Skin external use composition

Abstract

The present invention relates to a composition for external use on the skin, comprising the following components (A), (B) and (C); (A) a polymer having a polysiloxane structure, wherein the deformation ratio measured by a prescribed method (1) is 0.3 or more and 1 or less, and the minimum diameter of the cylindrical axis at which the polymer film does not crack in a bending resistance test by a cylindrical axis method performed by a prescribed method (2) is 2 mm or more and 25 mm or less: 1 to 30% by mass; (B) a volatile oil having a volatility of 14% or more after drying for 30 minutes at 1 atmosphere, 40°C and 60% RH; (C) a powder; the mass ratio of component (A) to component (C) (A) / (C) is 1 to 50; and the composition contains at least 0.1 to 30% by mass of an inorganic powder (C-1) having a refractive index of 1.3 to 1.8 as component (C).

Description

Technical Field

[0001] The present invention relates to a composition for external use on skin. Background Art

[0002] As people age, their skin becomes more wrinkled. This is one aspect of skin aging, which depends on many factors, such as changes in skin tissue and the effects of ultraviolet radiation.

[0003] In the prior art, skin care products for making skin wrinkles less noticeable are being studied, but the improvement effect is extremely low and cannot satisfy women who have wrinkle problems.

[0004] On the other hand, cosmetics that are formulated with film-forming polymers for the purpose of improving the uniformity of cosmetic films or the durability of cosmetics are known. For example, Patent Document 1 describes a cosmetic that contains a film-forming polymer having a predetermined functional group introduced into the backbone of a polycycloolefin polymer, and that has good durability and touch.

[0005] (Patent Document 1) Japanese Patent Application Publication No. 2012-17317 Summary of the invention

[0006] The present invention relates to a composition for external use on skin, comprising the following components (A), (B) and (C);

[0007] (A) a polymer having a polysiloxane structure, wherein the deformation ratio measured by the following method (1) is 0.3 or more and 1 or less, and the minimum diameter of the cylindrical axis at which the polymer film does not crack in a bending resistance test using a cylindrical axis method performed by the following method (2) is 2 mm or more and 25 mm or less: 1 to 30% by mass;

[0008] Method (1): prepare a 10 mass % hexamethyldisiloxane solution of the above polymer; apply 0.005 g of the solution on one side of a polyethylene sheet of 20 mm wide × 100 mm long × 0.03 mm thick from one end of the short side in the longitudinal direction to a range of 20 mm wide × 50 mm long, and dry in a constant temperature bath set at 40° C. for 10 minutes; the length of the polyethylene sheet on which the above solution has been applied is defined as L1, and the length of the polyethylene sheet on which the solution has been applied is defined as L2, and the value of L2 / L1 is used as the deformation ratio;

[0009] Method (2): preparing a 30% by mass hexamethyldisiloxane solution of the above polymer; applying the solution to a polyethylene terephthalate film of 50 mm in width × 100 mm in length × 0.1 mm in thickness using a 200 μm applicator, and drying the film in a constant temperature bath set at 40° C. for 120 minutes to prepare a test piece; using the test piece, conducting a bending resistance test according to the cylindrical axis method specified in JIS K5600-5-1:1999, and determining the minimum diameter of the cylindrical axis at which the polymer film on the test piece does not crack;

[0010] (B) a volatile oil having a volatility of 14% or more after drying at 1 atmosphere, 40°C, and 60% RH for 30 minutes;

[0011] (C) Powder;

[0012] The mass ratio of component (A) to component (C) (A) / (C) is 1 to 50;

[0013] The composition contains at least 0.1 to 30 mass % of (C-1) inorganic powder having a refractive index of 1.3 to 1.8 as a component (C). BRIEF DESCRIPTION OF THE DRAWINGS

[0014] Figure 1 This is a diagram for explaining the method for evaluating the deformation ratio (L2 / L1) of a polymer by method (1).

[0015] Figure 2 The diagram shows the state of applying each skin external preparation composition when evaluating the wrinkle improving effect in Examples. DETAILED DESCRIPTION

[0016] Conventional cosmetics containing film-forming polymers have insufficient wrinkle-improving effects and also have technical problems such as an unnatural oily makeup effect and a noticeable boundary between the coating film and the skin.

[0017] The present inventors have discovered that by combining an inorganic powder having a specific refractive index with a specific film-forming polymer in a specific ratio, a skin external preparation composition can be obtained that maintains high shrinkage and improves wrinkles while suppressing oiliness, achieving a natural and matte makeup effect, and having an indistinct boundary between the coating film and the skin, thereby completing the present invention.

[0018] The skin external preparation composition of the present invention can improve skin wrinkles and suppress oily shine, thereby obtaining a fine-textured, natural and evenly matte makeup effect, and the boundary between the coating film and the skin is not obvious.

[0019] The so-called "skin wrinkles" in this specification refer to the shape changes caused by sagging skin, and the bumps and lines that appear on the skin surface. Skin wrinkles are easy to appear around the lips, around the eyes, forehead, neck, body, etc. Small lines are small wrinkles, and large lines are large wrinkles. Large wrinkles occur due to the distribution of pores on the nasolabial folds, cheeks, etc. The skin topical composition of the present invention can exert the effect of making various wrinkles less noticeable, especially, even large wrinkles such as nasolabial folds can be improved in a non-invasive manner.

[0020] <Ingredients (A)>

[0021] The component (A) used in the present invention is a polymer having a polysiloxane structure, and its deformation ratio measured by the above-mentioned method (1) is greater than or equal to 0.3 and less than or equal to 1, and in the bending resistance test of the cylindrical mandrel method performed by the above-mentioned method (2), the minimum diameter of the cylindrical mandrel at which the polymer film does not crack is greater than or equal to 2 mm and less than or equal to 25 mm.

[0022] By making component (A) satisfy the above deformation ratio measured by method (1), for example, when a composition containing a polymer belonging to component (A) is applied to the skin around wrinkles, and then the composition is dried, the skin surface in close contact with the film shrinks as the film containing the polymer shrinks. This action stretches the skin at the wrinkled part, making the wrinkles less noticeable.

[0023] Reference Figure 1 The evaluation method of the deformation ratio (L2 / L1) of the component (A) measured by the above method (1) is described. First, a 10 mass % hexamethyldisiloxane solution of the component (A) used in the composition is prepared. 0.005 g of the solution is added to Figure 1 On one side of a polyethylene sheet 1 having a width (W) of 20 mm × a length (L0) of 100 mm × a thickness of 0.03 mm as shown in (a), a coating is applied from one end 1a of the short side of the polyethylene sheet 1 in the range of 20 mm in width × 50 mm in length in the longitudinal direction ( Figure 1 The portion 2 shown in (a) was dried in a thermostatic bath set at 40° C. for 10 minutes. Figure 1 (b) is a schematic diagram of a polyethylene sheet 1 coated with the above solution, in which a portion of the polyethylene sheet is deformed (bent) due to the shrinkage of the polymer as component (A) after the polyethylene sheet 1 is dried.

[0024] After drying, the polyethylene sheet ( Figure 1In (b), the length of the polyethylene sheet at the portion where the solution was applied was set to L1 (50 mm), and the length of the polyethylene sheet at the portion where the solution was applied was set to L2, and L2 / L1 was calculated, and this value was used as the deformation ratio. L2 was set to the average value of the values ​​measured on the two long sides of the polyethylene sheet 1. The larger the value of L2 / L1, the greater the shrinkage of the polymer caused by drying, and the upper limit of L2 / L1 is 1.

[0025] From the viewpoint of stretching skin wrinkles to make them less noticeable, the deformation ratio L2 / L1 of component (A) evaluated by the above method (1) is 0.3 or more, preferably 0.5 or more, more preferably 0.6 or more, further preferably 0.7 or more, further preferably 0.8 or more, further preferably 0.85 or more, further preferably 0.9 or more, further preferably 0.95 or more, and the upper limit is 1.

[0026] The deformation ratio can be specifically evaluated by the method described in Examples.

[0027] In addition, component (A) has excellent bending resistance. In the bending resistance test of the cylindrical mandrel method performed by the above method (2), the minimum diameter of the cylindrical mandrel at which the film of the polymer of component (A) does not crack is 2 mm or more and 25 mm or less. Therefore, the film formed by the composition containing component (A) is not prone to cracking and is easy to shrink in a state of following the shape of the skin.

[0028] The smaller the minimum diameter of the cylindrical shaft, the better the bending resistance. From the viewpoint of obtaining sufficient adhesion between the film and the skin surface when the film containing the polymer shrinks, the minimum diameter is 25 mm or less, preferably 20 mm or less, more preferably 12 mm or less, further preferably 8 mm or less, further preferably 6 mm or less, and further preferably 5 mm or less. On the other hand, from the viewpoint of imparting sufficient strength and shape control effect in order to stretch the skin wrinkles so that they are not obvious, the minimum diameter of the cylindrical shaft without cracks is 2 mm or more, preferably 3 mm or more. The specific range of the minimum diameter of the cylindrical shaft is 2 to 25 mm, preferably 2 to 20 mm, more preferably 2 to 12 mm, further preferably 2 to 8 mm, further preferably 3 to 6 mm, and further preferably 3 to 5 mm.

[0029] The bending resistance can be evaluated using a type 1 bending tester specified in JIS K5600-5-1:1999, specifically, by the method described in Examples.

[0030] In addition, from the viewpoint of the wrinkle-improving effect on the skin, for component (A), the ratio of the deformation ratio obtained by the above method (1) to the minimum diameter (mm) of the cylindrical axis obtained by the above method (2) [(deformation ratio) / (minimum diameter of the cylindrical axis)] is preferably 0.01 or more, more preferably 0.02 or more, further preferably 0.10 or more, and further preferably 0.15 or more. From the viewpoint of imparting sufficient strength and shape control effect to make skin wrinkles less noticeable, it is preferably 0.5 or less, and further preferably 0.4 or less. The specific range of the above ratio is preferably 0.01 to 0.5, more preferably 0.02 to 0.5, further preferably 0.10 to 0.5, further preferably 0.15 to 0.5, and further preferably 0.15 to 0.4.

[0031] In the present invention, the "polysiloxane structure" refers to a structure represented by the following general formula (I).

[0032]

[0033] In the general formula (I), R 1 Each independently represents a hydrocarbon group having 1 to 12 carbon atoms, and p is an integer greater than 1. From the viewpoint of making skin wrinkles less noticeable during application and obtaining a sufficient wrinkle improvement effect (hereinafter also referred to as "skin wrinkle improvement effect") and from the viewpoint of versatility, R 1 It 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 still more preferably a methyl group.

[0034] The polymer of component (A) may have a polysiloxane structure and may be a polymer consisting of only a polysiloxane structure. However, from the viewpoint of providing a polymer having the above-mentioned predetermined properties, a polymer having a polysiloxane structure in part is preferred.

[0035] In the case of a polymer having a polysiloxane structure in part, the polysiloxane structure may be present in any part of the main chain or the side chain in the polymer, but is preferably present in the side chain from the viewpoint of obtaining a polymer having the above-mentioned predetermined properties.

[0036] When the polysiloxane structure exists in the polymer main chain, there is no particular limitation on its bonding form. For example, the polysiloxane structure may exist at the end of the polymer main chain, or it may be a copolymer in which the polysiloxane structure is bonded in a block or random manner in the polymer main chain. In addition, a polymer graft-modified by a compound having a polysiloxane structure may also be used.

[0037] As component (A) used in the present invention, a polysiloxane-modified polymer is preferably used, and specific examples thereof include: polysiloxane-modified polymers containing norbornene structures such as polysiloxane-modified polynorbornene; polysiloxane-modified pullulan; silicic acid compounds containing polysiloxane structures such as trialkylsiloxysilicic acid, fluorine-modified alkylsiloxysilicic acid, and phenyl-modified alkylsiloxysilicic acid; polysiloxane dendrimers, etc.

[0038] (Norbornane structure-containing polysiloxane-modified polymer)

[0039] In the present invention, the "norbornane structure" refers to a structure represented by the following formula: The polysiloxane-modified polymer containing a norbornane structure may be a polysiloxane-modified polymer having the structure represented by the formula at any site in the polymer.

[0040]

[0041] Examples of the polysiloxane-modified polymer containing a norbornane structure include polymers having a repeating unit represented by the following general formula (1) or (2).

[0042]

[0043] In the formula, R 2 Each independently represents an alkyl group having 1 to 12 carbon atoms, and X represents 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.

[0044]

[0045] In the formula, R 1 Similar to the above, c is an integer of 1 to 5.

[0046]

[0047] 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.

[0048] In the above general formula (1), R 2 Each independently represents an alkyl group having 1 to 12 carbon atoms, and is preferably a methyl group, an ethyl group, an n-propyl group, a butyl group or a pentyl group, and more preferably a methyl group, from the viewpoint of the skin wrinkle improving effect and the viewpoint of versatility.

[0049] X is a group represented by the above formula (i), wherein R 1Each independently represents a hydrocarbon group having 1 to 12 carbon atoms. From the viewpoint of the wrinkle-improving effect on the skin and the viewpoint of versatility, R 1 It 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 further preferably a methyl group. c is an integer of 1 to 5, and from the viewpoint of versatility, c=1 is preferred. That is, X is preferably a trimethylsilyloxy group.

[0050] a is an integer of 1 to 3, and for example, a polymer may be a mixture of a repeating unit of 2 and a repeating unit of 3. From the viewpoint of versatility, a is preferably 3. b is an integer of 0 to 2, and from the same viewpoint, is preferably 0, 1 or a combination thereof, and more preferably 0.

[0051] In the above general formula (2), R 1 , R 2 and b are the same as above. d is an integer of 2 or more and 5 or less, and from the viewpoint of versatility, d=2 is preferred. With regard to the cyclic polysiloxane structure in the general formula (2), from the same viewpoint, R 1 and R 1 is a methyl group, and d is 2 or 3. That is, the cyclic polysiloxane structure in the general formula (2) is preferably a structure represented by the following formula (4) or (5).

[0052]

[0053] From the viewpoint of the wrinkle improvement effect on the skin, the ratio of the repeating unit represented by the above general formula (1) or (2) in the polysiloxane-modified polymer containing a norbornane structure is preferably 10% or more, more preferably 30% or more, and further preferably 50% or more of the total number of repeating units in the polymer. In addition, the upper limit is 100%, preferably 95% or less, more preferably 90% or less, and further preferably 70% or less. The specific range of the repeating unit represented by the above general formula (1) or (2) in the polysiloxane-modified polymer containing a norbornane structure is preferably 10 to 100%, more preferably 10 to 95%, further preferably 30 to 90%, and further preferably 50 to 70% of the total number of repeating units in the polymer.

[0054] The polysiloxane-modified polymer containing a norbornane structure may have a repeating unit represented by the following general formula (3) in addition to the repeating unit represented by the above general formula (1) or (2).

[0055]

[0056] In the formula, R 3 ~R 6 Each independently represents a substituent selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, and a halogenated hydrocarbon group, or an oxetanyl group, an alkoxycarbonyl group, a polyoxyalkylene group, a polyglyceryl group, or an alkoxysilyl group. 3 ~R 6 The two groups of may be combined with each other to form an alicyclic structure, an aromatic ring structure, a carbonimide group or an acid anhydride group. b is the same as above.

[0057] From the viewpoint of the wrinkle improvement effect on the skin, the proportion of the repeating unit represented by the above general formula (3) in the polysiloxane-modified polymer containing a norbornane structure is preferably 90% or less, more preferably 70% or less, and further preferably 50% or less, based on the total number of repeating units in the polymer. In addition, in the case of containing the repeating unit represented by the above general formula (3), its proportion is preferably 5% or more, more preferably 10% or more, and further preferably 30% or more, based on 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 polysiloxane-modified polymer containing a norbornane structure is preferably 5 to 90%, more preferably 10 to 70%, and further preferably 30 to 50%, based on the total number of repeating units in the polymer.

[0058] The ratio of the repeating units represented by the general formulae (1) to (3) in the polysiloxane-modified polymer containing a norbornane structure can be determined by 1 It was determined by H-NMR measurement.

[0059] The polysiloxane-modified polymer containing a norbornane structure is preferably a polysiloxane-modified polynorbornene, and more preferably a polysiloxane-modified polynorbornene represented by the following formula (6).

[0060]

[0061] In the formula, e and f are the numbers of repeating units, and each independently represents an integer of 1 or more.

[0062] From the viewpoint of the wrinkle-improving effect on the skin, the ratio of e to f in the general formula (6) is preferably e / f = 20 / 80 to 90 / 10 (mol / mol), more preferably 30 / 70 to 80 / 20 (mol / mol), and further preferably 50 / 50 to 70 / 30 (mol / mol).

[0063] The number average molecular weight Mn of the polysiloxane-modified polymer containing a norbornane structure is preferably 50,000 or more, more preferably 100,000 or more, and further preferably 200,000 or more, and is preferably 2,000,000 or less, more preferably 1,500,000 or less, further preferably 800,000 or less, and further preferably 600,000 or less, from the viewpoint of achieving both shrinkage resistance and bending resistance and the wrinkle-improving effect on the skin. The specific range of the number average molecular weight Mn of the polysiloxane-modified polymer containing a norbornane structure is preferably 50,000 to 2,000,000, more preferably 100,000 to 1,500,000, further preferably 200,000 to 800,000, and further preferably 200,000 to 600,000.

[0064] The number average molecular weight Mn of the polymer can be measured by a gel filtration chromatography (GPC) method using polystyrene as a standard substance, and specifically, can be measured by the method described in Examples.

[0065] The polysiloxane-modified polymer containing a norbornane structure is obtained by, for example, adding and polymerizing a polysiloxane-modified cyclic olefin monomer containing a norbornane structure or capable of forming a norbornane structure according to a known method.

[0066] For example, a polysiloxane-modified polymer having a norbornane structure and having a repeating unit represented by the general formula (1) or (2) can be obtained by addition polymerizing a cyclic olefin monomer represented by the general formula (1a) or (2a). Alternatively, a cyclic olefin monomer represented by the general formula (3a) can be copolymerized.

[0067]

[0068] In the formula, R 1 Each independently represents 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.

[0069]

[0070] In the formula, R 2 Each independently represents a hydrocarbon group having 1 to 12 carbon atoms, and c is an integer of 1 to 5.

[0071]

[0072] 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.

[0073]

[0074] In the formula, R3 ~R 6 Each independently represents a substituent selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, and a halogenated hydrocarbon group, or an oxetanyl group, an alkoxycarbonyl group, a polyoxyalkylene group, a polyglyceryl group, or an alkoxysilyl group. 3 ~R 6 The two groups of may be combined with each other to form an alicyclic structure, an aromatic ring structure, a carbonimide group or an acid anhydride group. b is the same as above.

[0075] When the cyclic olefin monomer represented by the general formula (3a) is copolymerized, from the viewpoint of the wrinkle-improving effect on the skin, the amount of the cyclic olefin monomer represented by the general formula (3a) used is preferably 90 mol% or less, more preferably 70 mol% or less, further preferably 50 mol% or less, and is preferably 5 mol% or more, more preferably 10 mol% or more, further preferably 30 mol% or more, when the total monomers used in the polymerization are set to 100 mol%.

[0076] The polysiloxane-modified polynorbornene represented by the above formula (6) can be obtained by subjecting tris(trimethylsilyloxy)silylnorbornene represented by the following formula (6a) to addition polymerization with norbornene.

[0077]

[0078] From the viewpoint of the wrinkle-improving effect on skin, the copolymerization ratio of tris(trimethylsilyloxy)silylnorbornene to norbornene is preferably 20 / 80 to 90 / 10 (mol / mol), more preferably 30 / 70 to 80 / 20 (mol / mol), and further preferably 50 / 50 to 70 / 30 (mol / mol).

[0079] The repeating units shown in the above general formulae (1) to (3) and the above formula (6) are all repeating units representing 2,3-addition structural units of the cyclic olefin monomers as the raw material monomers, but may also include repeating units that become 2,7-addition structural units by addition polymerization of the cyclic olefin monomers.

[0080] As the polysiloxane-modified polymer containing a norbornane structure, a norbornene / tris(trimethylsiloxy)silylnorbornene) copolymer is preferred, 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 (NORBORNENE / TRIS(TRIMETHYLSILOXY)SILYLNORBORNENE COPOLYMER).

[0081] Examples of commercially available polysiloxane-modified polymers containing a norbornane structure include NBN-30-ID (isododecane solution of a norbornene / tris(trimethylsilyloxy)silylnorbornene) copolymer manufactured by Shin-Etsu Chemical Co., Ltd., and the like.

[0082] (Polysilicone modified pullulan)

[0083] Examples of the polysiloxane-modified pullulan include pullulan having a polysiloxane structure in a side chain. Specifically, from the viewpoint of the wrinkle-improving effect on the skin and the viewpoint of versatility, a polysiloxane-modified pullulan in which at least a part of the hydrogen atoms of the OH group in the pullulan is substituted with a group represented by the following general formula (7) is preferred.

[0084] -Z 1 -SiX a R 2 3-a (7)

[0085] In the formula, Z 1 is a single bond or a divalent organic group, R 2 , X, and a are the same as above. From the same viewpoint, X is preferably a trimethylsilyloxy group, and a is preferably 3.

[0086] In general formula (7), from the same point of view, Z 1 It is preferably a divalent organic group, more preferably a divalent group represented by the following general formula (8) or (9), and still more preferably a divalent group represented by the following general formula (9).

[0087]

[0088] In the formula, R 11 The alkylene group has 1 to 10 carbon atoms, and examples thereof include methylene, ethylene, trimethylene, propylene, and butylene. From the same viewpoint, among these, ethylene, trimethylene, and propylene are preferred, and trimethylene or propylene is more preferred.

[0089] Examples of commercially available silicone-modified pullulan include TSPL-30-ID (tris(trimethylsiloxy)silylpropyl uric acid pullulan in isododecane solution) and TSPL-30-D5 (tris(trimethylsiloxy)silylpropyl uric acid pullulan in cyclopentasiloxane solution) manufactured by Shin-Etsu Chemical Co., Ltd.

[0090] (Silicic acid compound containing polysiloxane structure)

[0091] Examples of the polysiloxane structure-containing silicate compound used in the present invention include silicate compounds having a polysiloxane structure at the terminal, such as trialkylsiloxysilicic acid, fluorine-modified alkylsiloxysilicic acid, and phenyl-modified alkylsiloxysilicic acid.

[0092] The alkyl group in the trialkylsiloxysilicic acid preferably has 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms, and further preferably a methyl group, from the viewpoint of the wrinkle-improving effect on the skin and the versatility. Specific examples of the trialkylsiloxysilicic acid include trimethylsiloxysilicic acid.

[0093] Examples of fluorine-modified alkylsiloxysilicates include compounds in which at least a portion of hydrogen atoms in the alkyl group of trialkylsiloxysilicates are substituted with fluorine atoms, and specific examples thereof include trifluoropropyldimethylsiloxysilicate and trifluoropropyldimethyl / trimethylsiloxysilicate.

[0094] Examples of the phenyl-modified alkylsiloxysilicate include phenylpropyldimethylsiloxysilicate and phenylpropyldimethyl / trimethylsiloxysilicate.

[0095] Among the silicic acid compounds containing a polysiloxane structure, at least one selected from trialkylsiloxysilicic acid and fluorine-modified alkylsiloxysilicic acid is preferred from the viewpoint of the wrinkle-improving effect on the skin.

[0096] As commercially available silicate compounds containing a polysiloxane structure, trimethylsiloxysilicic acid (solutions) such as KF-7312J, KF-7312K, KF-7312T, KF-7312L, X-21-5249, X-21-5250, KF-9021, X-21-5595, X-21-5616, KF-9021L, X-21-5249L, and X-21-5250L manufactured by Shin-Etsu Chemical Co., Ltd., XS66-B8226 (cyclopentasiloxane solution of trifluoropropyldimethyl / trimethylsiloxysilicic acid), XS66-B8636 (polydimethylsiloxane solution of trifluoropropyldimethyl / trimethylsiloxysilicic acid), and SilShine 151 (phenylpropyldimethylsiloxysilicic acid) manufactured by Momentive Performance Materials Japan Co., Ltd. can be used.

[0097] (Polysiloxane Dendrimer)

[0098] Examples of polysiloxane dendrimers include vinyl polymers having a siloxane dendrimer structure in a side chain. Specifically, the siloxane dendrimer structure is preferably a group represented by the following general formula (10) from the viewpoint of skin wrinkle improvement effect and versatility.

[0099]

[0100] In the formula, R 1 Same as above, Z 2 is a single bond or a divalent organic group. 1 It is a group represented by the following general formula (11) when i=1, and i is an integer of 1 to 10 indicating the hierarchy of the group.

[0101]

[0102] In the formula, R 1 Same as above, R 12 is an alkyl group having 1 to 10 carbon atoms. 3 is an alkylene group having 2 or more and 10 or less carbon atoms. i+1 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group, or a group represented by the general formula (11), i It is an integer greater than or equal to 0 and less than or equal to 3.

[0103] In the general formula (10), Z 2 It is a single bond or a divalent organic group. From the viewpoint of versatility, it is preferably a divalent organic group, and more preferably a divalent group represented by the following general formula (12), (13) or (14).

[0104]

[0105] In the formula, R 13 It is an alkylene group having 1 to 10 carbon atoms, and examples thereof include methylene, ethylene, trimethylene, propylene, and butylene. From the viewpoint of versatility, ethylene, trimethylene, and propylene are preferred. 14 It is an alkyl group having 1 to 10 carbon atoms, and examples thereof include methyl group, ethyl group, propyl group and butyl group. From the same viewpoint, methyl group is preferred. 15 The alkylene group is an alkylene group having 1 to 10 carbon atoms, and examples thereof include methylene, ethylene, trimethylene, propylene, and butylene. From the same viewpoint, ethylene is preferred. q is an integer of 0 to 4, and r is 0 or 1.

[0106] Examples of the vinyl polymer having a siloxane dendron structure in a side chain (hereinafter also referred to simply as a vinyl polymer) include polymers having repeating units derived from a monomer represented by the following general formula (15).

[0107]

[0108] In the formula, R 1 and X 1 Same as above.Y is a group containing a vinyl bond, for example, vinyl, 2-acryloxyethyl, 3-acryloxypropyl, 2-methacryloxyethyl, 3-methacryloxypropyl, 4-vinylphenyl, 3-vinylphenyl, 4-(2-propenyl)phenyl, 3-(2-propenyl)phenyl, 2-(4-vinylphenyl)ethyl, 2-(3-vinylphenyl)ethyl, allyl, 5-hexenyl. Among these, from the viewpoint of versatility, preferably (meth)acryl or vinyl, more preferably (meth)acryl.

[0109] The vinyl polymer may further contain repeating units from vinyl monomers other than the monomers shown in the general formula (15). As the vinyl monomer, a monomer other than the monomer shown in the general formula (15) having a group containing a vinyl bond, such as (meth) acrylic acid, (meth) alkyl acrylate, (meth) hydroxyalkyl acrylate, (meth) acrylate containing aromatic rings, fatty acid vinyl esters, (meth) acrylamide, styrene or its derivatives, etc., and one or more of these can be used. Among these, from the viewpoint of versatility, (meth) acrylic acid, (meth) alkyl acrylate, (meth) hydroxyalkyl acrylate, (meth) acrylate containing aromatic rings, and other (meth) acrylic acid monomers are preferably used.

[0110] From the viewpoint of the wrinkle-improving effect on the skin, the content of the repeating units derived from the monomer represented by the general formula (15) in the vinyl polymer is preferably 0.1% by mass or more, more preferably 10% by mass or more, and even more preferably 20% by mass or more, relative to all the repeating units in the vinyl polymer. The upper limit is 100% by mass.

[0111] The vinyl polymer is more preferably an acrylic polymer. That is, a preferred polysiloxane dendrimer is an acrylic polymer having a siloxane dendrimer structure in a side chain (hereinafter also referred to as an acrylic polysiloxane dendrimer). The acrylic polysiloxane dendrimer is a polymer having repeating units derived from a monomer in which Y in the general formula (15) is a (meth)acryloyl group, and may further contain repeating units derived from a (meth)acrylic monomer other than the monomer represented by the general formula (15).

[0112] Examples of commercially available silicone dendrimers include acrylic silicone dendrimers such as FA 4001 CM Silicone Acrylate (a cyclopentasiloxane solution of an acrylate-polytrimethylsiloxymethacrylate copolymer) and FA 4002 ID Silicone Acrylate (an isododecane solution of an acrylate-polytrimethylsiloxymethacrylate copolymer) manufactured by Dow Corning Toray Co., Ltd.

[0113] As component (A), among the above polymers, from the viewpoint of the wrinkle-improving effect on the skin, preferably at least one selected from polysiloxane-modified polynorbornene, polysiloxane-modified pullulan, trimethylsiloxysilicic acid, trifluoropropyl dimethyl / trimethylsiloxysilicic acid, and acrylic polysiloxane dendrimer, and more preferably at least one selected from polysiloxane-modified polynorbornene, polysiloxane-modified pullulan, trimethylsiloxysilicic acid, and trifluoropropyl dimethyl / trimethylsiloxysilicic acid; from the viewpoint of the wrinkle-improving effect on the skin and the bending resistance, more preferably at least one selected from polysiloxane-modified polynorbornene and polysiloxane-modified pullulan, and even more preferably polysiloxane-modified polynorbornene.

[0114] One or more components (A) may be used in combination. From the viewpoint of the wrinkle-improving effect on the skin, the content of component (A) in the total composition is 1% by mass or more, preferably 2% by mass or more, more preferably 4% by mass or more, and further preferably 5% by mass or more, and is 30% by mass or less, preferably 25% by mass or less, more preferably 20% by mass or less, and further preferably 18% by mass or less. In addition, the content of component (A) in the total composition is 1 to 30% by mass, preferably 2 to 25% by mass, more preferably 4 to 20% by mass, and further preferably 5 to 18% by mass.

[0115] <Ingredient (B)>

[0116] The component (B) used in the present invention is a volatile oil having a volatility of 14% or more after drying at 1 atmosphere, 40°C, and 60% RH for 30 minutes. When the component (B) is contained, the drying speed of the composition containing the component (A) is increased, thereby accelerating the shrinkage of the component (A) during the drying process, and further improving the effect of stretching skin wrinkles to make them less noticeable.

[0117] From the viewpoint of obtaining the above-mentioned effect, the volatility of component (B) after drying for 30 minutes at 1 atmosphere, 40°C, and 60%RH is preferably 18% or more, more preferably 25% or more, further preferably 30% or more, further preferably 45% or more, further preferably 65% ​​or more, further preferably 80% or more, further preferably 95% or more. In addition, the upper limit is 100%.

[0118] The volatility of component (B) is obtained by placing 0.5 g of a sample in a glass petri dish having a diameter of 40 mm, leaving it to stand at 40° C. for 30 minutes under 1 atmosphere and 60% RH to dry it, setting the mass of the sample before drying to W0 (g) and the mass of the sample after drying to W1 (g), and calculating the value of {(W0-W1) / W0}×100. A larger value means a faster volatilization rate and easier drying.

[0119] Furthermore, two or more volatile oils may be used as the component (B).

[0120] The above-mentioned volatility can be specifically measured by the method described in Examples.

[0121] As component (B), from the viewpoint of improving the wrinkle-improving effect on the skin, for example, one or more oils selected from hydrocarbon oils and silicone oils, and having a volatility within the above range, are mentioned. Among these, one or more oils selected from isododecane (volatility 33%), hexamethyldisiloxane (volatility 100%), methyltrimethicone, and dimethylpolysiloxane having a kinematic viscosity of 2 cSt or less at 25° C. are preferred. In addition, the kinematic viscosity can be measured, for example, using an Ubbelohde viscometer.

[0122] From the viewpoint of enhancing the wrinkle-improving effect on the skin, component (B) is more preferably one or more selected from isododecane, hexamethyldisiloxane, and dimethylpolysiloxane having a kinetic viscosity at 25°C of 1.5 cSt or less, further preferably one or more selected from hexamethyldisiloxane and dimethylpolysiloxane having a kinetic viscosity at 25°C of 1 cSt or less, and further preferably hexamethyldisiloxane.

[0123] Examples of commercially available products of hexamethyldisiloxane and dimethylpolysiloxane having 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 Fluid1cs and SH200C Fluid 1.5cs manufactured by Dow Corning Toray Co., Ltd., TSF451-0.65 manufactured by Momentive Performance Materials Japan Co., Ltd., and BELSILDM0.65 manufactured by Asahi Kasei Wacker Silicone Co., Ltd.

[0124] One or more components (B) may be used in combination. From the viewpoint of improving the wrinkle-improving effect on the skin, the content of component (B) in the total composition is preferably 1% by mass or more, more preferably 30% by mass or more, more preferably 50% by mass or more, more preferably 70% by mass or more, and more preferably 75% by mass or more, and is preferably 99% by mass or less, more preferably 98% by mass or less, more preferably 97% by mass or less, more preferably 94% by mass or less, more preferably 92% by mass or less, and more preferably 90% by mass or less. In addition, the content of component (B) in the total composition is preferably 1 to 99% by mass, more preferably 1 to 98% by mass, more preferably 30 to 97% by mass, more preferably 50 to 94% by mass, more preferably 70 to 92% by mass, and more preferably 75 to 90% by mass.

[0125] In the present invention, from the viewpoint of the wrinkle-improving effect on the skin, the mass ratio (A) / (B) of the component (A) to the component (B) is preferably 0.02 or more, more preferably 0.03 or more, further preferably 0.04 or more, further preferably 0.05 or more, further preferably 0.1 or more, and is preferably 1 or less, more preferably 0.7 or less, further preferably 0.4 or less, further preferably 0.25 or less, further preferably 0.24 or less. In addition, the mass ratio (A) / (B) of the component (A) to the component (B) is preferably 0.02 to 1, more preferably 0.03 to 0.7, further preferably 0.04 to 0.4, further preferably 0.05 to 0.25, further preferably 0.1 to 0.24.

[0126] <Ingredient (C)>

[0127] The component (C) used in the present invention is a powder, and may be any type such as an organic powder or an inorganic powder.

[0128] Examples of the organic powder include: polyamide resin, nylon resin, polyester resin, polyethylene resin, polytetrafluoroethylene resin, polypropylene resin, polystyrene resin, benzoguanamine resin, polymethylbenzoguanamine resin, polymethyl methacrylate, polyurethane resin, vinyl resin, fluororesin, acrylic resin, melamine resin; polysiloxane elastomer obtained by crosslinking dimethylpolysiloxane, or polysiloxane resins such as polymethylsilsesquioxane; crosslinked or non-crosslinked organic powders such as powders of one or more polymers or copolymers selected from poly(meth)acrylic acid, sodium poly(meth)acrylate, poly(meth)acrylate, and poly(meth)acrylic acid alkylene glycol, such as butyl acrylate-vinyl acetate copolymer, styrene-acrylic acid copolymer, divinylbenzene-styrene copolymer, (lauryl methacrylate / ethylene glycol dimethacrylate) copolymer, etc.

[0129] Examples of the inorganic powder include talc, kaolin, mica, sericite, phlogopite, magnesium aluminum silicate, calcium silicate, aluminum silicate, magnesium silicate, barium silicate, strontium silicate, epoxy-treated aluminum, aluminum powder, calcium phosphate, silicic anhydride, aluminum silicic anhydride, pyrophyllite clay, bentonite, smectite, montmorillonite, vermiculite, hectorite, zeolite, alumina, silicon oxide, aluminum oxide, zirconium oxide, iron oxide (red iron oxide, yellow iron oxide, black iron oxide, γ-iron oxide), loess, oxide Titanium black, low titanium oxide, iron titanate, zinc oxide, aluminum hydroxide, aluminum oxide, aluminum cobalt oxide, chromium oxide, zirconium oxide, titanium oxide sol, iron oxide·titanium dioxide sintered product, cerium oxide, magnesium oxide, chromium hydroxide, titanium·titanium dioxide sintered product, cobalt titanate, manganese violet, cobalt violet, calcium carbonate, barium carbonate, magnesium carbonate, tungstate metal salt, barium sulfate, calcined calcium sulfate (calcined gypsum), bismuth oxychloride, hemimorphite, sodium rosinate treated magnesium oxide, fluoroapatite, hydroxyapatite, ceramic powder, metal soap (zinc myristate, calcium palmitate, aluminum stearate, etc.), etc., or composite powders of two or more of these can be cited. In addition, organic-inorganic composite powders such as acrylic resin coated aluminum powder and titanium oxide coated nylon powder can be cited.

[0130] Examples of natural fiber powders include silk powder, wool powder, and cellulose powder.

[0131] Examples of the pearlescent pigment include titanium mica, titanium mica coated with iron oxide, bismuth oxychloride coated with titanium oxide, talc coated with titanium oxide, glass flake coated with titanium oxide, and argentite.

[0132] From the viewpoint of suppressing oiliness, obtaining a natural and matte uniform makeup effect, and suppressing a clear boundary between the coating film and the skin, component (C) preferably contains at least (C-1) an inorganic powder having a refractive index of 1.3 to 1.8, more preferably contains an inorganic powder having a refractive index of 1.4 to 1.7, and further preferably contains an inorganic powder having a refractive index of 1.4 to 1.6.

[0133] Examples of such inorganic powder (C-1) include one or more selected from zeolite (refractive index 1.47 to 1.49), silica (refractive index 1.54), talc (refractive index 1.54 to 1.59), sericite (refractive index 1.58), mica (refractive index 1.58), barium carbonate (refractive index 1.6), barium sulfate (refractive index 1.64), hydroxyapatite (refractive index 1.65), calcium carbonate (refractive index 1.66), and aluminum oxide (refractive index 1.77); preferably, it contains one or more selected from zeolite, silica, talc, sericite, mica, barium carbonate, barium sulfate, hydroxyapatite, and calcium carbonate; more preferably, it contains one or more selected from silica, sericite, mica, and barium sulfate.

[0134] The inorganic powder having a refractive index of 1.3 to 1.8 as component (C-1) is preferably a hydrophobicized one from the viewpoint of not impairing the strength of the coating film on the skin after application and suppressing a clear boundary between the coating film and the skin.

[0135] The hydrophobic treatment is not limited as long as it is a treatment usually applied to cosmetic powders, and examples thereof include polysiloxane treatment, alkoxysilane treatment, fatty acid treatment, lauroyl lysine treatment, lecithin treatment, N-acyl amino acid treatment, metal soap treatment, fluorine compound treatment, etc. Among these, polysiloxane treatment is preferred. These treatments can be carried out by common methods.

[0136] From the viewpoint of maintaining the wrinkle improvement effect of the skin, suppressing oily shine, obtaining a natural and matte uniform makeup effect, and suppressing the obvious boundary between the coating film and the skin, the content of the inorganic powder of this component (C-1) in the total composition is 0.1% by mass or more, preferably 1% by mass or more, more preferably 2% by mass or more, and more preferably 3% by mass or more, and is 30% by mass or less, preferably 15% by mass or less, more preferably 10% by mass or less, and more preferably 8% by mass or less. In addition, the content of the component (C-1) in the total composition is 0.1 to 30% by mass, preferably 1 to 15% by mass, more preferably 2 to 10% by mass, and more preferably 3 to 8% by mass.

[0137] In the present invention, from the viewpoint of maintaining the wrinkle improvement effect of the skin, suppressing oiliness, obtaining a natural and matte uniform makeup effect, and suppressing a clear boundary between the coating film and the skin, the mass ratio (A) / (C-1) of the component (A) to the component (C-1) is preferably 1 or more, and is preferably 50 or less, more preferably 22 or less, further preferably 10 or less, and further preferably 5 or less. In addition, the mass ratio (A) / (C-1) of the component (A) to the component (C-1) is preferably 1 to 50, more preferably 1 to 22, further preferably 1 to 10, and further preferably 1 to 5.

[0138] In addition, from the viewpoint of suppressing oiliness and preventing a clear boundary between the coating film and the skin, the average particle size of component (C) is preferably 0.01 μm or more, more preferably 0.1 μm or more, and further preferably 1 μm or more, and is preferably 100 μm or less, more preferably 30 μm or less, and further preferably 15 μm or less. In addition, the particle size of component (C) is preferably 0.01 to 100 μm, more preferably 0.1 to 30 μm, and further preferably 1 to 15 μm.

[0139] In the present invention, the particle size is measured by electron microscope observation or a particle size distribution measuring machine of a laser diffraction / scattering method. Specifically, in the case of the laser diffraction / scattering method, the dispersion pressure is set to 0.1 bar in a dry manner in the measuring unit, and the particle size distribution is measured by a laser diffraction scattering particle size distribution measuring machine (e.g., Sympatec, HELOS & RODOS).

[0140] One or more components (C) may be used in combination. From the viewpoint of suppressing the oily shine of the makeup effect, the content of component (C) in the total composition (including the total content of component (C-1)) is preferably 0.1% by mass or more, more preferably 1% by mass or more, further preferably 2% by mass or more, and further preferably 3% by mass or more, and is preferably 40% by mass or less, more preferably 20% by mass or less, further preferably 15% by mass or less, and further preferably 10% by mass or less. In addition, the content of component (C) in the total composition is preferably 0.1 to 40% by mass, more preferably 1 to 20% by mass, further preferably 2 to 15% by mass, and further preferably 3 to 10% by mass.

[0141] In the present invention, from the viewpoint of suppressing the oily shine of makeup effect, the mass ratio (A) / (C) of the component (A) to the component (C) is preferably 1 or more, and is preferably 50 or less, more preferably 22 or less, further preferably 10 or less, and further preferably 5 or less. In addition, the mass ratio (A) / (C) of the component (A) to the component (C) is preferably 1 to 50, more preferably 1 to 22, further preferably 1 to 10, and further preferably 1 to 5.

[0142] <Other ingredients>

[0143] The skin external preparation composition of the present invention may further contain a surfactant, preferably an anionic surfactant, a cationic surfactant, a nonionic surfactant, or an amphoteric surfactant.

[0144] The surfactant is not limited as long as it is a component generally used in external skin preparations, but a nonionic surfactant is preferred from the viewpoint of being soluble in volatile oil and suppressing stickiness.

[0145] Examples of the nonionic surfactant include sorbitan fatty acid esters, glycerin fatty acid esters, polyglycerin fatty acid esters, propylene glycol fatty acid esters, polyethylene glycol fatty acid esters, sucrose fatty acid esters, polyoxyethylene fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene sorbitol fatty acid esters, polyoxyethylene glycerin fatty acid esters, polyoxyethylene propylene glycol fatty acid esters, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, polyoxyethylene hydrogenated castor oil fatty acid esters, polyoxyethylene phytostanol ethers, polyoxyethylene phytosterol ethers, polyoxyethylene cholestanol ethers, polyoxyethylene cholesterol ethers, alkyl glyceryl ether-modified polysiloxanes, polyoxyalkylene-modified polysiloxanes, polyoxyalkylene-alkyl co-modified polysiloxanes, and polyoxyalkylene-fluoroalkyl co-modified polysiloxanes.

[0146] Among these, from the viewpoint of improving the dispersibility and solubility of water and water-soluble components in oil, it is preferred to contain one or more of alkyl glyceryl ether-modified polysiloxane and polyoxyalkylene-modified polysiloxane, and it is more preferred to contain polyoxyalkylene-modified polysiloxane.

[0147] As the polyoxyalkylene-modified polysiloxane, commercially available products such as SH3771M, SH3772M, SH3773M, SH3775M, SH3749, and DC5200 manufactured by Dow Corning Toray Co., Ltd. or KF-6011, KF-6012, KF-6013, KF-6015, KF-6016, KF-6017, and KF-6004 manufactured by Shin-Etsu Chemical Co., Ltd. can be used.

[0148] The nonionic surfactant preferably has an HLB value of 1 to 7, and more preferably has an HLB value of 2 to 6, from the viewpoint of improving the dispersibility and solubility of water and water-soluble components in oil.

[0149] Here, HLB (Hydrophilic-Lipophilic Balance) indicates the molecular weight of the hydrophilic group portion in the total molecular weight of the surfactant, and for nonionic surfactants, it is a value obtained by Griffin's equation.

[0150] The HLB of a mixed surfactant composed of two or more nonionic surfactants is determined as follows: The HLB of the mixed surfactant is obtained by arithmetically averaging the HLB values ​​of the nonionic surfactants at their blending ratios.

[0151] Mixed HLB = Σ(HLBx×Wx) / ΣWx

[0152] HLBx represents the HLB value of nonionic surfactant X.

[0153] Wx is the weight (g) of the nonionic surfactant X having the HLBx value.

[0154] The nonionic surfactant may be used alone or in combination of two or more. From the viewpoint of solubility in volatile oil and suppression of stickiness, the content of the nonionic surfactant in the total composition is preferably 30% by mass or less, more preferably 10% by mass or less, further preferably 5% by mass or less, further preferably 3% by mass or less, further preferably 1% by mass or less.

[0155] In the present invention, from the viewpoint of maintaining the wrinkle-improving effect on the skin and obtaining a non-sticky feeling during use, the water content in the total composition is preferably 50% by mass or less, more preferably 30% by mass or less, further preferably 10% by mass or less, further preferably 5% by mass or less, and further preferably 1% by mass or less.

[0156] In addition to the above-mentioned ingredients, the skin external preparation composition of the present invention may also optionally contain various commonly used ingredients within the range that does not impair the effects of the present invention. Examples of these ingredients include oily ingredients other than the above-mentioned, water-soluble polymers, antioxidants, ultraviolet absorbers, vitamin preparations, preservatives, pH adjusters, fragrances, plant extracts, moisturizers, colorants, cooling agents, antiperspirants, bactericides, skin activators, etc.

[0157] The skin external preparation composition of the present invention can be applied in any form such as an oily composition or an emulsified composition which can be produced by a conventional method. As a preparation, it can be prepared into a liquid, emulsion, paste, cream, gel, solid, sheet, etc. for application.

[0158] The skin external application composition of the present invention can be used as cosmetics, quasi-drugs, and pharmaceuticals, and can be used as: skin care cosmetics such as lotions, emulsions, creams, essences, dispersions, gels, ointments, masks, mousses, aerosols, mud packs, and cleansers; ultraviolet protection cosmetics such as sunscreen lotions and sunscreen creams; and color cosmetics such as primers, foundations, concealers, blushers, eye shadows, mascara, eyeliners, eyebrow colors, setting agents, and lipsticks.

[0159] The skin external application composition of the present invention is suitable for use as a skin wrinkle improving agent.

[0160] Regarding the above-mentioned embodiment, the present invention further discloses the following composition.

[0161] <1> A composition for external use on skin, comprising the following components (A), (B) and (C);

[0162] (A) a polymer having a polysiloxane structure, wherein the deformation ratio measured by the following method (1) is 0.3 or more and 1 or less, and the minimum diameter of the cylindrical axis at which the polymer film does not crack in a bending resistance test by the cylindrical axis method performed by the following method (2) is 2 mm or more and 25 mm or less: 1 to 30% by mass;

[0163] Method (1): prepare a 10 mass % hexamethyldisiloxane solution of the above polymer; apply 0.005 g of the solution on one side of a polyethylene sheet of 20 mm wide × 100 mm long × 0.03 mm thick from one end of the short side in the longitudinal direction over a range of 20 mm wide × 50 mm long, and dry in a constant temperature bath set at 40° C. for 10 minutes; set the length of the portion of the polyethylene sheet coated with the above solution as L1, set the length of the portion of the polyethylene sheet deformed due to shrinkage after drying as L2, and use the value of L2 / L1 as the deformation ratio,

[0164] Method (2): A 30% by mass hexamethyldisiloxane solution of the above polymer is prepared; the solution is applied onto a polyethylene terephthalate film of 50 mm in width × 100 mm in length × 0.1 mm in thickness using a 200 μm applicator, and the film is dried in a constant temperature bath set at 40° C. for 120 minutes to prepare a test piece; the test piece is used to perform a bending resistance test in accordance with the cylindrical axis method specified in JIS K5600-5-1:1999, and the minimum diameter of the cylindrical axis at which the polymer film on the test piece does not crack is determined.

[0165] (B) a volatile oil having a volatility of 14% or more after drying at 1 atmosphere, 40°C, and 60% RH for 30 minutes;

[0166] (C) Powder;

[0167] The mass ratio of component (A) to component (C) (A) / (C) is 1 to 50;

[0168] The composition contains at least 0.1 to 30 mass % of (C-1) inorganic powder having a refractive index of 1.3 to 1.8 as a component (C).

[0169] <2> As mentioned above <1> The skin topical preparation composition described above, wherein, in component (A), the deformation ratio L2 / L1 evaluated by the above method (1) is preferably greater than 0.5, more preferably greater than 0.6, further preferably greater than 0.7, further preferably greater than 0.8, further preferably greater than 0.85, further preferably greater than 0.9, further preferably greater than 0.95.

[0170] <3> As mentioned above <1> or <2> The skin topical preparation composition described above, wherein, in component (A), in the bending resistance test of the cylindrical shaft method performed by the above-mentioned method (2), the minimum diameter of the cylindrical shaft at which the polymer film of component (A) does not crack is preferably 20 mm or less, more preferably 12 mm or less, further preferably 8 mm or less, further preferably 6 mm or less, further preferably 5 mm or less, and preferably 3 mm or more.

[0171] <4> As mentioned above <1> to <3> The skin topical preparation composition described in any one of the above, wherein in component (A), the ratio of the deformation ratio obtained by the above method (1) to the minimum diameter (mm) of the cylindrical axis obtained by the above method (2) [(deformation ratio) / (minimum diameter of the cylindrical axis)] is preferably greater than 0.01, more preferably greater than 0.02, further preferably greater than 0.10, further preferably greater than 0.15, and is preferably less than 0.5, more preferably less than 0.4.

[0172] <5> As mentioned above <1> to <4> In any one of the compositions for external use on skin, component (A) is preferably a polysiloxane-modified polymer, more preferably a polysiloxane-modified polymer containing a norbornane structure, a polysiloxane-modified pullulan, a silicic acid compound containing a polysiloxane structure, or a polysiloxane dendrimer.

[0173] <6> As mentioned above <1> to <5> The composition for external use on skin according to any one of the preceding claims, wherein component (A) is preferably a polysiloxane-modified polymer containing a norbornane structure, and more preferably a polymer having a repeating unit represented by the following general formula (1) or (2);

[0174]

[0175] In the formula, R 2 Each independently represents an alkyl group having 1 to 12 carbon atoms, X represents a group represented by the following formula (i); a is an integer of 1 to 3, b is an integer of 0 to 2,

[0176]

[0177] In the formula, R 1 As above, c is an integer of 1 to 5,

[0178]

[0179] 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.

[0180] <7> As mentioned above <1> to <6> The composition for external use on skin according to any one of the preceding claims, wherein component (A) is preferably a polysiloxane-modified polymer containing a norbornene structure, more preferably a polysiloxane-modified polynorbornene, and further preferably a polysiloxane-modified polynorbornene represented by the following formula (6):

[0181]

[0182] In the formula, e and f are the numbers of repeating units, and each independently represents an integer of 1 or more.

[0183] <8> As mentioned above <7> The composition for external use on skin, wherein in the general formula (6), the ratio of e to f is preferably e / f=20 / 80 to 90 / 10 (mol / mol), more preferably 30 / 70 to 80 / 20 (mol / mol), and further preferably 50 / 50 to 70 / 30 (mol / mol).

[0184] <9> As mentioned above <1> to <8> The skin topical preparation composition described in any one of the above, wherein component (A) is preferably one or more selected from polysiloxane-modified polynorbornene, polysiloxane-modified pullulan, trimethylsiloxysilicic acid, trifluoropropyl dimethyl / trimethylsiloxysilicic acid, and acrylic polysiloxane dendrimer, more preferably one or more selected from polysiloxane-modified polynorbornene, polysiloxane-modified pullulan, trimethylsiloxysilicic acid, and trifluoropropyl dimethyl / trimethylsiloxysilicic acid, further preferably one or more selected from polysiloxane-modified polynorbornene and polysiloxane-modified pullulan, and further preferably polysiloxane-modified polynorbornene.

[0185] <10> As mentioned above <1> to <9> The skin external preparation composition described in any one of the preceding claims, wherein the content of component (A) in the total composition is preferably 2% by mass or more, more preferably 4% by mass or more, further preferably 5% by mass or more, and is preferably 25% by mass or less, more preferably 20% by mass or less, further preferably 18% by mass or less.

[0186] <11> As mentioned above <1> to <10> The skin external preparation composition described in any one of the above, wherein the volatility of component (B) after drying for 30 minutes at 1 atmosphere, 40°C, and 60% RH is preferably 18% or more, more preferably 25% or more, further preferably 30% or more, further preferably 45% or more, further preferably 65% ​​or more, further preferably 80% or more, further preferably 95% or more.

[0187] <12> As mentioned above <1> to <11> The skin topical preparation composition described in any one of the above, wherein component (B) is preferably at least one selected from hydrocarbon oils and silicone oils, more preferably at least one selected from isododecane, hexamethyldisiloxane, methylpolytrimethylsiloxane, and dimethylpolysiloxane having a kinetic viscosity of less than 2 cSt at 25°C, further preferably at least one selected from isododecane, hexamethyldisiloxane, and dimethylpolysiloxane having a kinetic viscosity of less than 1.5 cSt at 25°C, further preferably at least one selected from hexamethyldisiloxane and dimethylpolysiloxane having a kinetic viscosity of less than 1 cSt at 25°C, further preferably hexamethyldisiloxane.

[0188] <13> As mentioned above <1> to <12> The skin external preparation composition described in any one of the preceding claims, wherein the content of component (B) in the total composition is preferably 1% by mass or more, more preferably 30% by mass or more, further preferably 50% by mass or more, further preferably 70% by mass or more, further preferably 75% by mass or more, and is preferably 99% by mass or less, more preferably 98% by mass or less, further preferably 97% by mass or less, further preferably 94% by mass or less, further preferably 92% by mass or less, further preferably 90% by mass or less.

[0189] <14> As mentioned above <1> to <13> The skin topical preparation composition described in any one of the preceding claims, wherein the mass ratio (A) / (B) of component (A) to component (B) is preferably 0.02 or more, more preferably 0.03 or more, further preferably 0.04 or more, further preferably 0.05 or more, further preferably 0.1 or more, and is preferably 1 or less, more preferably 0.7 or less, further preferably 0.4 or less, further preferably 0.25 or less, further preferably 0.24 or less.

[0190] <15> As mentioned above <1> to <14> The skin external preparation composition according to any one of the preceding claims, wherein the powder of component (C) contains (C-1) an inorganic powder having a refractive index of 1.3 to 1.8, preferably an inorganic powder having a refractive index of 1.4 to 1.7, and more preferably an inorganic powder having a refractive index of 1.4 to 1.6.

[0191] <16> As mentioned above <1> to <15> The skin topical preparation composition described in any one of the preceding claims, wherein the inorganic powder having a refractive index of 1.3 to 1.8 as component (C-1) is preferably one or more selected from zeolite (refractive index 1.47 to 1.49), silica (refractive index 1.54), talc (refractive index 1.54 to 1.59), sericite (refractive index 1.58), mica (refractive index 1.58), barium carbonate (refractive index 1.6), barium sulfate (refractive index 1.64), hydroxyapatite (refractive index 1.65), calcium carbonate (refractive index 1.66), and aluminum oxide (refractive index 1.77); more preferably one or more selected from zeolite, silica, talc, sericite, mica, barium carbonate, barium sulfate, hydroxyapatite, and calcium carbonate; and further preferably one or more selected from silica, sericite, mica, and barium sulfate.

[0192] <17> As mentioned above <1> to <16> In any one of the compositions for external use on skin, the inorganic powder having a refractive index of 1.3 to 1.8 as component (C-1) is preferably a hydrophobicized component, more preferably a silicone-treated component.

[0193] <18> As mentioned above <1> to <17> The skin external preparation composition described in any one of the preceding claims, wherein the content of the inorganic powder of component (C-1) in the total composition is preferably 1% by mass or more, more preferably 2% by mass or more, further preferably 3% by mass or more, and is preferably 15% by mass or less, more preferably 10% by mass or less, further preferably 8% by mass or less.

[0194] <19> As mentioned above <1> to <18> The skin external preparation composition described in any one of the preceding claims, wherein the mass ratio (A) / (C-1) of component (A) to component (C-1) is preferably 1 or more, and is preferably 50 or less, more preferably 22 or less, further preferably 10 or less, and further preferably 5 or less.

[0195] <20> As mentioned above <1> to <19> The composition for external use on skin described in any one of the preceding claims, wherein the average particle size of component (C) is preferably 0.01 μm or more, more preferably 0.1 μm or more, further preferably 1 μm or more, and is preferably 100 μm or less, more preferably 30 μm or less, further preferably 15 μm or less.

[0196] <21> As mentioned above <1> to <20> The skin external preparation composition described in any one of the preceding claims, wherein the content of component (C) in the total composition is preferably 0.1% by mass or more, more preferably 1% by mass or more, further preferably 2% by mass or more, further preferably 3% by mass or more, and is preferably 40% by mass or less, more preferably 20% by mass or less, further preferably 15% by mass or less, further preferably 10% by mass or less.

[0197] <22> As mentioned above <1> to <21> The skin external preparation composition described in any one of the preceding claims, wherein the mass ratio (A) / (C) of component (A) to component (C) is preferably 1 or more, and is preferably 50 or less, more preferably 22 or less, further preferably 10 or less, and further preferably 5 or less.

[0198] <23> A composition for external use on skin, comprising the following components (A), (B) and (C);

[0199] (A) at least one selected from polysiloxane-modified polynorbornene and polysiloxane-modified pullulan: 1 to 30% by mass;

[0200] (B) volatile oil having a volatility of 14% or more after drying at 1 atmosphere, 40° C., and 60% RH for 30 minutes: 1 to 99% by mass;

[0201] (C) Powder: 0.1 to 40% by mass;

[0202] The mass ratio of component (A) to component (C) (A) / (C) is 1 to 50;

[0203] The composition contains at least 0.1 to 30 mass % of (C-1) inorganic powder having a refractive index of 1.3 to 1.8 as a component (C).

[0204] <24> A composition for external use on skin, comprising the following components (A), (B) and (C);

[0205] (A) polysiloxane-modified polynorbornene: 1 to 30% by mass;

[0206] (B) volatile oil having a volatility of 14% or more after drying at 1 atmosphere, 40° C., and 60% RH for 30 minutes: 1 to 99% by mass;

[0207] (C) Powder: 0.1 to 40% by mass;

[0208] The mass ratio of component (A) to component (C) (A) / (C) is 1 to 50;

[0209] The composition contains at least 0.1 to 30 mass % of (C-1) inorganic powder having a refractive index of 1.3 to 1.8 as a component (C).

[0210] <25> A composition for external use on skin, comprising the following components (A), (B) and (C);

[0211] (A) at least one selected from polysiloxane-modified polynorbornene and polysiloxane-modified pullulan: 4 to 20% by mass;

[0212] (B) 50 to 94% by mass of volatile oils having a volatility of 14% or more after drying at 1 atmosphere, 40°C, and 60% RH for 30 minutes;

[0213] (C) Powder: 2-15% by mass;

[0214] The mass ratio of component (A) to component (C) (A) / (C) is 1 to 10;

[0215] The composition contains at least 2 to 10% by mass of (C-1) inorganic powder having a refractive index of 1.3 to 1.8 as a component (C).

[0216] <26> A composition for external use on skin, comprising the following components (A), (B) and (C);

[0217] (A) polysiloxane-modified polynorbornene: 4 to 20% by mass;

[0218] (B) 50 to 94% by mass of volatile oils having a volatility of 14% or more after drying at 1 atmosphere, 40°C, and 60% RH for 30 minutes;

[0219] (C) Powder: 2-15% by mass;

[0220] The mass ratio of component (A) to component (C) (A) / (C) is 1 to 10;

[0221] The composition contains at least 2 to 10% by mass of (C-1) inorganic powder having a refractive index of 1.3 to 1.8 as a component (C).

[0222] <27> As mentioned above <1> to <26> The composition for external use on skin described in any one of the above aspects preferably further contains a surfactant, more preferably a nonionic surfactant, and even more preferably a nonionic surfactant having an HLB value of 1 to 7.

[0223] <28> As mentioned above <27> The present invention relates to a composition for external use on skin, wherein the content of the nonionic surfactant in the total composition is preferably 30% by mass or less, more preferably 10% by mass or less, further preferably 5% by mass or less, further preferably 3% by mass or less, further preferably 1% by mass or less.

[0224] <29> As mentioned above <1> to <28> The skin external preparation composition described in any one of the preceding claims, wherein the water content in the total composition is preferably 50% by mass or less, more preferably 30% by mass or less, further preferably 10% by mass or less, further preferably 5% by mass or less, further preferably 1% by mass or less.

[0225] <30> Above <1> to <29> Use of any one of the skin external preparation compositions as a skin wrinkle improving agent.

[0226] [Example]

[0227] Hereinafter, the present invention will be described by way of examples, but the present invention is not limited to the scope of the examples. In addition, in the present examples, various measurements and evaluations were performed by the following methods.

[0228] (Number average molecular weight Mn)

[0229] The number average molecular weight of the polymer was measured by gel filtration chromatography (GPC) under the following conditions using polystyrene as a standard substance.

[0230] Measuring device: HLC-8320GPC (manufactured by Tosoh Corporation)

[0231] Column: K-806L (Shodex), 2 in series

[0232] Detector: RI

[0233] Eluent: 1mmol / L-Farmin DM20 (manufactured by Kao Corporation) / CHCl3

[0234] Flow rate: 1.0mL / min

[0235] Column temperature: 40℃

[0236] (Deformation ratio)

[0237] A 10 mass % hexamethyldisiloxane solution of the polymer of component (A) used in each composition was prepared. 0.005 g of the solution was added to Figure 1On one side of a polyethylene sheet 1 (LL film manufactured by ENSHU Chemical Industry Co., Ltd.) having a width (W) of 20 mm × a length (L0) of 100 mm × a thickness of 0.03 mm as shown in (a), a coating is applied in an area of ​​20 mm in width × 50 mm in length (L0) from one end 1a of the short side of the polyethylene sheet 1 in the longitudinal direction. Figure 1 (a) 2) was dried in a thermostatic oven set at 40°C for 10 minutes. Figure 1 In (b), the length of the polyethylene sheet at the portion where the solution was applied was defined as L1 (50 mm), and the length of the polyethylene sheet at the portion where the shrinkage (curling) occurred after drying was defined as L2, and L2 / L1 was calculated and used as the deformation ratio of the polymer. L2 is the average value of the values ​​measured on the two long sides of the polyethylene sheet 1.

[0238] (Bending resistance)

[0239] A 30% by mass hexamethyldisiloxane solution of the polymer of component (A) used in each composition was prepared. The solution was applied to a polyethylene terephthalate film (Lumirror 100T60 manufactured by Toray Industries, Inc.) having a width of 50 mm×length of 100 mm×thickness of 0.1 mm using a 200 μm applicator, and dried in a thermostatic chamber set at 40° C. for 120 minutes to prepare a film (test piece) having a polymer film.

[0240] The obtained test piece was used to perform a bending resistance test according to the cylindrical shaft method specified in JIS K5600-5-1:1999. A bending test device of type 1 (Bending Tester manufactured by Erichsen, Model 266) was used, with the surface of the polymer film side of the test piece as the outer side, and cylindrical shafts with diameters of 32mm, 25mm, 20mm, 16mm, 12mm, 10mm, 8mm, 6mm, 4mm, 3mm and 2mm were used to perform bending resistance tests in order from the cylindrical shaft with a larger diameter. The test was terminated at the point when cracks occurred in the polymer film, and the minimum diameter (mm) of the cylindrical shaft without cracks was used as the value of bending resistance. The smaller the value, the better the bending resistance.

[0241] (Volatization rate)

[0242] 0.5 g of the sample was placed in a glass petri dish with a diameter of 40 mm, and dried on a hot plate set at 40°C for 30 minutes under 1 atmosphere and 60% RH. The mass of the sample before drying was set as W0 (g), and the mass of the sample after drying was set as W1 (g), and the value of {(W0-W1) / W0}×100 was taken as the volatility (%). The larger the value, the faster the volatilization speed, and the easier it is to dry.

[0243] (Wrinkle improvement effect)

[0244] Five specialized functional inspectors will Figure 2 0.2 g of each composition was applied with fingers to the nasolabial folds around the corners of the mouth on half of the face in the manner shown. After drying at room temperature (25°C) for 10 minutes, the wrinkle improvement effect was sensory evaluated according to the following criteria. The results are expressed as the total score of 5 people.

[0245] 5: Wrinkles become considerably shallower.

[0246] 4: Wrinkles become lighter.

[0247] 3: Wrinkles become slightly lighter.

[0248] 2: Wrinkles remain and there is little change.

[0249] 1: No change.

[0250] (Suppression of oily sheen)

[0251] After each composition was applied to the skin and dried, five specialized sensory inspectors conducted sensory evaluation of the oiliness of the coating film on the skin according to the following criteria. The results are shown as the total score of the five inspectors.

[0252] 5: No oily sheen.

[0253] 4: Not too oily.

[0254] 3: Some parts are slightly oily.

[0255] 2: Some parts appear oily.

[0256] 1: The whole body is shiny.

[0257] (Makeup effect (even))

[0258] After applying each composition to the skin and drying it, five specialized sensory inspectors conducted sensory evaluation on the uniformity of the makeup effect according to the following criteria. The results are shown as the total score of the five inspectors.

[0259] 5: The makeup effect is quite even.

[0260] 4: The makeup effect is even.

[0261] 3: The makeup effect is slightly more even.

[0262] 2: The makeup effect is slightly uneven.

[0263] 1: The makeup effect is uneven.

[0264] (The inconspicuousness of the boundary between the coating film and the skin)

[0265] After each composition was applied to the skin and dried, five specialized sensory inspectors conducted sensory evaluation on the inconspicuousness of the boundary between the coating film and the skin according to the following criteria. The results are shown as the total score of the five inspectors.

[0266] 5: The boundary is not obvious.

[0267] 4: The boundary is not very obvious.

[0268] 3: The boundary is slightly obvious.

[0269] 2: The boundaries are clear.

[0270] 1: The boundary is very clear.

[0271] (The texture of the makeup effect)

[0272] After applying each composition to the skin and drying it, five specialized sensory inspectors conducted sensory evaluation on the makeup effect on the skin according to the following criteria. The results are shown as the total score of the five inspectors.

[0273] 5: The makeup texture is quite delicate.

[0274] 4: The makeup texture is delicate.

[0275] 3: The makeup texture is slightly delicate.

[0276] 2: The makeup texture is not very delicate.

[0277] 1: The makeup texture is not delicate.

[0278] [Examples 1 to 12, Comparative Examples 1 to 2]

[0279] Skin external preparation compositions (liquid form) having the compositions shown in Table 1 were prepared and evaluated for wrinkle improvement effect, oiliness suppression, makeup effect (uniformity), inconspicuousness of the boundary between the coating film and the skin, and fine texture of the makeup effect.

[0280] (Manufacturing method)

[0281] The oil phase component obtained by mixing components (A), (B) and (C) is dispersed using a disperser and then stirred using a homomixer to obtain a skin external preparation composition (liquid form).

[0282]

[0283] In Table 1, *1 to *3 are as follows.

[0284] *1: An isododecane solution of a copolymer of norbornene / tri(trimethylsiloxane)silylnorbornene (in the following formula (6), e / f=60 / 40 (mol / mol), Mn=360,000, active ingredient concentration: 30% by mass) of NBN-30-ID manufactured by Shin-Etsu Chemical Co., Ltd. was dried under reduced pressure at 50°C for 12 hours, and the resulting solid was used.

[0285]

[0286] *2: TSPL-30-ID (tris(trimethylsiloxane)silylpropyl uric acid pullulan in isododecane solution, active ingredient concentration: 30% by mass) manufactured by Shin-Etsu Chemical Co., Ltd. was dried under reduced pressure at 50° C. for 12 hours, and the resulting solid was used.

[0287] *3: A solid obtained by drying X21-5595 (trimethylsiloxysilicic acid in isododecane solution, active ingredient concentration: 60% by mass) manufactured by Shin-Etsu Chemical Co., Ltd. at 50°C under reduced pressure for 12 hours was used.

[0288] [Examples 13 to 16]

[0289] In the same manner as in Examples 1 to 12, skin external preparation compositions having the compositions shown in Table 2 were produced.

[0290] The obtained skin external preparation compositions can improve wrinkles, inhibit oily shine, have fine textures, obtain uniform makeup effects, and have an inconspicuous boundary between the coating film and the skin.

[0291]

[0292] In Table 2, *4 means as follows.

[0293] *4: A solid product obtained by drying XS66-B8226 (cyclopentasiloxane solution of trifluoropropyldimethyl / trimethylsiloxysilicic acid, active ingredient concentration: 50% by mass) manufactured by Momentive Performance Materials Japan Co., Ltd. at 50°C under reduced pressure for 12 hours was used.

[0294] [Explanation of symbols]

[0295] 1: Polyethylene sheet

[0296] 1a: One end of the short side of the polyethylene sheet 1

[0297] 2: The part coated with the polymer solution.

Claims

1. A composition for external use on skin, wherein: Containing the following ingredients (A), (B) and (C); (A) a polymer having a polysiloxane structure, wherein the deformation ratio measured by the following method (1) is 0.3 or more and 1 or less, and the minimum diameter of the cylindrical axis at which the polymer film does not crack in a bending resistance test using a cylindrical axis method performed by the following method (2) is 2 mm or more and 25 mm or less: 1 to 30% by mass; Method (1): preparing a 10 mass % hexamethyldisiloxane solution of the polymer; applying 0.005 g of the solution on one side of a polyethylene sheet of 20 mm wide × 100 mm long × 0.03 mm thick from one end of the short side in the length direction over a range of 20 mm wide × 50 mm long, and drying in a constant temperature bath set at 40° C. for 10 minutes; setting the length of the portion of the polyethylene sheet coated with the solution as L1, setting the length of the portion of the polyethylene sheet deformed due to shrinkage after drying as L2, and taking the value of L2 / L1 as the deformation ratio; Method (2): preparing a 30 mass % hexamethyldisiloxane solution of the polymer; applying the solution onto a polyethylene terephthalate film of 50 mm wide × 100 mm long × 0.1 mm thick using a 200 μm applicator, and drying the film in a constant temperature bath set at 40° C. for 120 minutes to prepare a test piece; using the test piece, conducting a bending resistance test according to the cylindrical axis method specified in JIS K5600-5-1:1999, and determining the minimum diameter of the cylindrical axis at which the polymer film on the test piece does not crack; (B) Volatile oils with a volatility of 14% or more after drying at 1 atmosphere, 40°C, and 60% RH for 30 minutes; (C) Powder; The component (A) is a polysiloxane-modified polynorbornene represented by the following formula (6): In the formula, e and f are the numbers of repeating units, and each independently represents an integer greater than 1; The mass ratio of component (A) to component (C) (A) / (C) is 1 to 50; The composition contains at least 0.1 to 30 mass % of (C-1) inorganic powder having a refractive index of 1.3 to 1.8 as a component (C).

2. The composition for external use on skin according to claim 1, wherein The content of the component (B) is 1 to 99% by mass.

3. The composition for external use on skin according to claim 1, wherein Component (C-1) is one or more inorganic powders selected from the group consisting of zeolite, silica, talc, sericite, mica, barium carbonate, barium sulfate, hydroxyapatite and calcium carbonate.

4. The composition for external use on skin according to any one of claims 1 to 3, wherein The content of the component (C) is 0.1 to 40% by mass.

5. The composition for external use on skin according to any one of claims 1 to 3, wherein The mass ratio (A) / (C-1) of the component (A) to the component (C-1) is 1 to 50.

6. The composition for external use on skin according to any one of claims 1 to 3, wherein The mass ratio (A) / (B) of the component (A) to the component (B) is 0.02 to 1.

7. The composition for external use on skin according to claim 1, wherein In the component (A), the ratio of e to f in the formula (6) is e / f=20 / 80 to 90 / 10 mol / mol.

8. Use of the composition for external application to skin according to any one of claims 1 to 7 as a skin wrinkle improving agent for non-therapeutic purposes.

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