Skin topical composition

Abstract

To provide a skin external preparation composition which can improve wrinkles of the skin, forms a coating film having an even thickness and suppresses whitening during drying after application.SOLUTION: There is provided a skin external preparation composition which comprises the following components (A), (B) and (C), and a mass ratio (A) / (C) of the component (A) to the component (C) is 3 to 200, where the components are (A) 1 to 30 mass% of a polymer having a silicone structure in which a deformation rate measured by a predetermined method (1) is 0.3 or more and 1 or less, and a minimum diameter of a cylindrical mandrel which causes no cracks in a film of the polymer is 2 mm or more and 25 mm or less in a flex resistance test by a cylindrical mandrel method performed by a predetermined method (2), (B) a volatile oil having a volatilization rate of 14% or more after drying for 30 minutes under 1 atm., 40°C and 60% R.H, and (C) a polyol.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a skin external preparation composition. [Background technology]

[0002] As we age, our skin becomes more wrinkled, which is part of the skin aging process and is influenced by several factors, including changes in skin tissue and the effects of ultraviolet radiation exposure. Previously, skin care products aimed at making wrinkles less noticeable have been studied, but the improvement effect has been extremely low, and women who are concerned about wrinkles have not been satisfied with these products. On the other hand, cosmetics containing film-forming polymers are known for the purpose of improving the uniformity of the cosmetic film and the long-lasting properties of the cosmetic. For example, Patent Document 1 describes that cosmetics containing a film-forming polymer in which a specific functional group has been introduced into the backbone of a polycycloolefin polymer have good cosmetic long-lasting properties and a good feel to the touch. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2012-17317 Summary of the Invention [Problem to be solved by the invention]

[0004] However, cosmetics containing film-forming polymers have problems such as insufficient wrinkle improvement effects, unevenness in the thickness of the coating film, and noticeable whitening during drying. [Means for solving the problem]

[0005] The present inventors have discovered that by combining a specific film-forming polymer with a polyol in a specific ratio, it is possible to obtain a skin topical preparation composition that maintains high shrinkage, improves skin wrinkles, and provides a coating film with a uniform thickness and that suppresses whitening during drying after application, thereby completing the present invention.

[0006] The present invention comprises the following components (A), (B) and (C): (A) 1 to 30 mass% of a polymer having a silicone structure, wherein the deformation ratio measured by the following method (1) is 0.3 or more and 1 or less, and in a bending resistance test using a cylindrical mandrel method performed by the following method (2), the minimum diameter of the cylindrical mandrel at which cracks do not occur in the polymer film is 2 mm or more and 25 mm or less; Method (1): A 10% by weight solution of the polymer in hexamethyldisiloxane was prepared. 0.005 g of this solution was applied to one side of a 20 mm wide, 100 mm long, and 0.03 mm thick polyethylene sheet, starting from one end of the short side and working in the lengthwise direction, over an area measuring 20 mm wide and 50 mm long. The sheet was then dried for 10 minutes in a thermostatic chamber set at 40°C. The length of the polyethylene sheet where the solution was applied was designated L1, and the length of the polyethylene sheet where it had deformed due to shrinkage after drying was designated L2. The value L2 / L1 was used as the deformation ratio. Method (2): A 30% by weight solution of the polymer in hexamethyldisiloxane is prepared. The solution is applied to a polyethylene terephthalate film measuring 50 mm wide, 100 mm long, and 0.1 mm thick using a 200 μm applicator, and the film is dried for 120 minutes in a thermostatic chamber set at 40°C to prepare a test specimen. The test specimen is subjected to a bending resistance test in accordance with the cylindrical mandrel method specified in JIS K5600-5-1:1999, and the minimum diameter of the cylindrical mandrel at which cracks do not occur in the polymer film on the test specimen is determined. (B) a volatile oil having a volatilization rate of 14% or more after drying at 1 atmosphere, 40°C, and 60% RH for 30 minutes; (C) Polyol The present invention relates to an external skin preparation composition comprising the above, wherein the mass ratio (A) / (C) of component (A) to component (C) is 3 to 200. [Effects of the Invention]

[0007] The skin external preparation composition of the present invention can improve skin wrinkles, and also provides a coating film with a uniform thickness and inhibits whitening during drying after application. As used herein, "skin wrinkles" refers to changes in shape that occur due to sagging skin, and refers to unevenness and lines that appear on the skin surface. Skin wrinkles tend to appear around the mouth, eyes, forehead, neck, body, etc. Small lines are fine wrinkles, while large lines are macro wrinkles, which occur due to pore flow in nasolabial folds, cheeks, etc. The topical skin preparation composition of the present invention has the effect of making all types of wrinkles less noticeable, and in particular, can improve even macro wrinkles such as nasolabial folds in a non-invasive manner. [Brief explanation of the drawings]

[0008] [Figure 1] FIG. 1 is an explanatory diagram of a method for evaluating the deformation ratio (L2 / L1) of a polymer by method (1). [Figure 2] FIG. 1 shows the application form of each topical skin preparation composition when evaluating the wrinkle improvement effect in the examples. DETAILED DESCRIPTION OF THE INVENTION

[0009] <Component (A)> Component (A) used in the present invention is a polymer having a silicone structure, which has a deformation ratio of 0.3 to 1 as measured by the above method (1), and in a bending resistance test using a cylindrical mandrel as performed by the above method (2), the minimum diameter of the cylindrical mandrel at which no cracks occur in the polymer film is 2 mm to 25 mm. When component (A) satisfies the above-mentioned deformation ratio measured by method (1), for example, when a composition containing the polymer of component (A) is applied to the skin around the wrinkles and then dried, the film containing the polymer shrinks, and the skin surface in close contact with the film shrinks as well. This action stretches the skin in the wrinkled areas, making the wrinkles less noticeable.

[0010] The method for evaluating the deformation ratio (L2 / L1) of component (A) using method (1) is described with reference to FIG. 1. First, a 10% by mass hexamethyldisiloxane solution of component (A) to be used in the composition is prepared. 0.005 g of this solution is applied to one side of a polyethylene sheet 1 (shown in FIG. 1(a)) measuring 20 mm in width (W), 100 mm in length (L0), and 0.03 mm in thickness, from one end 1a of the short side of the polyethylene sheet 1 in the longitudinal direction, over an area of ​​20 mm in width and 50 mm in length (part 2 shown in FIG. 1(a)). The polyethylene sheet is then dried for 10 minutes in a thermostatic chamber set at 40°C. FIG. 1(b) is a schematic diagram of the polyethylene sheet 1 to which the solution was applied, after drying, with a portion of the polyethylene sheet deformed (curled) due to shrinkage of the polymer (component (A)). In the dried polyethylene sheet (Fig. 1(b)), the length of the polyethylene sheet where the solution was applied is L1 (50 mm), and the length of the polyethylene sheet where it was deformed due to shrinkage after drying is L2. L2 / L1 is calculated and this value is used as the deformation ratio. L2 is the average value of the values ​​measured on the two long sides of polyethylene sheet 1. The larger the L2 / L1 value, the greater the amount of shrinkage of the polymer due to drying, and the upper limit of L2 / L1 is 1.

[0011] From the viewpoint of smoothing out and making skin wrinkles 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, even more preferably 0.7 or more, still more preferably 0.8 or more, still more preferably 0.85 or more, still more preferably 0.9 or more, and still more preferably 0.95 or more, with the upper limit being 1. Specifically, the deformation rate can be evaluated by the method described in the Examples.

[0012] Furthermore, component (A) has excellent flex resistance, and in a flex resistance test using the cylindrical mandrel method performed by the method (2) described above, the minimum diameter of the cylindrical mandrel at which cracks do not occur in the polymer film of component (A) is 2 mm or more and 25 mm or less. This makes the film formed from the composition containing component (A) less likely to crack and more likely to shrink while conforming to the shape of the skin. The smaller the minimum diameter of the cylindrical mandrel, the better the bending resistance. From the viewpoint of ensuring sufficient adhesion between the film containing the polymer and the skin surface when the film shrinks, the minimum diameter is 25 mm or less, preferably 20 mm or less, more preferably 12 mm or less, even more preferably 8 mm or less, still more preferably 6 mm or less, and even more preferably 5 mm or less. On the other hand, from the viewpoint of imparting sufficient strength and shape control effect to smooth out and reduce the visibility of wrinkles on the skin, the minimum diameter of the cylindrical mandrel at which cracks do not occur is 2 mm or more, preferably 3 mm or more. The specific range of the minimum diameter of the cylindrical mandrel is 2 to 25 mm, preferably 2 to 20 mm, more preferably 2 to 12 mm, even more preferably 2 to 8 mm, still more preferably 3 to 6 mm, and even more preferably 3 to 5 mm. The flex resistance can be evaluated using a type 1 bending tester specified in JIS K5600-5-1:1999, specifically by the method described in the examples.

[0013] Furthermore, the ratio of the deformation rate of component (A) determined by method (1) to the minimum mandrel diameter (mm) determined by method (2) [(deformation rate) / (minimum mandrel diameter)] is preferably 0.01 or more, more preferably 0.02 or more, even more preferably 0.10 or more, and even more preferably 0.15 or more, from the viewpoint of the skin wrinkle improvement effect, and is preferably 0.5 or less, more preferably 0.4 or less, from the viewpoint of imparting sufficient strength and shape control effect to smooth out and make wrinkles inconspicuous. The specific range of this ratio is preferably 0.01 to 0.5, more preferably 0.02 to 0.5, even more preferably 0.10 to 0.5, still more preferably 0.15 to 0.5, and even more preferably 0.15 to 0.4.

[0014] In the present invention, the term "silicone structure" refers to a structure represented by the following general formula (I).

[0015] [ka]

[0016] In general formula (I), R 1 are each independently a hydrocarbon group having 1 to 12 carbon atoms, and p is an integer of 1 or more. From the viewpoint of smoothing and reducing the appearance of wrinkles on the skin when applied, and obtaining a sufficient wrinkle improvement effect (hereinafter also referred to as "skin wrinkle improvement effect"), as well as from the viewpoint of versatility, R 1 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, even more preferably an alkyl group having 1 to 3 carbon atoms, and still more preferably a methyl group.

[0017] The polymer of component (A) may have a silicone structure, and may be a polymer consisting of only a silicone structure. However, from the viewpoint of obtaining a polymer having the above-mentioned predetermined properties, it is preferable that the polymer has a silicone structure in part, and the D unit (R 1 2SiO 2 / 2 ) structure as well as M units (R1 3SiO 1 / 2 ) structure, T unit (R 1 SiO 3 / 2 ) structure, Q unit (SiO 4 / 2 ) structure may be included. In the case of a polymer having a silicone structure in part, the silicone structure may be present in either the main chain or a side chain of the polymer, and from the viewpoint of obtaining a polymer having the above-mentioned predetermined properties, it is preferable that the silicone structure be present in the side chain. When a silicone structure is present in the polymer main chain, there is no particular limitation on the bonding form, and for example, the silicone structure may be present at the end of the polymer main chain, or the silicone structure may be a copolymer in which the silicone structure is bonded in a block or random manner in the polymer main chain. Also, polymers graft-modified with a compound having a silicone structure can be used.

[0018] The component (A) used in the present invention is preferably a silicone-modified polymer, and specific examples thereof include silicone-modified polymers containing a norbornane structure, such as silicone-modified polynorbornene; silicone-modified pullulan; silicone-structure-containing silicate compounds, such as trialkylsiloxysilicic acid, fluorine-modified alkylsiloxysilicic acid, and phenyl-modified alkylsiloxysilicic acid; and silicone dendrimers.

[0019] (Silicone-modified polymer containing norbornane structure) In the present invention, the norbornane structure refers to a structure represented by the following formula: The norbornane structure-containing silicone-modified polymer may be any silicone-modified polymer having the structure represented by this formula at any site within the polymer.

[0020] [ka]

[0021] Examples of the norbornane structure-containing silicone-modified polymer include polymers having a repeating unit represented by the following general formula (1) or (2).

[0022] [ka]

[0023] In the formula, R 2 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.

[0024] [ka]

[0025] In the formula, R 1 is the same as above, and c is an integer of 1 or more and 5 or less.

[0026] [ka]

[0027] 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.

[0028] In the general formula (1), R 2 are each independently an alkyl group having 1 to 12 carbon atoms, and from the viewpoint of the skin wrinkle improving effect and versatility, a methyl group, an ethyl group, an n-propyl group, a butyl group, or a pentyl group is preferred, and a methyl group is more preferred. X is a group represented by the formula (i), and in the formula (i), R 1 are each independently a hydrocarbon group having 1 to 12 carbon atoms. From the viewpoint of the skin wrinkle improvement effect and versatility, R 1is 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 or phenyl group having 1 to 12 carbon atoms, even more preferably an alkyl group having 1 to 3 carbon atoms, and still more 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 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 where a=2 and a repeating unit where a=3 are mixed. 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.

[0029] In the 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 preferable. From the same viewpoint, the cyclic silicone structure in 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).

[0030] [ka]

[0031] From the viewpoint of the skin wrinkle improvement effect, the proportion of 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.

[0032] 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).

[0033] [ka]

[0034] 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 from 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.

[0035] From the viewpoint of the skin wrinkle improvement effect, 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. Furthermore, when the repeating unit represented by the above general formula (3) is contained, the proportion thereof 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.

[0036] 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).

[0037] [ka]

[0038] 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 the effect of improving skin wrinkles, the ratio of e to 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).

[0039] From the viewpoint of achieving both shrinkage and flex resistance and of improving skin wrinkles, the number-average molecular weight Mn of the norbornane structure-containing silicone-modified polymer is preferably at least 50,000, more preferably at least 100,000, and even more preferably at least 200,000, and is preferably at most 2,000,000, more preferably at most 1,500,000, even more preferably at most 800,000, and still more preferably at most 600,000. The specific range of the number-average molecular weight Mn of the norbornane structure-containing silicone-modified polymer is preferably from 50,000 to 2,000,000, more preferably from 100,000 to 1,500,000, even more preferably from 200,000 to 800,000, and even more preferably from 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.

[0040] The norbornane structure-containing silicone-modified polymer can be obtained, for example, by addition polymerization of a silicone-modified cyclic olefin monomer that contains a norbornane structure or that can form a norbornane structure, using a known method. For example, a norbornane structure-containing silicone-modified polymer having a repeating unit represented by the general formula (1) or (2) 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 (3a) may be copolymerized.

[0041] [ka]

[0042] 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.

[0043] [ka]

[0044] 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.

[0045] [ka]

[0046] 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.

[0047] [ka]

[0048] 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 from 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.

[0049] When the cyclic olefin monomer represented by the general formula (3a) is copolymerized, the amount used is, from the viewpoint of the skin wrinkle improving effect, preferably 90 mol % or less, more preferably 70 mol % or less, even more preferably 50 mol % or less, and also preferably 5 mol % or more, more preferably 10 mol % or more, even more preferably 30 mol % or more, based on 100 mol % of all monomers used in the polymerization.

[0050] 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.

[0051] [ka]

[0052] From the viewpoint of the skin wrinkle improving effect, 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).

[0053] 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.

[0054] The norbornane structure-containing silicone-modified polymer is preferably a (norbornene / tris(trimethylsiloxy)silylnorbornene) copolymer, 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. Examples of commercially available silicone-modified polymers containing norbornane structures include "NBN-30-ID" (a solution of norbornene / tris(trimethylsiloxy)silylnorbornene) copolymer in isododecane, manufactured by Shin-Etsu Chemical Co., Ltd.

[0055] (Silicone-modified pullulan) Examples of silicone-modified pullulan include pullulan having a silicone structure in the side chain. Specifically, from the viewpoint of the skin wrinkle improving effect and versatility, silicone-modified pullulan in which at least some of the hydrogen atoms of the OH groups in pullulan have been substituted with a group represented by the following general formula (7) is preferred.

[0056] [ka]

[0057] In the formula, Z 1 is a single bond or a divalent organic group. 2 , X and a are the same as above, and from the same viewpoint, X is preferably a trimethylsiloxy group, and a is preferably 3.

[0058] 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).

[0059] [ka]

[0060] In the formula, R 11 is an alkylene group having from 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 preferred, and a trimethylene group or a propylene group is more preferred.

[0061] 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.

[0062] (silicic acid compound containing silicone structure) The silicone structure-containing silicate compound used in the present invention includes silicate compounds having a silicone structure at the terminal, such as trialkylsiloxysilicic acid, fluorine-modified alkylsiloxysilicic acid, and phenyl-modified alkylsiloxysilicic acid. From the viewpoint of the skin wrinkle improving effect and versatility, the alkyl group in the trialkylsiloxysilicate preferably has 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms, and even more preferably a methyl group. A specific example of the trialkylsiloxysilicate is trimethylsiloxysilicate. Fluorine-modified alkylsiloxysilicic acids include compounds in which at least some of the hydrogen atoms in the alkyl groups of trialkylsiloxysilicic acids have been substituted with fluorine atoms, such as trifluoropropyldimethylsiloxysilicic acid and trifluoropropyldimethyl / trimethylsiloxysilicic acid. Examples of phenyl-modified alkylsiloxysilicic acids include phenylpropyldimethylsiloxysilicic acid and phenylpropyldimethyl / trimethylsiloxysilicic acid.

[0063] Among the silicone structure-containing silicate compounds, from the viewpoint of the effect of improving skin wrinkles, one or more compounds selected from the group consisting of trialkylsiloxysilicic acid and fluorine-modified alkylsiloxysilicic acid are preferred.

[0064] Commercially available silicone structure-containing silicate compounds include trimethylsiloxysilicate (solution) 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.; and "XS66-B8226" (cyclopentasiloxane solution of trifluoropropyldimethyl / trimethylsiloxysilicate), "XS66-B8636" (dimethicone solution of trifluoropropyldimethyl / trimethylsiloxysilicate), and "SilShine151" (phenylpropyldimethylsiloxysilicate) manufactured by Momentive Performance Materials Japan, LLC.

[0065] (Silicone dendrimer) Examples of silicone dendrimers include vinyl polymers having a siloxane dendrimer structure in their side chains. From the viewpoints of skin wrinkle improvement effect and versatility, the siloxane dendrimer structure is preferably a group represented by the following general formula (10):

[0066] [ka]

[0067] In the formula, R 1 is the same as above. Z 2 is a single bond or a divalent organic group. 1 is a group represented by the following general formula (11) when i=1, and i is an integer of 1 or more and 10 or less that indicates the generation of the group.

[0068] [ka]

[0069] In the formula, R 1 is the same as above, and R 12is an alkyl group having 1 to 10 carbon atoms. 3 is an alkylene group having 2 to 10 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 general formula (11), i is an integer between 0 and 3 inclusive.

[0070] In general formula (10), Z 2 is a single bond or a divalent organic group, and from the viewpoint of versatility, is preferably a divalent organic group, and more preferably a divalent group represented by the following general formula (12), (13) or (14).

[0071] [ka]

[0072] In the formula, R 13 R 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, and a butylene group. From the viewpoint of versatility, an ethylene group, a trimethylene group, or a propylene group is preferred. 14 R is an alkyl group having 1 to 10 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, and a butyl group. From the same viewpoint, a methyl group is preferred. 15 is an alkylene group having 1 to 10 carbon atoms, such as a methylene group, an ethylene group, a trimethylene group, a propylene group, or a butylene group, and from the same viewpoint, an ethylene group is preferred. q is an integer of 0 to 4, and r is 0 or 1.

[0073] Examples of the vinyl polymer having the above-mentioned siloxane dendrimer structure in its side chain (hereinafter simply referred to as "vinyl polymer") include polymers having a repeating unit derived from a monomer represented by the following general formula (15).

[0074] [ka]

[0075] In the formula, R 1 and X 1 is the same as above. Y is a group containing a vinyl bond, and examples thereof include vinyl group, 2-acryloyloxyethyl group, 3-acryloyloxypropyl group, 2-methacryloyloxyethyl group, 3-methacryloyloxypropyl group, 4-vinylphenyl group, 3-vinylphenyl group, 4-(2-propenyl)phenyl group, 3-(2-propenyl)phenyl group, 2-(4-vinylphenyl)ethyl group, 2-(3-vinylphenyl)ethyl group, allyl group, and 5-hexenyl group. Of these, from the viewpoint of versatility, a (meth)acryloyl group or vinyl group is preferred, and a (meth)acryloyl group is more preferred.

[0076] The vinyl polymer may further contain a repeating unit derived from a vinyl monomer other than the monomer represented by the general formula (15). The vinyl monomer is a monomer having a group containing a vinyl bond and other than the monomer represented by the general formula (15). Examples of the vinyl monomer include (meth)acrylic acid, alkyl (meth)acrylates, hydroxyalkyl (meth)acrylates, aromatic ring-containing (meth)acrylates, fatty acid vinyl esters, (meth)acrylamide, styrene, and derivatives thereof. One or more of these may be used. Among these, (meth)acrylic monomers such as (meth)acrylic acid, alkyl (meth)acrylates, hydroxyalkyl (meth)acrylates, and aromatic ring-containing (meth)acrylates are preferred from the viewpoint of versatility.

[0077] From the viewpoint of the skin wrinkle improving effect, the content of the repeating unit 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, based on the total repeating units in the vinyl polymer, with the upper limit being 100% by mass.

[0078] The vinyl polymer is more preferably an acrylic polymer. That is, a preferred silicone dendrimer is an acrylic polymer having a siloxane dendrimer structure in its side chain (hereinafter also referred to as "acrylic silicone dendrimer"). The acrylic silicone dendrimer is a polymer having a repeating unit derived from a monomer in which Y is a (meth)acryloyl group in the general formula (15), and may further contain a repeating unit derived from a (meth)acrylic monomer other than the monomer represented by the general formula (15).

[0079] Commercially available silicone dendrimers include acrylic silicone dendrimers such as "FA 4001 CM Silicone Acrylate" (a solution of acrylate-polytrimethylsiloxymethacrylate copolymer in cyclopentasiloxane) and "FA 4002 ID Silicone Acrylate" (a solution of acrylate-polytrimethylsiloxymethacrylate copolymer in isododecane), manufactured by Dow Corning Toray Co., Ltd.

[0080] As component (A), among the above polymers, from the viewpoint of the skin wrinkle improvement effect, one or more selected from the group consisting of silicone-modified polynorbornene, silicone-modified pullulan, trimethylsiloxysilicate, trifluoropropyldimethyl / trimethylsiloxysilicate, and acrylic silicone dendrimer are preferred, and one or more selected from the group consisting of silicone-modified polynorbornene, silicone-modified pullulan, trimethylsiloxysilicate, and trifluoropropyldimethyl / trimethylsiloxysilicate are more preferred. From the viewpoint of the skin wrinkle improvement effect and flex resistance, one or more selected from the group consisting of silicone-modified polynorbornene and silicone-modified pullulan are even more preferred, and silicone-modified polynorbornene is even more preferred.

[0081] Component (A) can be used alone or in combination of two or more, and the solid content is 1% by mass or more, preferably 2% by mass or more, more preferably 4% by mass or more, even more preferably 5% by mass or more, and 30% by mass or less, preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 18% by mass or less, based on the total composition from the viewpoint of the skin wrinkle improvement effect. The solid content of component (A) is 1 to 30% by mass, preferably 2 to 25% by mass, more preferably 4 to 20% by mass, and even more preferably 5 to 18% by mass, based on the total composition.

[0082] <Ingredient (B)> Component (B) used in the present invention is a volatile oil that has a volatilization rate of 14% or more after drying for 30 minutes at 1 atmosphere, 40°C, and 60% RH. The inclusion of component (B) improves the drying rate of a composition containing component (A), thereby accelerating the contraction of component (A) during the drying process, further improving the effect of smoothing out and reducing the appearance of wrinkles on the skin. From the viewpoint of achieving the above-mentioned effects, the volatilization rate 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, even more preferably 30% or more, still more preferably 45% or more, still more preferably 65% ​​or more, still more preferably 80% or more, and still more preferably 95% or more, with the upper limit being 100%. The volatilization rate of component (B) is calculated by placing 0.5 g of sample in a 40 mm diameter glass petri dish, leaving it to dry at 40°C for 30 minutes under 1 atmosphere and 60% RH, and calculating the value of {(W0-W1) / W0} x 100, where W0 (g) is the sample mass before drying and W1 (g) is the sample mass after drying. The larger this value, the faster the volatilization rate and the easier it is to dry. Two or more types of volatile oils may be used as component (B). The volatilization rate can be measured specifically by the method described in the Examples.

[0083] From the viewpoint of enhancing the skin wrinkle improvement effect, component (B) may be one or more oils selected from hydrocarbon oils and silicone oils, and having a volatility within the above range. Among these, one or more oils selected from the group consisting of isododecane (volatility 33%), hexamethyldisiloxane (volatility 100%), methyltrimethicone, and dimethylpolysiloxanes having a kinematic viscosity of 2 cSt or less at 25°C are preferred, and one or more oils selected from isododecane, hexamethyldisiloxane, methyltrimethicone, and octamethyldimethylpolysiloxane are more preferred. The kinematic viscosity can be measured, for example, using an Ubbelohde viscometer. From the viewpoint of enhancing the skin wrinkle improvement effect, component (B) is more preferably one or more selected from the group consisting of isododecane, hexamethyldisiloxane, and dimethylpolysiloxanes having a kinematic viscosity at 25°C of 1.5 cSt or less, even more preferably one or more selected from the group consisting of hexamethyldisiloxane and dimethylpolysiloxanes having a kinematic viscosity at 25°C of 1 cSt or less, and even more preferably hexamethyldisiloxane.

[0084] Commercially available hexamethyldisiloxane and dimethylpolysiloxanes 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; "TSF451-0.65" manufactured by Momentive Performance Materials Japan, LLC; and "BELSIL DM0.65" manufactured by Wacker Asahi Kasei Silicones.

[0085] Component (B) can be used alone or in combination of two or more, and from the viewpoint of enhancing the skin wrinkle improvement effect, the content is preferably 1% by mass or more of the total composition, more preferably 30% by mass or more, even more preferably 50% by mass or more, even more preferably 70% by mass or more, even more preferably 72% by mass or more, preferably 98% by mass or less, more preferably 97% by mass or less, even more preferably 94% by mass or less, even more preferably 92% by mass or less, and even more preferably 90% by mass or less. The content of component (B) is preferably 1 to 98% by mass of the total composition, more preferably 30 to 97% by mass, more preferably 50 to 94% by mass, even more preferably 70 to 92% by mass, and even more preferably 72 to 90% by mass.

[0086] In the present invention, from the viewpoint of the skin wrinkle improvement effect, the mass ratio (A) / (B) of component (A) to component (B) is preferably 0.02 or more, more preferably 0.03 or more, even more preferably 0.04 or more, even more preferably 0.05 or more, even more preferably 0.1 or more, preferably 1 or less, more preferably 0.7 or less, even more preferably 0.4 or less, and even more preferably 0.25 or less. Furthermore, the mass ratio (A) / (B) of component (A) to component (B) is preferably 0.02 to 1, more preferably 0.03 to 0.7, even more preferably 0.04 to 0.4, even more preferably 0.05 to 0.25, and even more preferably 0.1 to 0.25.

[0087] <Component (C)> The polyol of component (C) used in the present invention is a compound having two or more hydroxyl groups in the molecule, and may be any of those used in ordinary external skin preparations. Examples of dihydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, butylene glycol, and propanediol. Examples of trihydric alcohols include glycerin and trimethylolpropane. Examples of tetrahydric alcohols include diglycerin and erythritol. Examples of pentahydric or higher polyhydric alcohols include polyglycerins such as triglycerin; sugars and sugar alcohols such as glucose, maltose, maltose, sucrose, xylitol, sorbitol, malbitol, polyoxyethylene methyl glucoside, polyoxyethylene ethyl glucoside, and polyoxyethylene propylene glucoside.

[0088] From the viewpoints of achieving a uniform, even thickness, beautiful, natural finish, and suppressing whitening, component (C) is preferably one or more selected from glycol, glycerin, and sugar, and more preferably contains at least one or more selected from propylene glycol, butylene glycol, glycerin, polypropylene glycol, and sorbitol.

[0089] Component (C) can be used alone or in combination of two or more, and from the viewpoints of achieving a uniform, even thickness, a beautiful, natural finish, and suppressing whitening, the content is preferably 0.1 mass% or more of the total composition, more preferably 0.2 mass% or more, even more preferably 0.3 mass% or more, even more preferably 0.4 mass% or more, preferably 20 mass% or less, more preferably 10 mass% or less, even more preferably 6 mass% or less, and even more preferably 4.5 mass% or less. The content of component (C) is preferably 0.1 to 20 mass% of the total composition, more preferably 0.2 to 10 mass%, even more preferably 0.3 to 6 mass%, and even more preferably 0.4 to 4.5 mass%.

[0090] In the present invention, the mass ratio (A) / (C) of (A) to component (C) is 3 or more, preferably 4 or more, more preferably 5 or more, and 200 or less, preferably 100 or less, more preferably 50 or less, and even more preferably 34 or less, from the viewpoints of improving wrinkles, achieving uniform thickness of the coating film, and suppressing whitening during drying after application. Furthermore, the mass ratio (A) / (C) of (A) to component (C) is 3 to 200, preferably 3 to 100, more preferably 4 to 50, and even more preferably 5 to 34.

[0091] <Ingredient (D)> The skin external preparation composition of the present invention may further contain (D) a surfactant, and anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants are preferred. The surfactant for component (D) is not limited as long as it is one that is commonly used in topical skin preparations, but nonionic surfactants are preferred from the viewpoints of dissolving in volatile oils, suppressing stickiness, and preventing peeling and whitening of the coating film over time. Examples of nonionic surfactants 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 ether, polyoxyethylene phytosterose ether, polyoxyethylene cholestanol ether, polyoxyethylene cholesteryl ether, alkyl glyceryl ether-modified silicones, polyoxyalkylene-modified silicones, and polyoxyalkylene-fluoroalkyl-co-modified silicones.

[0092] Of these, from the viewpoint of enhancing the dispersibility and solubility of water and water-soluble components in oil, silicone surfactants are preferred, and those containing one or more alkyl glyceryl ether-modified silicones and polyoxyalkylene-modified silicones are more preferred, and those containing polyoxyalkylene-modified silicones are even more preferred. Examples of polyoxyalkylene-modified silicones that can be used include commercially available products such as SH3771M, SH3772M, SH3773M, SH3775M, SH3749, and DC5200 manufactured by Dow Corning Toray Co., Ltd., and KF-6011, KF-6012, KF-6013, KF-6015, KF-6016, KF6017, and KF-6004 manufactured by Shin-Etsu Chemical Co., Ltd.

[0093] From the viewpoint of enhancing the dispersibility and solubility of water and water-soluble components in oil, the nonionic surfactant preferably has an HLB value of 1 or more and 7 or less, and more preferably an HLB value of 2 or more and 6 or less.

[0094] 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 can be calculated using Griffin's formula. The HLB of a surfactant mixture consisting of two or more nonionic surfactants can be calculated as follows: The HLB of the surfactant mixture is the arithmetic average of the HLB values ​​of each nonionic surfactant based on their blending ratio.

[0095] Mixed HLB=Σ(HLBx×Wx) / ΣWx HLBx indicates the HLB value of nonionic surfactant X. Wx is the weight (g) of nonionic surfactant X having a value of HLBx

[0096] The nonionic surfactants can be used alone or in combination of two or more. From the viewpoint of dissolving in volatile oils and suppressing stickiness, the content is preferably 30% by mass or less of the total composition, more preferably 10% by mass or less, even more preferably 5% by mass or less, even more preferably 3% by mass or less, and even more preferably 1% by mass or less.

[0097] <Ingredient (E)> The topical skin composition of the present invention may further contain (E) a non-volatile oil. The term "non-volatile" refers to an oil whose mass loss is 1% or less after 1 g of the oil is spread on a 48 mm diameter glass petri dish and left at 25°C and normal pressure for 24 hours. The non-volatile oil of component (E) may be any oil commonly used in cosmetics, and may be in liquid, paste, or solid form, such as ester oil, hydrocarbon oil, ether oil, higher alcohol, silicone oil, and solid wax.

[0098] Examples of ester oils include isononyl isononanoate, isodecyl isononanoate, isotridecyl isononanoate, tricyclodecanemethyl isononanoate, hexyl laurate, octyldodecyl malate, cetyl 2-ethylhexanoate, 2-hexyldecyl 2-ethylhexanoate, isopropyl myristate, 2-hexyldecyl myristate, octyldodecyl myristate, isopropyl palmitate, 2-ethylhexyl palmitate, ethyl isostearate, isopropyl isostearate, and isostearic acid Isobutyl, 2-hexyldecyl isostearate, 2-ethylhexyl hydroxystearate, octyldodecyl oleate, oleyl oleate, octyldodecyl ricinoleate, octyl p-methoxycinnamate, monoester oils such as propylene carbonate; di-2-hexylhexyl succinate, bis-ethoxydiglycol succinate, di(caprylic / capric acid)propanediol, neopentyl glycol diisononanoate, neopentyl glycol dicaprate, glyceryl diisostearate, poly(ethylene glycol) diisostearate Diester oils such as glyceryl, propanediol diisostearate, diisostearyl malate, di(phytosteryl / octyldodecyl) lauroyl glutamate, di(cholesteryl / behenyl / octyldodecyl) lauroyl glutamate, di(octyldodecyl / phytosteryl / behenyl) lauroyl glutamate, neopentyl glycol di-2-ethylhexanoate, neopentyl glycol dioctanoate; trimethylolpropane triisostearate, glyceryl triisostearate, triisostearin Triester oils such as diglyceryl triate, jojoba oil, trimethylolpropane tri-2-ethylhexanoate, glyceryl tri-2-ethylhexanoate, caprylic / capric triglyceride, glyceryl trioctanoate, tritridecyl trimellitate, macadamia nut oil, olive oil, castor oil, jojoba oil, avocado oil, and sunflower oil; pentaerythrityl tetraoctanoate, diglyceryl tetraisostearate, dipentaerythrityl tetraisostearate, and pentaerythrityl tetraisostearate.

[0099] Examples of hydrocarbon oils include squalane, liquid paraffin, liquid isoparaffin, polybutene, hydrogenated polyisobutene, hydrogenated polydecene, and petrolatum. Examples of ether oils include cetyl dimethyl butyl ether and dicaprylyl ether.

[0100] Examples of higher alcohols include those having a linear or branched alkyl or alkenyl group having 10 to 24 carbon atoms, such as lauryl alcohol, myristyl alcohol, isocetyl alcohol, isostearyl alcohol, 2-octyldodecanol, and oleyl alcohol. Examples of silicone oils include dimethylpolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, acrylic-modified silicone, and fluorine-modified silicone.

[0101] Examples of solid waxes include oily components that are solid at 25°C, such as vegetable waxes such as candelilla wax, rice wax, sunflower wax, carnauba wax, and Japan wax; animal waxes such as beeswax and spermaceti; mineral waxes such as montan wax and ozokerite; petroleum waxes such as microcrystalline wax, paraffin, and ceresin; synthetic waxes such as hydrogenated castor oil, hydrogenated jojoba oil, 12-hydroxystearic acid, stearic acid amide, phthalimide anhydride, silicone wax, fluorine-based wax, polyethylene wax, and synthetic beeswax; fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, and lanolin fatty acid; and higher alcohols such as cetyl alcohol, stearyl alcohol, behenyl alcohol, and hydrogenated dilinoleyl alcohol.

[0102] From the viewpoint of obtaining a uniform, beautiful, and natural finish and suppressing whitening, component (E) preferably contains ester oil, hydrocarbon oil, or silicone oil, and among these, non-volatile oils that are liquid at 25°C are preferred.

[0103] From the viewpoints of achieving a uniform, beautiful, and natural finish and suppressing whitening, component (E) preferably contains at least one or more (E-1) ester oils, more preferably monoester oils, diester oils, and triester oils, even more preferably contains at least a diester oil, and even more preferably a diester oil that is liquid at 25°C.

[0104] Component (E) can be used alone or in combination of two or more, and from the viewpoints of obtaining a uniform, beautiful, and natural finish and suppressing whitening, the content is preferably 0.1 mass% or more of the total composition, more preferably 0.2 mass% or more, even more preferably 0.4 mass% or more, preferably 20 mass% or less, more preferably 15 mass% or less, even more preferably 10 mass% or less, and even more preferably 8 mass% or less. The content of component (E) is preferably 0.1 to 20 mass% of the total composition, more preferably 0.2 to 15 mass%, even more preferably 0.2 to 10 mass%, and even more preferably 0.4 to 8 mass%.

[0105] <Other ingredients> In the present invention, the water content is preferably 50% by mass or less of the total composition, more preferably 30% by mass or less, even more preferably 10% by mass or less, even more preferably 5% by mass or less, and even more preferably 1% by mass or less, from the viewpoint of obtaining a non-sticky feel while maintaining the wrinkle improvement effect on skin.

[0106] In addition to the above-mentioned components, the topical skin preparation composition of the present invention can optionally contain various commonly used components within the scope of not impairing the effects of the present invention. These components include, for example, oily components other than those mentioned above, water-soluble polymers, antioxidants, ultraviolet absorbers, vitamins, preservatives, pH adjusters, fragrances, plant extracts, moisturizers, colorants, cooling agents, antiperspirants, disinfectants, skin activators, etc.

[0107] The skin external preparation composition of the present invention can be applied in any form, such as an oily composition or an emulsion composition, which can be produced by a conventional method. The formulation can be applied in the form of a liquid, emulsion, paste, cream, gel, solid, sheet, etc. The skin topical preparation composition of the present invention can be used for cosmetics, quasi-drugs, and pharmaceutical applications, and can be applied as skin care cosmetics such as lotions, emulsions, creams, serums, dispersions, gels, ointments, packs, mousses, aerosols, poultices, and cleansers; UV protection cosmetics such as sunscreen emulsions and sunscreen creams; and makeup cosmetics such as makeup bases, foundations, concealers, blushers, eye shadows, mascaras, eyeliners, eyebrow products, overcoats, and lipsticks. Examples of containers for storing the external skin preparation composition include bottles, jars, tubes, pumps, syringe containers, mist containers, and pillow containers. The skin external preparation composition of the present invention is suitable for use as an agent for improving skin wrinkles.

[0108] In relation to the above-mentioned embodiment, the present invention further discloses the following composition.

[0109] <1> The following components (A), (B), and (C): (A) 1 to 90% by mass of a polymer having a silicone structure, wherein the deformation ratio measured by the following method (1) is 0.3 or more and 1 or less, and in a bending resistance test using a cylindrical mandrel method performed by the following method (2), the minimum diameter of the cylindrical mandrel at which cracks do not occur in the polymer film is 2 mm or more and 25 mm or less; Method (1): A 10% by weight solution of the polymer in hexamethyldisiloxane was prepared. 0.005 g of this solution was applied to one side of a 20 mm wide, 100 mm long, and 0.03 mm thick polyethylene sheet, starting from one end of the short side and working in the lengthwise direction, over an area measuring 20 mm wide and 50 mm long. The sheet was then dried for 10 minutes in a thermostatic chamber set at 40°C. The length of the polyethylene sheet where the solution was applied was designated L1, and the length of the polyethylene sheet where it had deformed due to shrinkage after drying was designated L2. The value L2 / L1 was used as the deformation ratio. Method (2): A 30% by weight solution of the polymer in hexamethyldisiloxane is prepared. The solution is applied to a polyethylene terephthalate film measuring 50 mm wide, 100 mm long, and 0.1 mm thick using a 200 μm applicator, and the film is dried for 120 minutes in a thermostatic chamber set at 40°C to prepare a test specimen. The test specimen is subjected to a bending resistance test in accordance with the cylindrical mandrel method specified in JIS K5600-5-1:1999, and the minimum diameter of the cylindrical mandrel at which cracks do not occur in the polymer film on the test specimen is determined. (B) a volatile oil having a volatilization rate of 14% or more after drying at 1 atmosphere, 40°C, and 60% RH for 30 minutes; (C) Polyol wherein the mass ratio (A) / (C) of component (A) to component (C) is 3 to 200.

[0110] <2> In the component (A), the deformation ratio L2 / L1 evaluated by the method (1) is preferably 0.5 or more, more preferably 0.6 or more, even more preferably 0.7 or more, even more preferably 0.8 or more, even more preferably 0.85 or more, even more preferably 0.9 or more, and even more preferably 0.95 or more. <1> The skin topical composition described above. <3> In the component (A), in a bending resistance test by a cylindrical mandrel method carried out by the method (2), the minimum diameter of the cylindrical mandrel at which cracks do not occur in the polymer film of the component (A) is preferably 20 mm or less, more preferably 12 mm or less, even more preferably 8 mm or less, even more preferably 6 mm or less, even more preferably 5 mm or less, and preferably 3 mm or more. <1> or <2> The skin topical composition described above. <4> In component (A), the ratio of the deformation rate determined by method (1) to the minimum diameter (mm) of the mandrel determined by method (2) [(deformation rate) / (minimum diameter of the mandrel)] is preferably 0.01 or more, more preferably 0.02 or more, even more preferably 0.10 or more, even more preferably 0.15 or more, and is preferably 0.5 or less, more preferably 0.4 or less; <1> ~ <3> The skin topical preparation composition according to any one of the above.

[0111] <5> The component (A) is preferably a silicone-modified polymer, and more preferably a norbornane structure-containing silicone-modified polymer, a silicone-modified pullulan, a silicone structure-containing silicic acid compound, or a silicone dendrimer. <1> ~ <4> The skin topical preparation composition according to any one of the above. <6> The component (A) is preferably a norbornane structure-containing silicone-modified polymer, more preferably a polymer having a repeating unit represented by the following general formula (1) or (2): <1> ~ <5> The skin topical preparation composition according to any one of the above.

[0112] [ka]

[0113] In the formula, R 2 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.

[0114] [ka]

[0115] In the formula, R 1 is the same as above, and c is an integer of 1 or more and 5 or less.

[0116] [ka]

[0117] 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.

[0118] <7> Component (A) is preferably a norbornane structure-containing silicone-modified polymer, more preferably a silicone-modified polynorbornene, and even more preferably a silicone-modified polynorbornene represented by the following formula (6): <1> ~ <6> The skin topical preparation composition according to any one of the above.

[0119] [ka]

[0120] In the formula, e and f are the numbers of repeating units, and each is independently an integer of 1 or more.

[0121] <8> 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 even more preferably 50 / 50 to 70 / 30 (mol / mol). <7> The skin topical composition described above. <9> Component (A) is preferably at least one selected from the group consisting of silicone-modified polynorbornene, silicone-modified pullulan, trimethylsiloxysilicate, trifluoropropyldimethyl / trimethylsiloxysilicate, and acrylic silicone dendrimer, more preferably at least one selected from the group consisting of silicone-modified polynorbornene, silicone-modified pullulan, trimethylsiloxysilicate, and trifluoropropyldimethyl / trimethylsiloxysilicate, even more preferably at least one selected from the group consisting of silicone-modified polynorbornene and silicone-modified pullulan, and even more preferably silicone-modified polynorbornene. <1> ~ <8> The skin topical preparation composition according to any one of the above. <10> The content of component (A) is preferably 2% by mass or more, more preferably 4% by mass or more, and even more preferably 5% by mass or more, and is preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 18% by mass or less, based on the total composition. <1> ~ <9> The skin topical preparation composition according to any one of the above.

[0122] <11> In the component (B), the volatilization rate after drying for 30 minutes at 1 atmosphere, 40°C and 60% RH is preferably 18% or more, more preferably 25% or more, even more preferably 30% or more, even more preferably 45% or more, even more preferably 65% ​​or more, even more preferably 80% or more, and even more preferably 95% or more. <1> ~ <10> The skin topical preparation composition according to any one of the above. <12> Component (B) is preferably at least one selected from hydrocarbon oils and silicone oils, more preferably at least one selected from the group consisting of isododecane, hexamethyldisiloxane, methyltrimethicone, and dimethylpolysiloxanes having a kinematic viscosity at 25°C of 2 cSt or less, even more preferably at least one selected from the group consisting of isododecane, hexamethyldisiloxane, and dimethylpolysiloxanes having a kinematic viscosity at 25°C of 1.5 cSt or less, even more preferably at least one selected from the group consisting of hexamethyldisiloxane and dimethylpolysiloxanes having a kinematic viscosity at 25°C of 1 cSt or less, and even more preferably hexamethyldisiloxane; <1> ~ <11> The skin topical preparation composition according to any one of the above.

[0123] <13> The content of component (B) is preferably 1% by mass or more, more preferably 30% by mass or more, even more preferably 50% by mass or more, even more preferably 70% by mass or more, even more preferably 72% by mass or more, and is preferably 98% by mass or less, more preferably 97% by mass or less, even more preferably 94% by mass or less, even more preferably 92% by mass or less, and even more preferably 90% by mass or less. <1> ~ <12> The skin topical preparation composition according to any one of the above. <14> The mass ratio (A) / (B) of component (A) to component (B) is preferably 0.02 or more, more preferably 0.03 or more, even more preferably 0.04 or more, still more preferably 0.05 or more, still more preferably 0.1 or more, and is preferably 1 or less, more preferably 0.7 or less, still more preferably 0.4 or less, and still more preferably 0.25 or less. <1> ~ <13> The skin topical preparation composition according to any one of the above.

[0124] <15> The component (C) is preferably one or more selected from glycol, glycerin, and sugar, and more preferably one or more selected from propylene glycol, butylene glycol, glycerin, polypropylene glycol, and sorbitol. <1> ~ <14> The skin topical preparation composition according to any one of the above. <16> The content of component (C) is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, even more preferably 0.3% by mass or more, even more preferably 0.4% by mass or more, and is preferably 20% by mass or less, more preferably 10% by mass or less, even more preferably 6% by mass or less, and even more preferably 4.5% by mass or less, based on the total composition. <1> ~ <15> The skin topical preparation composition according to any one of the above. <17> The mass ratio (A) / (C) of the component (A) to the component (C) is preferably 4 or more, more preferably 5 or more, and is preferably 100 or less, more preferably 50 or less, and even more preferably 34 or less. <1> ~ <16> The skin topical preparation composition according to any one of the above.

[0125] <18> The following components (A), (B), and (C): (A) 1 to 30% by mass of one or more selected from the group consisting of silicone-modified polynorbornene and silicone-modified pullulan, (B) 1 to 98% by mass of a volatile oil having a volatilization rate of 14% or more after drying at 1 atmosphere, 40°C, and 60% RH for 30 minutes; (C) Polyol 0.1 to 20% by mass wherein the mass ratio (A) / (C) of component (A) to component (C) is 3 to 200. <19> The following components (A), (B), and (C): (A) 1 to 30 mass% of silicone-modified polynorbornene, (B) 1 to 98% by mass of a volatile oil having a volatilization rate of 14% or more after drying at 1 atmosphere, 40°C, and 60% RH for 30 minutes; (C) Polyol 0.1 to 20% by mass wherein the mass ratio (A) / (C) of component (A) to component (C) is 3 to 200.

[0126] <20> The following components (A), (B), and (C): (A) 4 to 20% by mass of one or more selected from the group consisting of silicone-modified polynorbornene and silicone-modified pullulan, (B) 70 to 92 mass% of a volatile oil having a volatilization rate of 14% or more after drying at 1 atmosphere, 40°C, and 60% RH for 30 minutes; (C) Polyol 0.2 to 10 mass% wherein the mass ratio (A) / (C) of component (A) to component (C) is 3 to 100. <21> The following components (A), (B), and (C): (A) 4 to 20 mass% of silicone-modified polynorbornene, (B) 70 to 92 mass% of a volatile oil having a volatilization rate of 14% or more after drying at 1 atmosphere, 40°C, and 60% RH for 30 minutes; (C) Polyol 0.2 to 10 mass% wherein the mass ratio (A) / (C) of component (A) to component (C) is 3 to 100.

[0127] <22> It is preferable that the composition further contains a surfactant, more preferably a nonionic surfactant, and even more preferably a nonionic surfactant with an HLB of 1 to 7. <1> ~ <21> The skin topical preparation composition according to any one of the above. <23> The content of the nonionic surfactant is preferably 30% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, even more preferably 3% by mass or less, and even more preferably 1% by mass or less, based on the total composition. <22> The skin topical composition described above.

[0128] <24> Furthermore, it is preferable that the composition further contains a non-volatile oil, more preferably contains one or more selected from ester oil, hydrocarbon oil, and silicone, even more preferably contains at least an ester oil, and even more preferably contains at least a diester oil. <1> ~ <23> The skin topical preparation composition according to any one of the above. <25> The content of non-volatile oil is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, even more preferably 0.4% by mass or more, and is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, and even more preferably 8% by mass or less, based on the total composition. <24> The skin topical composition described above. <26> The content of water is preferably 50% by mass or less, more preferably 30% by mass or less, even more preferably 10% by mass or less, still more preferably 5% by mass or less, and even more preferably 1% by mass or less, based on the total composition. <1> ~ <25> The skin topical preparation composition according to any one of the above. <27> The aforementioned <1> ~ <26> Use of the skin topical preparation composition according to any one of the above items as a skin wrinkle improving agent. [Example]

[0129] The present invention will be described below with reference to examples, but the present invention is not limited to the scope of the examples. In the examples, various measurements and evaluations were carried out by the following methods.

[0130] (Number average molecular weight Mn) The number average molecular weight of the polymer was measured by gel permeation chromatography (GPC) using polystyrene as a standard substance under the following conditions. Measuring device: HLC-8320GPC (Tosoh Corporation) Column: K-806L (Shodex), 2 columns in series Detector: RI Eluent: 1 mmol / L-Farmin DM20 (Kao Corporation) / CHCl3 Flow rate: 1.0mL / min Column temperature: 40℃

[0131] (Deformation ratio) A 10% by weight solution of the polymer (A) used in each composition was prepared in hexamethyldisiloxane. 0.005 g of this solution was applied to one side of a polyethylene sheet 1 ("LL Film" manufactured by Enshu Chemical Industry Co., Ltd.) measuring 20 mm in width (W), 100 mm in length (L0), and 0.03 mm in thickness, as shown in Figure 1(a). The polyethylene sheet was then dried for 10 minutes in a thermostatic chamber set at 40°C. The length of the polyethylene sheet (Figure 1(b)) where the solution was applied was defined as L1 (50 mm), and the length of the polyethylene sheet that had deformed (curled) due to shrinkage after drying was defined as L2. L2 / L1 was calculated as the polymer deformation ratio. L2 was the average of the values ​​measured along the two long sides of polyethylene sheet 1.

[0132] (Bending resistance) A 30% by mass solution of the polymer (A) used in each composition in hexamethyldisiloxane was prepared. This solution was applied to a 50 mm wide, 100 mm long, and 0.1 mm thick polyethylene terephthalate film ("Lumirror 100T60" manufactured by Toray Industries, Inc.) using a 200 μm applicator, and then dried for 120 minutes in a thermostatic oven set at 40°C to produce a film with a polymer film (test piece). The resulting test specimens were subjected to a bending resistance test in accordance with the cylindrical mandrel method specified in JIS K5600-5-1:1999. Using a Type 1 bending tester (Erichsen bending tester, Model 266), the polymer film side of the test specimen was placed on the outside, and the bending resistance test was performed using cylindrical mandrels with diameters of 32 mm, 25 mm, 20 mm, 16 mm, 12 mm, 10 mm, 8 mm, 6 mm, 4 mm, 3 mm, and 2 mm, starting with the largest diameter. The test was terminated when cracks appeared in the polymer film, and the smallest diameter (mm) of the cylindrical mandrel that did not cause cracks was taken as the bending resistance value. A smaller value indicates better bending resistance.

[0133] (volatility rate) 0.5 g of sample was placed in a 40 mm diameter glass petri dish and dried for 30 minutes on a hot plate set at 40°C under 1 atmosphere and 60% RH. The mass of the sample before drying was W0 (g), and the mass of the sample after drying was W1 (g), and the value of {(W0 - W1) / W0} x 100 was taken as the volatilization rate (%). The larger this value, the faster the volatilization rate and the easier it was to dry.

[0134] (wrinkle improvement effect) Five expert panelists applied 0.2 g of each composition with their fingers to one side of the face, pinching the nasolabial folds around the mouth, in the manner shown in Figure 2. After drying for 10 minutes at room temperature (25°C), the anti-wrinkle effect was evaluated sensorily according to the following criteria. The results are shown as the total score of the five panelists. 5: Wrinkles have become significantly lighter. 4: Wrinkles have become less noticeable. 3: Wrinkles have become slightly lighter. 2: Wrinkles remain and there is not much change. 1: No change.

[0135] (Thickness of the coating film after application and drying) Each composition was applied to the skin by five expert panelists, and after drying, the thickness of the coating film was evaluated according to the following criteria. The results were expressed as the total score of the five panelists. 5;There is no unevenness in thickness. 4;There is almost no variation in thickness. 3: The thickness is slightly uneven. 2: The thickness is uneven. 1: There is noticeable unevenness in thickness.

[0136] (Whitening during drying after application) Each composition was applied to the skin by five expert panelists, and the state of whitening during drying was evaluated according to the following criteria. The results were expressed as the total score of the five panelists. 5;It doesn't look white. 4;It doesn't look very white. 3;Some parts appear slightly white. 2: Partially appears white. 1;The whole thing looks white.

[0137] Examples 1 to 14, Comparative Example 1 A liquid skin external preparation composition was prepared with the composition shown in Table 1, and the wrinkle improvement effect, the thickness of the coating film after application and drying, and the whitening state during drying after application were evaluated. The results are also shown in Table 1.

[0138] (Manufacturing method) The oil phase component, a mixture of components (A), (B), and (C), was dispersed using a disper and then stirred using a homomixer to obtain a skin external preparation composition.

[0139] [Table 1]

[0140] In Table 1, *1 to *3 are as follows. *1: An isododecane solution of norbornene / tris(trimethylsiloxy)silylnorbornene copolymer (e / f=60 / 40 (mol / mol), Mn=360,000 in the following formula (6)) manufactured by Shin-Etsu Chemical Co., Ltd., active ingredient concentration: 30% by mass, was dried under reduced pressure at 50°C for 12 hours, and the obtained solid was used.

[0141] [ka]

[0142] *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 resulting solid was used. *3: "X21-5595" manufactured by Shin-Etsu Chemical Co., Ltd. (a solution of trimethylsiloxysilicate in isododecane, active ingredient concentration: 60% by mass) was dried under reduced pressure at 50°C for 12 hours, and the obtained solid was used.

[0143] Examples 15 to 17 In the same manner as in Examples 1 to 14, external skin preparation compositions having the compositions shown in Table 2 were produced. All of the obtained skin external preparation compositions were able to improve wrinkles, had a uniform coating thickness, and were inhibited from whitening during drying after application.

[0144] [Table 2]

[0145] In Table 2, *4 is as follows. *4: "XS66-B8226" manufactured by Momentive Performance Materials Japan, LLC (cyclopentasiloxane solution of trifluoropropyldimethyl / trimethylsiloxysilicate, active ingredient concentration: 50% by mass) was dried under reduced pressure at 50°C for 12 hours, and the resulting solid was used.

[0146] Examples 18-19 In the same manner as in Examples 1 to 14, external skin preparation compositions having the compositions shown in Table 3 were produced. All of the obtained skin external preparation compositions were able to improve wrinkles, had a uniform coating thickness, and were inhibited from whitening during drying after application.

[0147] [Table 3]

[0148] Example 20 A liquid skin topical composition having the composition of Example 1 shown in Table 1 was prepared and filled into a mist container. The skin topical composition was sprayed from this mist container onto the nasolabial folds and surrounding areas of the face, and the wrinkle improvement effect after drying, the state of the coating film thickness after application and drying, and the state of whitening during drying after application were evaluated. As a result, an excellent wrinkle improvement effect was achieved, and a clean coating film with uniform thickness and reduced whitening was obtained. [Explanation of symbols]

[0149] 1 polyethylene sheet 1a One end of the short side of polyethylene sheet 1 2. Polymer solution applied area

Claims

1. The following components (A), (B), and (C): (A) 4 to 30 mass% of a norbornane structure-containing silicone-modified polymer, which has a deformation ratio of 0.3 to 1 as measured by the following method (1), and which has a minimum cylindrical mandrel diameter of 2 mm to 25 mm at which cracks do not occur in the polymer film in a bending resistance test using a cylindrical mandrel method as performed by the following method (2), Method (1): A 10% by weight solution of the polymer in hexamethyldisiloxane is prepared. 0.005 g of the solution is applied to one side of a 20 mm wide, 100 mm long, and 0.03 mm thick polyethylene sheet, starting from one end of the short side and working in the longitudinal direction, over an area measuring 20 mm wide and 50 mm long, and then dried for 10 minutes in a thermostatic chamber set to 40°C. The length of the polyethylene sheet at the portion where the solution was applied was defined as L1, and the length of the polyethylene sheet at the portion deformed by shrinkage after drying was defined as L2, and the value of L2 / L1 was defined as the deformation ratio. Method (2): A 30% by weight solution of the polymer in hexamethyldisiloxane is prepared. The solution is applied to a polyethylene terephthalate film measuring 50 mm wide, 100 mm long, and 0.1 mm thick using a 200 μm applicator, and the film is dried for 120 minutes in a thermostatic chamber set at 40°C to prepare a test specimen. The test specimen is subjected to a bending resistance test in accordance with the cylindrical mandrel method specified in JIS K5600-5-1:1999, and the minimum diameter of the cylindrical mandrel at which cracks do not occur in the polymer film on the test specimen is determined. (B) a volatile oil having a volatilization rate of 14% or more after drying at 1 atmosphere, 40°C, and 60% R.H. for 30 minutes; (C) Polyol wherein the mass ratio (A) / (C) of component (A) to component (C) is 3 to 100.

2. The external skin preparation composition according to claim 1, wherein the content of component (B) is 1 to 98% by mass.

3. 3. The external skin preparation composition according to claim 1, wherein component (C) is one or more selected from the group consisting of glycol, glycerin and sugar.

4. The external skin preparation composition according to any one of claims 1 to 3, wherein the content of component (C) is 0.1 to 20% by mass.

5. 5. The external skin preparation composition according to claim 1, wherein the mass ratio (A) / (B) of component (A) to component (B) is 0.02 to 1.

6. The external skin preparation composition according to any one of claims 1 to 5, further comprising (D) a surfactant.

7. The external skin preparation composition according to any one of claims 1 to 6, wherein component (A) is a norbornene / tris(trimethylsiloxy)silylnorbornene copolymer.

8. The skin external preparation composition according to any one of claims 1 to 6, wherein component (A) is a silicone-modified polynorbornene represented by the following formula (6): 【Chemistry 1】 In the formula, e and f are the numbers of repeating units, and each is independently an integer of 1 or more.

9. 9. The external skin preparation composition according to claim 8, wherein component (A) is a compound represented by formula (6) in which the ratio of e to f is e / f = 20 / 80 to 90 / 10 (mol / mol).

10. Use of the skin external preparation composition according to any one of claims 1 to 9 as a skin wrinkle improving agent.

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