and has an excellent effect of thickening oil. Specifically, it is preferable to use a premix gel in which the organic modified clay mineral is dispersed in a solvent in advance. The solvent is not limited as long as it can be thickened by the organic modified clay mineral, but from the viewpoint of the thickening effect of oil, octyl dodecanol, mineral oil, etc. are preferable. In addition, from the viewpoint of efficiently dispersing the organic modified clay mineral and expressing the thickening effect, it is preferable to contain polar additives such as propylene carbonate, ethanol, water, and various surfactants. The content of the organically modified clay mineral in the premix gel is preferably 5 to 25% by mass from the viewpoints of improving workability, thickening effect of oil, and suppressing oil separation from the thickened oily gel itself. As the premix gel, commercially available products such as Bentone Gel EUGV, Bentone Gel MIOV, Bentone Gel ISDV, Bentone Gel VS-5 PCV, and Bentone Gel PTMV (all manufactured by Elementis Japan) can be used.

[0116] As the oil-based gelling agent of component (D), (D5) an organically modified clay mineral is preferred.

[0117] Component (D) may be used alone or in combination of two or more, and the content is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and even more preferably 0.3% by mass or more, based on the total composition, from the viewpoint of excellent adhesion to the skin and uniform finish, and is preferably 10% by mass or less, more preferably 7% by mass or less, and even more preferably 4% by mass or less. The content of component (D) is preferably 0.1 to 10% by mass, more preferably 0.2 to 7% by mass, and even more preferably 0.3 to 4% by mass, based on the total composition.

[0118] In the present invention, the mass ratio (C) / (D) of component (C) to component (D) is preferably 0.5 or more, more preferably 0.8 or more, and even more preferably 1.5 or more, and is preferably 20 or less, more preferably 10 or less, and even more preferably 8 or less, from the viewpoints of suppressing sliding on the skin during application, excellent adhesion to the skin, and suppressing makeup smudging when applied over a liquid foundation. In addition, the mass ratio (C) / (D) of component (C) to component (D) is preferably 0.5 to 20, more preferably 0.8 to 10, and even more preferably 1.5 to 8.

[0119] The water-in-oil emulsion cosmetic of the present invention may further contain a volatile oil. Volatile means that it has a flash point of −4 to 88° C. Examples of volatile oils include volatile silicone oils and volatile hydrocarbon oils. Examples of volatile silicone oils include linear dimethylpolysiloxanes such as hexamethyldisiloxane, octamethyltrisiloxane (1cs), decamethyltetrasiloxane (1.5cs), and dimethylpolysiloxane (2cs); branched siloxanes such as methyltrimethicone, tris(trimethylsilyl)methylsilane, and tetrakis(trimethylsilyl)silane; and cyclic dimethylsiloxanes such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane. Examples of volatile hydrocarbon oils include paraffinic hydrocarbon oils such as n-decane, n-undecane, and n-dodecane; isoparaffinic hydrocarbon oils such as isodecane, isododecane, and hydrogenated polyisobutene; and cyclic paraffinic hydrocarbon oils such as cyclodecane and cyclododecane. Among these, hydrocarbon oils having 8 to 16 carbon atoms are preferred, hydrocarbon oils having 10 to 16 carbon atoms are more preferred, and hydrocarbon oils having 12 carbon atoms are even more preferred.

[0120] As the volatile oil, from the viewpoint of enhancing the dispersibility and solubility of component (D) and controlling the shape of the skin, one or more types selected from hydrocarbon oils and silicone oils are preferred, and one or more types selected from the group consisting of isododecane, hexamethyldisiloxane, methyltrimethicone, and dimethylpolysiloxane having a kinetic viscosity of 2 cSt or less at 25°C are preferred, and one or more types selected from isododecane, hexamethyldisiloxane, and methyltrimethicone are more preferred, and it is even more preferred that the oil contains at least hexamethyldisiloxane. The kinematic viscosity can be measured, for example, by using an Ubbelohde viscometer.

[0121] Commercially available products of hexamethyldisiloxane and dimethylpolysiloxane with a kinematic viscosity of 2 cSt or less at 25°C include "KF-96L-0.65cs" (hexamethyldisiloxane), "TMF1.5", "KF-96L-1cs" (octamethyltrisiloxane), "KF-96L-1.5cs", and "KF-96L-2cs" manufactured by Shin-Etsu Chemical Co., Ltd., "SH200C Fluid 1cs" and "SH200C Fluid 1.5cs" manufactured by Dow Corning Toray Co., Ltd., "TSF451-0.65" manufactured by Momentive Performance Materials Japan, LLC, "BELSIL DM0.65" manufactured by Wacker Asahi Kasei Silicone Co., Ltd., and "XIAMETER PMX-200 SILICONE FLUID 0.65CS" manufactured by Dow Toray Co., Ltd., and the like.

[0122] The volatile oil may be used alone or in combination of two or more, and the content is preferably 5% by mass or more in the total composition, more preferably 15% by mass or more, even more preferably 30% by mass or more, even more preferably 50% by mass or more, preferably 75% by mass or less, more preferably 70% by mass or less, and even more preferably 65% ​​by mass or less, from the viewpoint of increasing the dispersibility and solubility of component (D) and controlling the shape of the skin. The content of the volatile oil is preferably 5 to 75% by mass in the total composition, more preferably 15 to 70% by mass, even more preferably 30 to 65% by mass, and even more preferably 50 to 65% by mass.

[0123] The water-in-oil emulsion cosmetic of the present invention may further contain a powder. As the powder, those generally used in cosmetics, such as color pigments, extender pigments, and luster pigments, can be used. The color pigments are those used in ordinary cosmetics, such as metal oxides such as titanium oxide, zinc oxide, cerium oxide, aluminum oxide, yellow iron oxide, black iron oxide, red ocher, Prussian blue, ultramarine, chromium oxide, and chromium hydroxide, metal complexes such as manganese violet and cobalt titanate, and inorganic pigments such as carbon black; Red No. 3, Red No. 104, Red No. 106, Red No. 201, Red No. 202, Red No. 204, Red No. 205, Red No. 206, Red No. 207, Red No. 209, Red No. 300, Red No. 301, Red No. 302, Red No. 303, Red No. 304, Red No. 305, Red No. 306, Red No. 307, Red No. 309, Red No. 308, Red No. 309, Red No. 310, Red No. 311, Red No. 312, Red No. 313, Red No. 314, Red No. 315, Red No. 316, Red No. 317, Red No. 318, Red No. 319, Red No. 320, Red No. 321, Red No. 322, Red No. 323, Red No. 324, Red No. 325, Red No. 326, Red No. 327, Red No. 328, Red No. 329, Red No. 330, Red No. 331, Red No. 332, Red No. 333, Red No. 334, Red No. 335, Red No. 336, Red No. 337, Red No. 338, Red No. 339, Red No. 339, Red No synthetic organic pigments such as Red No. 20, Red No. 226, Red No. 227, Red No. 228, Red No. 230, Red No. 401, Red No. 405, Red No. 505, Orange No. 203, Orange No. 204, Orange No. 205, Yellow No. 4, Yellow No. 5, Yellow No. 401, Blue No. 1, and Blue No. 404; natural organic pigments such as β-carotene, caramel, and paprika color, and composites of these color pigments and composite pigments combining these color pigments with pearl pigments. Examples of the pearl pigments to be treated include natural or synthetic inorganic powders such as mica, phlogopite, talc, silica, sericite, glass, kaolin, bismuth oxychloride, cerium oxide, calcium sulfate, barium sulfate, magnesium sulfate, and plate-like alumina powder. Specific examples of composite pigments include titanium oxide-coated mica, iron oxide-coated mica, iron oxide-coated titanium mica, iron oxide-coated synthetic phlogopite, chromium oxide-coated titanium mica, titanium oxide-coated glass powder, iron oxide-coated glass powder, titanium oxide-containing glass powder, and iron oxide-containing glass powder.

[0124] Examples of the extender pigments include those used in ordinary cosmetics, such as inorganic extender pigments such as magnesium silicate, aluminum silicate, talc, sericite, mica, synthetic fluorophlogopite, glass powder, phlogopite, kaolin, clay, bentonite, hectorite, zeolite, bismuth oxychloride, zirconium oxide, magnesium oxide, aluminum oxide, calcium sulfate, barium sulfate, magnesium sulfate, calcium carbonate, and magnesium carbonate, as well as composite powders of these.

[0125] The luster pigments may be those used in ordinary cosmetics, such as plate-like powders of mica, synthetic phlogopite, glass, silica, alumina, etc., the surface of which is coated with colorants such as titanium oxide, iron oxide, silicon oxide, Prussian blue, chromium oxide, tin oxide, chromium hydroxide, gold, silver, carmine, organic pigments, etc., and film rolls cut into any shape such as polyethylene terephthalate-polymethyl methacrylate laminated powder, polyethylene terephthalate-aluminum vapor-deposited powder, and polyethylene terephthalate-gold vapor-deposited laminated powder may also be used. Further, organic powders such as polyethylene powder, polypropylene powder, polymethyl methacrylate powder, nylon powder, polytetrafluoroethylene powder, silicone powder, silicone rubber powder, silk powder, urethane powder, cellulose powder, starch powder, and polyethylene fluoride; inorganic powders such as silica, magnesium carbonate, and calcium carbonate; acylated lysine powders such as lauroyl lysine; and metal soap powders which are higher fatty acid metal salts can be used.

[0126] These powders may be used as they are, or may be subjected to a hydrophobic treatment by a conventional method before use. Examples of the hydrophobic treatment include surface treatments such as silicone treatment, alkyl treatment, alkylsilane treatment, metal soap treatment, water-soluble polymer treatment, amino acid treatment, acylated amino acid treatment, lecithin treatment, organic titanate treatment, polyol treatment, acrylic resin treatment, methacrylic resin treatment, and urethane resin treatment.

[0127] The powder may be used alone or in combination of two or more kinds, and the content is preferably 0.1% by mass or more, more preferably 1% by mass or more, and even more preferably 2% by mass or more, based on the total composition from the viewpoint of thin and uniform adhesion to the skin, and is preferably 30% by mass or less, more preferably 20% by mass or less, and even more preferably 10% by mass or less. The powder content is preferably 0.1 to 30% by mass, more preferably 1 to 20% by mass, and even more preferably 2 to 10% by mass, based on the total composition.

[0128] In the water-in-oil emulsion cosmetic of the present invention, the water content is preferably 5 to 60 mass %, more preferably 10 to 50 mass %, and even more preferably 15 to 35 mass %, from the viewpoint of thin and uniform adhesion to the skin.

[0129] In addition to the above-mentioned components, the water-in-oil emulsion cosmetic of the present invention can optionally contain various components that are commonly used in cosmetics. These components include, for example, oily components other than those mentioned above, surfactants, water-soluble polymers, antioxidants, UV absorbers, vitamins, preservatives, pH adjusters, fragrances, plant extracts, moisturizers, colorants, cooling agents, antiperspirants, disinfectants, skin activators, etc.

[0130] The water-in-oil emulsion cosmetic of the present invention can be produced according to a conventional method, and can be made into a formulation such as a liquid, emulsion, paste, cream, gel, or solid. Furthermore, the water-in-oil emulsion cosmetic of the present invention can be used, for example, as makeup cosmetics such as makeup base, foundation, concealer, blusher, eye shadow, mascara, eyeliner, eyebrow, overcoat agent, and lipstick; UV protection cosmetics such as sunscreen lotion and sunscreen cream; and skin care cosmetics such as skin care lotion, skin care cream, BB cream, and beauty serum. EXAMPLES

[0131] Production Example 1 (Production of poly(N-propionylethyleneimine) modified silicone) 12.9 g (0.13 mol) of 2-ethyl-2-oxazoline and 27.7 g of ethyl acetate were mixed, and the mixture was dehydrated with 2.0 g of molecular sieves (Zeorum A-4, manufactured by Tosoh Corporation) at 28° C. for 15 hours. In addition, 100 g of side chain primary aminopropyl modified polydimethylsiloxane (KF-8015, Shin-Etsu Silicones, weight average molecular weight 100,000, amine equivalent 20,000) was mixed with 203 g of ethyl acetate, and the mixture was dehydrated with 15.2 g of molecular sieves at 28°C for 15 hours. To the above-mentioned dehydrated 2-ethyl-2-oxazoline in ethyl acetate solution, 0.77 g (0.005 mol) of diethyl sulfate was added, and the mixture was heated under reflux at 80°C for 8 hours under a nitrogen atmosphere to synthesize terminal-reactive poly(N-propionylethyleneimine). The number average molecular weight measured by GPC was 2700. This terminally reactive poly(N-propionylethyleneimine) solution was added all at once to the above dehydrated side chain primary aminopropyl modified polydimethylsiloxane solution, and the mixture was heated to reflux at 80° C. for 10 hours. The reaction mixture was concentrated under reduced pressure to obtain N-propionylethyleneimine-dimethylsiloxane copolymer as a white rubbery solid (108 g). The mass ratio of the organopolysiloxane segment in the final product was 0.87, and the weight average molecular weight of the final product was 115,000.

[0132] Examples 1 to 10, Comparative Examples 1 to 2 Water-in-oil emulsion cosmetics with the compositions shown in Table 1 were prepared and evaluated for resistance to slipping during application, adhesion of the coating film, and the lack of makeup smudging when applied over a liquid foundation. The results are also shown in Table 1.

[0133] (Manufacturing method) The oil phase components including components (A), (B), (C) and (D) were dispersed using a disperser. The aqueous phase components were then added and dispersed using a disperser, and the mixture was stirred using a homomixer to produce a water-in-oil emulsion cosmetic (wrinkle improvement agent).

[0134] (Evaluation method) Five expert panelists applied each water-in-oil emulsion cosmetic (wrinkle improvement agent) to the skin and evaluated it based on the following criteria: how easily it slipped on the skin during application, how well the coating adhered, and how well it kept makeup from smudging when applied over a liquid foundation (Revue Essence in Moisture Liquid n). The results are shown as the cumulative scores of the five panelists.

[0135] (1) Difficulty in sliding on the surface during application; 5;No slipping at all. 4;Does not slip upwards. 3;Doesn't slide much. 2;Slips slightly upwards. 1;Slide upwards.

[0136] (2) Good adhesion of the coating: 5;The cosmetics adhere firmly to the skin. 4;The cosmetics are in close contact with the skin. 3; The cosmetics are slightly in contact with the skin. 2;The cosmetics are not in close contact with the skin. 1; The cosmetics are not in close contact with the skin.

[0137] (3) No smudging when applied over liquid foundation: 5; Makeup smudging is not noticeable. 4; Makeup smudging is barely noticeable. 3; Makeup smudging is less noticeable. 2; Makeup smudging is noticeable. 1; Makeup smudging is very noticeable.

[0138] [Table 1]

[0139] In Table 1, *1 and *2 are as follows. *1: Shin-Etsu Chemical Co., Ltd. "NBN-30-ID" (e / f=60 / 40 (mol / mol), Mn=360,000 in the following formula (6)) isododecane solution of norbornene / tris(trimethylsiloxy)silylnorbornene copolymer, effective component concentration: 30% by mass

[0140] [ka]

[0141] *2: "TSPL-30-ID" manufactured by Shin-Etsu Chemical Co., Ltd. (a solution of tri(trimethylsiloxy)silylpropylcarbamic acid pullulan in isododecane, active ingredient concentration: 30% by mass) was dried under reduced pressure at 50°C for 12 hours, and the obtained solid was used.

[0142] Examples 11 to 17 The water-in-oil emulsion cosmetics having the compositions shown in Tables 2 and 3 are produced in the same manner as in Examples 1-10. All of the water-in-oil emulsion cosmetics of Examples 11 to 17 did not slide easily during application, had excellent adhesion between the skin and the cosmetics, and did not cause noticeable makeup smudging when applied over a liquid foundation (Revue Essence in Moisture Liquid n).

[0143] [Table 2]

[0144] [Table 3]

Claims

1. The following components (A), (B), (C), and (D): (A) Polymers containing norbornane structures and / or silicone-modified pullulans, (B) Phenyl-modified silicone oil, (C) Polyether-modified silicone, (D) Oily gelling agent A water-in-oil emulsion cosmetic containing the following ingredients.

2. The water-in-oil emulsion cosmetic according to claim 1, wherein component (A) is a norbornane structure-containing silicone-modified polymer.

3. The water-in-oil emulsion cosmetic composition according to claim 1 or 2, wherein component (A) is a silicone-modified polynorbornene represented by the following formula (6). 【Chemistry 1】 In the formula, e and f are repeating units, and are independent integers of 1 or greater.

4. The water-in-oil emulsion cosmetic composition according to claim 1 or 2, wherein the content of component (A) is 0.1 to 30% by mass, the content of component (B) is 0.1 to 30% by mass, the content of component (C) is 0.1 to 15% by mass, and the content of component (D) is 0.1 to 10% by mass.

5. The water-in-oil emulsion cosmetic composition according to claim 1 or 2, wherein the oily gelling agent of component (D) is one or more selected from organopolysiloxanes formed by the bonding of poly(N-acylalkyleneimine) segments, styrene copolymers, glycerin fatty acid esters that are solid at 25°C, dextrin fatty acid esters, and organically modified clay minerals.

6. The water-in-oil emulsion cosmetic composition according to claim 1 or 2, wherein the mass ratio (A) / (B) of component (A) to component (B) is 0.2 to 30.

7. The water-in-oil emulsion cosmetic composition according to claim 1 or 2, wherein the mass ratio (A) / (C) of component (A) to component (C) is 0.3 to 30.

8. The water-in-oil emulsion cosmetic composition according to claim 1 or 2, wherein the mass ratio (C) / (D) of component (C) to component (D) is 0.5 to 20.

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