Skin external use composition

Abstract

The present invention provides a skin topical composition, which contains the following components (A), (B) and (C), and the mass ratio (A) / (C) of component (A) to component (C) is 3 to 200, (A) 1 to 30% by mass of a polymer, which is a polymer having a silicone structure, and the deformation ratio measured by a specified method (1) is greater than 0.3 and less than 1, and in a bending resistance test based on a cylindrical mandrel method conducted by a specified method (2), the minimum diameter of a cylindrical mandrel on which no cracks are generated on a film of the polymer is greater than 2 mm and less than 25 mm; (B) a volatile oil having a volatility of greater than 14% after drying at 40°C and 60% RH for 30 minutes under 1 standard atmosphere; and (C) a polyol.

Description

Technical Field

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

[0002] As people age, their skin will develop more wrinkles. This is part of the aging process and is affected by many factors, including changes in skin tissue and the effects of ultraviolet radiation.

[0003] Skin care products and the like have been developed in the past to make wrinkles on the skin less noticeable, but the improvement effect is extremely low and has not satisfied women who have wrinkle problems.

[0004] On the other hand, cosmetics containing 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 states that cosmetics containing film-forming polymers have good durability or good touch, wherein the film-forming polymers are formed by introducing predetermined functional groups into the skeleton of polycycloolefin polymers.

[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), wherein the mass ratio (A) / (C) of the component (A) to the component (C) is 3 to 200,

[0007] (A) 1 to 30% 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 the minimum diameter of a cylindrical mandrel on which cracks are not generated in a film of the polymer in a bending resistance test based on a cylindrical mandrel method performed by the following method (2) is 2 mm or more and 25 mm or less;

[0008] 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 having a width of 20 mm, a length of 100 mm, and a thickness of 0.03 mm, from one end of the short side to the length direction within a range of 20 mm in width and 50 mm in length, and drying in a constant temperature bath set at 40° C. for 10 minutes; setting the length of the polyethylene sheet having the solution applied thereon as L1, setting the length of the polyethylene sheet having the shrinkage deformed after drying as L2, and setting the value of L2 / L1 as the deformation ratio;

[0009] Method (2): preparing a 30 mass % hexamethyldisiloxane solution of the 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 thermostatic chamber set at 40° C. for 120 minutes to prepare a test piece; conducting a bending resistance test using the test piece according to the cylindrical mandrel method specified in JIS K5600-5-1:1999, and determining the minimum diameter of the cylindrical mandrel that does not cause cracks on the polymer film on the test piece;

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

[0011] (C) Polyol. BRIEF DESCRIPTION OF THE DRAWINGS

[0012] Figure 1 This is a diagram for explaining the method for evaluating the deformation ratio (L2 / L1) of a polymer obtained by the method (1).

[0013] Figure 2 This is a diagram showing the manner of applying each skin external preparation composition when evaluating the wrinkle-improving effect in Examples.

[0014] [Explanation of symbols]

[0015] 1 Polyethylene sheet

[0016] 1a One end of the short side of the polyethylene sheet 1

[0017] 2. The part coated with polymer solution DETAILED DESCRIPTION

[0018] Conventional cosmetics containing film-forming polymers have problems such as insufficient wrinkle-improving effects, uneven thickness of the coating film, and noticeable whitening during drying.

[0019] The present inventors have found that by using a polyol in combination with a specific film-forming polymer at a specific ratio, a skin external preparation composition can be obtained which maintains high shrinkage, improves skin wrinkles, has no uneven thickness of the coating film, and suppresses whitening during drying after application, thereby completing the present invention.

[0020] The skin external preparation composition of the present invention can improve skin wrinkles, has no uneven thickness of the coating film, and suppresses whitening during drying after application.

[0021] In this specification, the so-called "skin wrinkles" are changes in shape due to skin relaxation, meaning the bumps and textures that appear on the skin surface. Skin wrinkles tend to appear around the mouth, eyes, forehead, neck, body and other parts. Small textures are small wrinkles, and large textures are large wrinkles. Large wrinkles are caused by the distribution of pores on the nasolabial folds, cheeks, etc. The skin topical composition of the present invention has the effect of making any wrinkles inconspicuous, and in particular, even large wrinkles such as nasolabial folds can be improved non-invasively.

[0022] <Ingredients (A)>

[0023] The component (A) used in the present invention is a polymer having a silicone structure, and the deformation ratio measured by the above-mentioned method (1) is greater than 0.3 and less than 1, and in the bending resistance test based on the cylindrical mandrel method conducted by the above-mentioned method (2), the minimum diameter of the cylindrical mandrel on which no cracks are generated on the film of the polymer is greater than 2 mm and less than 25 mm.

[0024] When the component (A) satisfies the deformation ratio measured by the method (1), for example, when a composition containing a polymer as the component (A) is applied to the skin around wrinkles and then dried, the film containing the polymer shrinks and the surface of the skin attached to the film shrinks. This action stretches the skin at the wrinkled part, making the wrinkles less noticeable.

[0025] Reference Figure 1 The evaluation method of the deformation ratio (L2 / L1) of the component (A) obtained by the above method (1) is described below. 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 (a) shows a single surface of a polyethylene sheet 1 having a width (W) of 20 mm × a length (L0) of 100 mm × a thickness of 0.03 mm, and a range of 20 mm in width × 50 mm in length (L0) extending from one end 1a of the short side of the polyethylene sheet 1 in the longitudinal direction. Figure 1 The portion 2 shown in (a) was applied and dried in a thermostatic bath set at 40° C. for 10 minutes. Figure 1 (b) is a schematic diagram of a polyethylene sheet in which a portion of the polyethylene sheet 1 coated with the solution is deformed (curled) due to the shrinkage of the polymer as the component (A) after drying.

[0026] The dried 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 deformation occurred due to shrinkage after drying 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.

[0027] From the viewpoint of making the wrinkles of the skin less noticeable, the deformation ratio L2 / L1 of component (A) evaluated by the above-mentioned 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.

[0028] Specifically, the deformation ratio can be evaluated by the method described in Examples.

[0029] In addition, component (A) has excellent bending resistance, and in the bending resistance test based on the cylindrical mandrel method performed by the above method (2), the minimum diameter of the cylindrical mandrel that does not cause cracks on the film of the polymer as component (A) is 2 mm or more and 25 mm or less. Therefore, the film formed from the composition containing component (A) is not prone to cracks and is easy to shrink in a state of following the shape of the skin.

[0030] The smaller the minimum diameter of the cylindrical mandrel, the better the bending resistance. From the perspective 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 more preferably 6 mm or less, further more preferably 5 mm or less. On the other hand, from the perspective of providing sufficient strength and shape control effect in order to make the wrinkles of the skin stretch and not conspicuous, the minimum diameter of the cylindrical mandrel that does not produce cracks 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, further preferably 2 to 8 mm, further more preferably 3 to 6 mm, further more preferably 3 to 5 mm.

[0031] The bending resistance can be evaluated specifically according to the method described in Examples using a type 1 bending tester specified in JIS K5600-5-1:1999.

[0032] In addition, the ratio of the deformation ratio of component (A) obtained by the above method (1) to the minimum diameter (mm) of the mandrel obtained by the above method (2) [(deformation ratio) / (minimum diameter of mandrel)] is preferably 0.01 or more, more preferably 0.02 or more, further preferably 0.10 or more, further more preferably 0.15 or more from the viewpoint of the wrinkle improvement effect on the skin, and preferably 0.5 or less, further more preferably 0.4 or less from the viewpoint of providing sufficient strength and shape control effect in order to make the wrinkles of the skin extend and inconspicuous. 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 more preferably 0.15 to 0.5, further more preferably 0.15 to 0.4.

[0033] In the present invention, the "silicone structure" refers to a structure represented by the following general formula (I).

[0034]

[0035] In the general formula (I), R 1 Each independently represents a hydrocarbon group having 1 to 12 carbon atoms, and p represents an integer greater than 1. In view of the fact that wrinkles on the skin are extended and thus inconspicuous when applied, thereby obtaining a sufficient wrinkle improvement effect (hereinafter also referred to as "skin wrinkle improvement effect") and from the perspective 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 more preferably a methyl group.

[0036] The polymer of component (A) may be any polymer as long as it has a silicone structure, and may be a polymer consisting only of a silicone structure. From the viewpoint of obtaining a polymer having the above-mentioned characteristics, a polymer having a part of a silicone structure is preferred. 1 2 SiO 2 / 2 ) structure, and also contains M unit (R 1 3 SiO 1 / 2 ) structure, T unit (R 1 SiO 3 / 2 ) structure, Q unit (SiO 4 / 2 )structure.

[0037] In the case of a polymer having a silicone structure in part, the silicone structure may be present in the main chain or in the side chain in the polymer, but preferably in the side chain from the viewpoint of obtaining a polymer having the above-mentioned predetermined properties.

[0038] When the silicone structure exists in the polymer main chain, there is no particular limitation on its bonding method. For example, the silicone structure may exist at the end of the polymer main chain, or it may be a copolymer in which the silicone structure is bonded to the polymer main chain in a block or random manner. In addition, a polymer graft-modified with a compound having a silicone structure may also be used.

[0039] As component (A) used in the present invention, a silicone-modified polymer is preferred, and specific examples thereof include: silicone-modified polymers containing norbornene structure such as silicone-modified polynorbornene; silicone-modified pullulan; silicic acid compounds containing silicone structure such as trialkylsiloxysilicic acid, fluorine-modified alkylsiloxysilicic acid, and phenyl-modified alkylsiloxysilicic acid; silicone dendrimers, etc.

[0040] (Silicone modified polymer containing norbornane structure)

[0041] In the present invention, the norbornane structure means a structure represented by the following formula: The silicone-modified polymer containing a norbornane structure may be a silicone-modified polymer having the structure represented by the formula at any site in the polymer.

[0042]

[0043] Examples of the silicone-modified polymer containing a norbornane structure include polymers having a repeating unit represented by the following general formula (1) or (2).

[0044]

[0045] In the formula, R 2 Each of them is independently an alkyl group having 1 to 12 carbon atoms, 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.

[0046]

[0047] In the formula, R 1 Similar to the above, c is an integer of 1 to 5.

[0048]

[0049] 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.

[0050] In the above general formula (1), R 2Each independently is 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 from the viewpoint of the skin wrinkle improving effect and the viewpoint of versatility, and is more preferably a methyl group.

[0051] X is a group represented by the above formula (i), wherein R 1 Each of them is independently 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 more preferably a methyl group. c is an integer of 1 to 5, and from the perspective of versatility, c=1 is preferred. That is, X is preferably a trimethylsilyloxy group.

[0052] a is an integer of 1 to 3, and for example, a polymer may be a mixture of a repeating unit of a=2 and a repeating unit of a=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.

[0053] In the above general formula (2), R 1 , R 2 and b are the same as above. d is an integer of 2 to 5, and d=2 is preferred from the viewpoint of versatility. Regarding the cyclic silicone structure in the general formula (2), from the same viewpoint, R 1 and R 2 is a methyl group, and d is 2 or 3. That is, the cyclic silicone structure in the general formula (2) is preferably a structure represented by the following formula (4) or (5).

[0054]

[0055] From the viewpoint of the wrinkle-improving effect on the skin, the ratio of the repeating units represented by the general formula (1) or (2) in the silicone-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. 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 number of repeating units represented by the general formula (1) or (2) in the silicone-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.

[0056] The silicone-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).

[0057]

[0058] In the formula, R 3 ~R 6 Each of them is independently a hydrogen atom, a halogen atom, a substituent selected from an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, and a halogenated hydrocarbon group having 1 to 10 carbon atoms, or an oxetanyl group, an alkoxycarbonyl group, a polyoxyalkylene group, a polyglyceryl group, or an alkoxysilyl group. 3 ~R 6 The two groups selected in may be bonded to each other to form an alicyclic structure, an aromatic ring structure, a carbonamide group or an acid anhydride group. b is the same as above.

[0059] The ratio of the repeating unit represented by the general formula (3) in the silicone-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, from the viewpoint of the wrinkle-improving effect on the skin. In addition, when the repeating unit represented by the general formula (3) is included, the ratio 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 general formula (3) in the silicone-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.

[0060] The ratio of the repeating units represented by the general formulae (1) to (3) in the silicone-modified polymer containing a norbornane structure can be determined by 1 It can be determined by H-NMR measurement.

[0061] The silicone-modified polymer containing a norbornane structure is preferably a silicone-modified polynorbornene, and more preferably a silicone-modified polynorbornene represented by the following formula (6).

[0062]

[0063] In the formula, e and f are the numbers of repeating units, and are each independently an integer of 1 or more.

[0064] From the viewpoint of the wrinkle-improving effect on 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 still more preferably 50 / 50 to 70 / 30 (mol / mol).

[0065] The number average molecular weight Mn of the silicone-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 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 and bending resistance and the effect of improving skin wrinkles. The specific range of the number average molecular weight Mn of the silicone-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.

[0066] The number average molecular weight Mn of the polymer can be measured by gel filtration chromatography (GPC) using polystyrene as a standard substance, and specifically, can be measured by the method described in Examples.

[0067] The silicone-modified polymer containing a norbornane structure is obtained, for example, by addition-polymerizing a silicone-modified cyclic olefin monomer containing a norbornane structure or capable of forming a norbornane structure by a known method.

[0068] For example, a silicone-modified polymer containing a norbornane structure 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 general formula (1a) or (2a) below. It can also be copolymerized with a cyclic olefin monomer represented by the general formula (3a) below.

[0069]

[0070] In the formula, R 1 Each of them is independently an alkyl group having 1 to 12 carbon atoms, 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.

[0071]

[0072] 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.

[0073]

[0074] In the formula, R1 , R 2 and b are the same as above, and d is an integer of 2 or more and 5 or less.

[0075]

[0076] In the formula, R 3 ~R 6 Each of them is independently a hydrogen atom, a halogen atom, a substituent selected from an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, and a halogenated hydrocarbon group having 1 to 10 carbon atoms, or an oxetanyl group, an alkoxycarbonyl group, a polyoxyalkylene group, a polyglyceryl group, or an alkoxysilyl group. 3 ~R 6 The two groups selected in may be bonded to each other to form an alicyclic structure, an aromatic ring structure, a carbonamide group or an acid anhydride group. b is the same as above.

[0077] When the cyclic olefin monomer represented by the general formula (3a) is copolymerized, the amount used is preferably 90 mol% or less, more preferably 70 mol% or less, and further preferably 50 mol% or less, based on 100 mol% of the total monomers used for the polymerization, and is preferably 5 mol% or more, more preferably 10 mol% or more, and further preferably 30 mol% or more, from the viewpoint of the wrinkle-improving effect on the skin.

[0078] The silicone-modified polynorbornene represented by the above formula (6) can be obtained by addition-polymerizing tris(trimethylsiloxy)silylnorbornene represented by the following formula (6a) with norbornene.

[0079]

[0080] From the viewpoint of the wrinkle-improving effect on skin, the copolymerization ratio of tris(trimethylsiloxy)silylnorbornene to norbornene is preferably 20 / 80 to 90 / 10 (mol / mol), more preferably 30 / 70 to 80 / 20 (mol / mol), and still more preferably 50 / 50 to 70 / 30 (mol / mol).

[0081] The repeating units represented by the above general formulae (1) to (3) and the above formula (6) all represent 2,3-addition structural units of the cyclic olefin monomers as raw material monomers, and may also include structural units that become 2,7-addition structural units obtained by addition polymerization of the cyclic olefin monomers.

[0082] As the silicone-modified polymer containing a norbornane structure, a norbornene / tris(trimethylsiloxy)silylnorbornene) copolymer is preferred, which is a compound marked with the INCI name (International Cosmetic Ingredient Dictionary and Handbook 16th edition, Vol. 2, 2016, p. 2274): NORBORNENE / TRIS(TRIMETHYLSILOXY)SILYLNORBORNENE COPOLYMER.

[0083] Examples of commercially available silicone-modified polymers containing a norbornane structure include "NBN-30-ID" (isododecane solution of a norbornene / tris(trimethylsiloxy)silylnorbornene) copolymer manufactured by Shin-Etsu Chemical Co., Ltd.).

[0084] (Silicone modified pullulan)

[0085] Examples of silicone-modified pullulan include pullulan having a silicone structure in a side chain. Specifically, from the viewpoint of skin wrinkle improvement effect and versatility, silicone-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.

[0086] -Z 1 -SiX a R 2 3-a (7)

[0087] In the formula, Z 1 is a single bond or a divalent organic group. 2 , X, and a are the same as above. From the same viewpoint, X is preferably trimethylsilyloxy, and a is preferably 3.

[0088] 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 more preferably a divalent group represented by the following general formula (9).

[0089]

[0090] In the formula, R 11 Examples of the alkylene group having 1 to 10 carbon atoms include methylene, ethylene, trimethylene, propylene, butylene, etc. Among these, ethylene, trimethylene, and propylene are preferred, and trimethylene or propylene is more preferred from the same viewpoint.

[0091] Examples of commercially available silicone-modified pullulan include “TSPL-30-ID” (an isododecane solution of tris(trimethylsiloxy)silylpropylcarbamate pullulan) and “TSPL-30-D5” (a cyclopentasiloxane solution of tris(trimethylsiloxy)silylpropylcarbamate pullulan) manufactured by Shin-Etsu Chemical Co., Ltd.

[0092] (Silicic acid compounds containing silicone structure)

[0093] Examples of the silicone structure-containing silicic acid compound used in the present invention include silicate compounds having a silicone structure at the terminal, such as trialkylsiloxysilicic acid, fluorine-modified alkylsiloxysilicic acid, and phenyl-modified alkylsiloxysilicic acid.

[0094] 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.

[0095] Examples of fluorine-modified alkylsiloxysilicic acid include compounds in which at least a portion of hydrogen atoms in the alkyl group of trialkylsiloxysilicic acid are substituted with fluorine atoms, and specific examples thereof include trifluoropropyldimethylsiloxysilicic acid and trifluoropropyldimethyl / trimethylsiloxysilicic acid.

[0096] Examples of the phenyl-modified alkylsiloxysilicic acid include phenylpropyldimethylsiloxysilicic acid and phenylpropyldimethyl / trimethylsiloxysilicic acid.

[0097] Among the silicic acid compounds containing a silicone structure, from the viewpoint of the wrinkle-improving effect on the skin, at least one selected from trialkylsiloxysilicic acid and fluorine-modified alkylsiloxysilicic acid is preferred.

[0098] As commercially available silicate compounds containing a silicone 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 LLC can be used.

[0099] (Silicone Dendrimer)

[0100] Examples of silicone 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.

[0101]

[0102] In the formula, R 1 Same as above. 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.

[0103]

[0104] 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 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 the general formula (11), i It is an integer greater than or equal to 0 and less than or equal to 3.

[0105] In the general formula (10), Z 2It 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).

[0106]

[0107] In the formula, R 13 The alkylene group has 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 has 1 to 10 carbon atoms, and examples thereof include methylene, ethylene, trimethylene, propylene, butylene, etc. From the same viewpoint, ethylene is preferred. q is an integer of 0 to 4, and r is 0 or 1.

[0108] Examples of the vinyl polymer having a siloxane dendron structure in a side chain (hereinafter also simply referred to as "vinyl polymer") include polymers having repeating units derived from a monomer represented by the following general formula (15).

[0109]

[0110] 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 perspective of versatility, preferably (meth)acryl or vinyl, more preferably (meth)acryl.

[0111] The ethylene polymer may further include repeating units from ethylene monomers other than the monomers represented by the general formula (15). As the ethylene monomer, a monomer other than the monomer represented by the general formula (15) having a group containing a vinyl bond, such as (meth) acrylic acid, (meth) alkyl acrylate, (meth) hydroxyalkyl acrylate, aromatic ring-containing (meth) acrylic acid ester, fatty acid vinyl ester, (meth) acrylamide, styrene or its derivatives, etc., can be used with one or more than two of these. Among these, from the perspective of versatility, preferably (meth) acrylic acid, (meth) alkyl acrylate, (meth) hydroxyalkyl acrylate, aromatic ring-containing (meth) acrylic acid ester (meth) (meth) (meth) acrylic acid monomers.

[0112] The content of the repeating unit derived from the monomer represented by the general formula (15) in the ethylene-based polymer is preferably 0.1% by mass or more, more preferably 10% by mass or more, and still more preferably 20% by mass or more, relative to the total repeating units in the ethylene-based polymer, from the viewpoint of the wrinkle-improving effect on the skin. The upper limit is 100% by mass.

[0113] 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 a side chain (hereinafter also referred to as "acrylic silicone dendrimer"). The acrylic silicone 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).

[0114] Examples of commercially available silicone dendrimers include acrylic silicone dendrimers such as “FA4001CM 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.

[0115] As component (A), among the above polymers, from the viewpoint of the wrinkle-improving effect on skin, preferably at least one selected from silicone-modified polynorbornene, silicone-modified pullulan, trimethylsiloxysilicic acid, trifluoropropyl dimethyl / trimethylsiloxysilicic acid, and acrylic silicone dendrimer, more preferably at least one selected from silicone-modified polynorbornene, silicone-modified pullulan, trimethylsiloxysilicic acid, and trifluoropropyl dimethyl / trimethylsiloxysilicic acid, and from the viewpoint of the wrinkle-improving effect on skin and the bending resistance, further preferably at least one selected from silicone-modified polynorbornene and silicone-modified pullulan, further more preferably silicone-modified polynorbornene.

[0116] Component (A) may be used alone or in combination of two or more. The solid content is 1% by mass or more, preferably 2% by mass or more, more preferably 4% by mass or more, and more preferably 5% by mass or more in the total composition from the viewpoint of the wrinkle improvement effect on the skin, and is 30% by mass or less, preferably 25% by mass or less, more preferably 20% by mass or less, and more preferably 18% by mass or less. In addition, 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 more preferably 5 to 18% by mass in the total composition.

[0117] <Ingredient (B)>

[0118] The component (B) used in the present invention is a volatile oil having a volatility of 14% or more after drying at 40°C and 60% RH for 30 minutes under 1 standard atmosphere. By including the component (B), the drying speed of the composition containing the component (A) is increased, thereby accelerating the shrinkage of the component (A) during the drying process, further improving the effect of smoothing the wrinkles of the skin and making them less noticeable.

[0119] From the viewpoint of obtaining the above-mentioned effect, the volatility of component (B) after drying at 40°C and 60%RH for 30 minutes under 1 standard atmosphere 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. The upper limit is 100%.

[0120] The volatility of component (B) is determined by placing 0.5 g of a sample in a glass dish having a diameter of 40 mm, leaving the dish to dry at 40° C. for 30 minutes under 1 standard atmosphere and 60% RH. The mass of the sample before drying is defined as W. 0 (g), the mass of the sample after drying is set as W 1 (g), with {(W 0 -W 1 ) / W0 The larger the value, the faster the volatilization speed and the easier it is to dry.

[0121] Furthermore, two or more volatile oils may be used as the component (B).

[0122] The above-mentioned volatility can be specifically measured by the method described in Examples.

[0123] As component (B), from the viewpoint of improving the wrinkle improvement effect of the skin, one or more oils selected from hydrocarbon oils and silicone oils and having a volatility within the above range can be cited. 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, 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.

[0124] From the viewpoint of improving 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 more preferably hexamethyldisiloxane.

[0125] 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 Fluid 1cs” and “SH200C Fluid 1.5cs” manufactured by Dow Corning Toray Co., Ltd., “TSF451-0.65” manufactured by Momentive Performance Materials Japan LLC, and “BELSILDM0.65” manufactured by Wacker Asahikasei Silicone Co., Ltd.

[0126] Component (B) can be used alone or in combination of two or more. The content 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, more preferably 72% by mass or 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 the total composition from the viewpoint of improving the wrinkle improvement effect of the skin. In addition, the content of component (B) is 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 72 to 90% by mass in the total composition.

[0127] In the present invention, 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 more preferably 0.1 or more, and preferably 1 or less, more preferably 0.7 or less, further preferably 0.4 or less, further more preferably 0.25 or less, from the viewpoint of the wrinkle-improving effect on the skin. Furthermore, 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 more preferably 0.05 to 0.25, further more preferably 0.1 to 0.25.

[0128] <Ingredient (C)>

[0129] The polyol as the component (C) used in the present invention is a compound having two or more hydroxyl groups in the molecule and may be any component generally used in external preparations for skin.

[0130] Examples of diols include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, butylene glycol, propylene glycol, etc. Examples of triols include glycerol, trimethylolpropane, etc. Examples of tetraols include diglycerol, erythritol, etc. Examples of polyols with a valency of 5 or more include polyglycerols such as triglycerol, and sugars and sugar alcohols such as glucose, maltose, maltitol, sucrose, xylitol, sorbitol, mannitol, polyoxyethylene methyl glucoside, polyoxyethylene ethyl glucoside, and polyoxyethylene propylene glucoside.

[0131] As component (C), from the viewpoint of uniformity without uneven thickness, obtaining a beautiful and natural makeup, and suppressing whitening, it is preferably one or more selected from glycols, glycerin, and sugars, and more preferably at least one or more selected from propylene glycol, butylene glycol, glycerin, polypropylene glycol, and sorbitol.

[0132] Component (C) can be used in one kind or in combination of two or more kinds. The content is preferably 0.1% by mass or more in the total composition, more preferably 0.2% by mass or more, and further preferably 0.3% by mass or more, and further preferably 0.4% by mass or more, preferably 20% by mass or less, more preferably 10% by mass or less, further preferably 6% by mass or less, and further preferably 4.5% by mass or less. In addition, the content of component (C) is preferably 0.1-20% by mass, more preferably 0.2-10% by mass, further preferably 0.3-6% by mass, and further more preferably 0.4-4.5% by mass in the total composition, from the viewpoint of uniformity and no uneven thickness, beautiful and natural makeup, and suppression of whitening.

[0133] In the present invention, the mass ratio (A) / (C) of the component (A) to the component (C) is 3 or more, preferably 4 or more, more preferably 5 or more, and is 200 or less, preferably 100 or less, more preferably 50 or less, and further preferably 34 or less, from the viewpoint of improving wrinkles, making the coating film thickness non-uniform, and suppressing whitening during drying after coating. The mass ratio (A) / (C) of the component (A) to the component (C) is 3 to 200, preferably 3 to 100, more preferably 4 to 50, and further preferably 5 to 34.

[0134] <Ingredient (D)>

[0135] The skin external preparation composition of the present invention may further contain (D) a surfactant, preferably an anionic surfactant, a cationic surfactant, a nonionic surfactant, or an amphoteric surfactant.

[0136] The surfactant of component (D) is not limited as long as it is a surfactant commonly used in skin external preparations, but a nonionic surfactant is preferred from the viewpoint of being soluble in volatile oils, suppressing stickiness, and suppressing flaking or whitening of the coating film over time.

[0137] 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 cholesteryl ethers, polyoxyethylene cholesterol ethers, alkyl glyceryl ether-modified silicones, polyoxyalkylene-modified silicones, polyoxyalkylene-alkyl co-modified silicones, and polyoxyalkylene-fluoroalkyl co-modified silicones.

[0138] Among these, from the viewpoint of improving the dispersibility and solubility of water and water-soluble components in oil, silicone surfactants are preferred, and one or more alkyl glyceryl ether-modified silicones and polyoxyalkylene-modified silicones are more preferred, and polyoxyalkylene-modified silicones are further preferred.

[0139] As the polyoxyalkylene-modified silicone, 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, KF6017, and KF-6004 manufactured by Shin-Etsu Chemical Co., Ltd. can be used.

[0140] The nonionic surfactant preferably has an HLB value of 1 or more and 7 or less, and more preferably has an HLB value of 2 or more and 6 or less, from the viewpoint of improving the dispersion and solubility of water and water-soluble components in oil.

[0141] Here, HLB (Hydrophilic-Lypophilic Balance) represents the molecular weight of the hydrophilic group portion in the total molecular weight of the surfactant, and is calculated by Griffin's formula for nonionic surfactants.

[0142] 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 adding and averaging the HLB values ​​of the respective nonionic surfactants based on the blending ratio.

[0143] Mixed HLB = Σ(HLBx×Wx) / ΣWx

[0144] HLBx represents the HLB value of nonionic surfactant X.

[0145] Wx is the weight (g) of nonionic surfactant X having the value of HLBx

[0146] The nonionic surfactant may be used alone or in combination of two or more. The content is preferably 30% by mass or less, more preferably 10% by mass or less, further preferably 5% by mass or less, further more preferably 3% by mass or less, further more preferably 1% by mass or less, in the total composition from the viewpoint of dissolving in volatile oil and suppressing greasiness.

[0147] <Ingredient (E)>

[0148] The skin external preparation composition of the present invention may further contain (E) non-volatile oil. Non-volatile means that the mass reduction rate after 1 g of the oil is spread in a glass dish with a diameter of 48 mm and left at 25°C and normal pressure for 24 hours is 1% or less.

[0149] The nonvolatile oil of component (E) may be any nonvolatile oil commonly used in cosmetics, and may be in liquid, paste or solid form, and examples thereof include ester oils, hydrocarbon oils, ether oils, higher alcohols, silicone oils, solid waxes and the like.

[0150] Examples of the ester oil include isononyl isononanoate, isodecyl isononanoate, tridecyl isononanoate, tricyclodecyl methyl 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, Isobutyl isostearate, 2-hexyldecyl isostearate, 2-ethylhexyl hydroxystearate, octyldodecyl oleate, oleic acid oil, octyldodecyl ricinoleate, octyl p-methoxycinnamate, propylene carbonate and other monoester oils; 2-ethylhexyl succinate, bisethoxydiethylene glycol succinate, di(caprylic / capric)propylene glycol ester, neopentyl glycol diisononanoate, neopentyl glycol dicaprate, glyceryl diisostearate, diisostearate Polyglyceryl fatty acid esters, propylene glycol diisostearate, diisostearate 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 dicaprylate and other diester oils; trimethylolpropane triisostearate, glyceryl triisostearate Esters, triisostearate diglyceryl, jojoba oil, trimethylolpropane tri-2-ethylhexanoate, tri-2-ethylhexanoin, tri(capryl / capric)glyceryl, tricaprylyl, tridecyl trimellitate, macadamia oil, olive oil, castor oil, jojoba oil, avocado oil, sunflower oil and other triester oils; pentaerythrityl tetraoctanoate, diglyceryl tetraisostearate, dipentaerythrityl tetraisostearate, pentaerythrityl tetraisostearate, etc.

[0151] Examples of the hydrocarbon oil include squalane, liquid paraffin, liquid isoparaffin, polybutene, hydrogenated polyisobutene, hydrogenated polydecene, and vaseline.

[0152] Examples of the ether oil include cetyl dimethyl butyl ether and dicaprylyl ether.

[0153] Examples of the higher alcohol include higher alcohols 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.

[0154] Examples of the silicone oil include dimethyl polysiloxane, methylphenyl polysiloxane, methyl hydrogen polysiloxane, acrylic modified silicone, and fluorine modified silicone.

[0155] Solid waxes are oily components that are solid at 25°C, and examples thereof include: vegetable waxes such as candelilla wax, rice bran wax, sunflower wax, carnauba wax, and wood 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, stearamide, phthalic anhydride imide, silicone wax, fluorine wax, polyethylene wax, and synthetic beeswax; fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, and lanolin fatty acid; higher alcohols such as cetyl alcohol, stearyl alcohol, behenyl alcohol, and hydrogenated dimer linoleyl alcohol, and the like.

[0156] Component (E) preferably contains ester oil, hydrocarbon oil, or silicone oil, and among them, nonvolatile oil that is liquid at 25° C. is preferred, from the viewpoint of obtaining a uniform, beautiful, and natural makeup and suppressing whitening.

[0157] As component (E), from the viewpoint of obtaining a uniform, beautiful and natural makeup and suppressing whitening, it is preferred that at least one or two or more (E-1) ester oils are contained, more preferably monoester oils, diester oils, and triester oils, further preferably at least diester oils are contained, and further preferably diester oils that are liquid at 25°C.

[0158] Component (E) can be used alone or in combination of two or more. The content is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and further preferably 0.4% by mass or more, preferably 20% by mass or less, more preferably 15% by mass or less, further preferably 10% by mass or less, and further preferably 8% by mass or less, in the total composition, from the viewpoint of obtaining a uniform, beautiful and natural makeup and suppressing whitening. In addition, the content of component (E) is preferably 0.1 to 20% by mass, more preferably 0.2 to 15% by mass, further preferably 0.2 to 10% by mass, and further preferably 0.4 to 8% by mass in the total composition.

[0159] <Other ingredients>

[0160] In the present invention, the water content is preferably 50% by mass or less, more preferably 30% by mass or less, further preferably 10% by mass or less, further more preferably 5% by mass or less, further more preferably 1% by mass or less, in the total composition from the viewpoint of maintaining the wrinkle-improving effect on the skin and obtaining a non-sticky feeling during use.

[0161] In addition to the above-mentioned ingredients, the skin external preparation composition of the present invention can also use any commonly used various 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, vitamins, preservatives, pH adjusters, fragrances, plant extracts, moisturizers, colorants, cooling agents, antiperspirants, bactericides, skin revitalizers, etc.

[0162] 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 applied in the form of a liquid, emulsion, paste, cream, gel, solid, sheet, etc.

[0163] The skin topical composition of the present invention can be used as a cosmetic, quasi-drug, or pharmaceutical product, and can be made into skin care cosmetics such as lotions, emulsions, creams, beauty essences, dispersions, gels, ointments, facial masks, mousses, aerosols, compresses, and detergents; UV protection cosmetics such as sunscreen lotions and sunscreen creams; and color cosmetics such as makeup bases, pressed powders, concealers, blushers, eye shadows, mascara, eyeliners, eyebrow pencils, covering agents, and lipsticks.

[0164] Examples of the container for housing the composition for external skin application include bottles, jars, tubes, pumps, syringe containers, spray containers, pillow containers, and the like.

[0165] The skin external application composition of the present invention is suitable for use as a skin wrinkle improving agent.

[0166] Regarding the above-mentioned embodiment, the present invention further discloses the following composition.

[0167] <1> A composition for external use on skin comprising the following components (A), (B) and (C), wherein the mass ratio of the component (A) to the component (C) (A) / (C) is 3 to 200,

[0168] (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 the minimum diameter of a cylindrical mandrel that does not cause cracks in a film of the polymer in a bending resistance test based on a cylindrical mandrel method performed by the following method (2) is 2 mm or more and 25 mm or less;

[0169] Method (1): preparing a 10 mass % hexamethyldisiloxane solution of the above polymer; applying 0.005 g of the solution on one side of a polyethylene sheet having a width of 20 mm, a length of 100 mm, and a thickness of 0.03 mm from one end of the short side to the length direction in a range of 20 mm in width and 50 mm in length, and drying in a thermostatic bath set at 40° C. for 10 minutes; setting the length of the portion of the polyethylene sheet coated with the above solution as L1, setting the length of the portion of the polyethylene sheet deformed due to shrinkage after drying as L2, and setting the value of L2 / L1 as the deformation ratio;

[0170] Method (2): preparing a 30 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 thermostatic chamber set at 40° C. for 120 minutes to prepare a test piece; conducting a bending resistance test using the test piece according to the cylindrical mandrel method specified in JIS K5600-5-1:1999, and determining the minimum diameter of the cylindrical mandrel that does not cause cracks in the polymer film on the test piece;

[0171] (B) a volatile oil having a volatility of 14% or more after drying at 40°C and 60% RH for 30 minutes under 1 standard atmosphere;

[0172] (C) Polyol.

[0173] <2> The skin external preparation composition as described in <1> above, wherein, in component (A), the deformation ratio L2 / L1 evaluated by the above method (1) is 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.

[0174] <3> A skin topical preparation composition as described in <1> or <2> above, wherein, in component (A), in a bending resistance test based on a cylindrical mandrel method performed by the above method (2), the minimum diameter of a cylindrical mandrel that does not produce cracks on a film of a polymer serving as component (A) is preferably 20 mm or less, more preferably 12 mm or less, further preferably 8 mm or less, further more preferably 6 mm or less, further more preferably 5 mm or less, and preferably 3 mm or more.

[0175] <4> A skin topical preparation composition as described in any one of <1> to <3> above, wherein, in component (A), the ratio of the deformation ratio obtained by the above method (1) to the minimum diameter (mm) of the mandrel obtained by the above method (2) [(deformation ratio) / (minimum diameter of the mandrel)] is preferably 0.01 or more, more preferably 0.02 or more, further preferably 0.10 or more, further preferably 0.15 or more, preferably 0.5 or less, more preferably 0.4 or less.

[0176] <5> The skin external preparation composition as described in any one of <1> to <4> above, wherein component (A) is preferably a silicone-modified polymer, and more preferably a silicone-modified polymer containing a norbornane structure, a silicone-modified pullulan, a silicic acid compound containing a silicone structure, or a silicone dendrimer.

[0177] <6> The composition for external use on skin according to any one of <1> to <5> above, wherein component (A) is preferably a silicone-modified polymer containing a norbornane structure, and more preferably a polymer having a repeating unit represented by the following general formula (1) or (2),

[0178]

[0179] In the formula, R 2 Each independently represents an alkyl group having 1 to 12 carbon atoms, 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;

[0180]

[0181] In the formula, R 1 As above, c is an integer greater than or equal to 1 and less than or equal to 5;

[0182]

[0183] 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.

[0184] <7> The composition for external use on skin according to any one of <1> to <6>, wherein component (A) is preferably a silicone-modified polymer having a norbornane structure, more preferably a silicone-modified polynorbornene, and still more preferably a silicone-modified polynorbornene represented by the following formula (6):

[0185]

[0186] In the formula, e and f are the numbers of repeating units, and are each independently an integer of 1 or more.

[0187] <8> The skin external preparation composition as described in <7> above, wherein 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 even more preferably 50 / 50 to 70 / 30 (mol / mol).

[0188] <9> A composition for external use on skin as described in any one of <1> to <8> above, wherein component (A) is preferably one or more selected from silicone-modified polynorbornene, silicone-modified pullulan, trimethylsiloxysilicic acid, trifluoropropyl dimethyl / trimethylsiloxysilicic acid, and acrylic silicone dendrimer, more preferably one or more selected from silicone-modified polynorbornene, silicone-modified pullulan, trimethylsiloxysilicic acid, and trifluoropropyl dimethyl / trimethylsiloxysilicic acid, further preferably one or more selected from silicone-modified polynorbornene and silicone-modified pullulan, and further more preferably silicone-modified polynorbornene.

[0189] <10> A skin topical preparation composition as described in any one of <1> to <9> above, wherein the content of component (A) is preferably 2% by mass or more, more preferably 4% by mass or more, and further preferably 5% by mass or more, and is preferably 25% by mass or less, more preferably 20% by mass or less, and further preferably 18% by mass or less in the total composition.

[0190] <11> A skin topical preparation composition as described in any one of <1> to <10> above, wherein in component (B), the volatility after drying at 40°C and 60% RH at 1 standard atmosphere for 30 minutes 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.

[0191] <12> A composition for external use on skin as described in any one of <1> to <11> 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, methyltrimethicone, and dimethylpolysiloxane having a kinetic viscosity of 2 cSt or less at 25°C, further preferably at least one selected from isododecane, hexamethyldisiloxane, and dimethylpolysiloxane having a kinetic viscosity of 1.5 cSt or less at 25°C, further more preferably at least one selected from hexamethyldisiloxane and dimethylpolysiloxane having a kinetic viscosity of 1 cSt or less at 25°C, further more preferably hexamethyldisiloxane.

[0192] <13> A skin topical preparation composition as described in any one of <1> to <12> above, wherein the content of component (B) 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 more preferably 72% by mass or more, preferably 98% by mass or less, more preferably 97% by mass or less, further preferably 94% by mass or less, further more preferably 92% by mass or less, further more preferably 90% by mass or less.

[0193] <14> A skin topical preparation composition as described in any one of <1> to <13> above, 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, preferably 1 or less, more preferably 0.7 or less, further preferably 0.4 or less, further more preferably 0.25 or less.

[0194] <15> A skin external application composition as described in any one of <1> to <14> above, wherein component (C) is preferably one or more selected from glycols, glycerol, and sugars, and more preferably contains one or more selected from propylene glycol, butylene glycol, glycerol, polypropylene glycol, and sorbitol.

[0195] <16> A skin topical preparation composition as described in any one of <1> to <15> above, wherein the content of component (C) is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, further preferably 0.3% by mass or more, further more preferably 0.4% by mass or more, preferably 20% by mass or less, more preferably 10% by mass or less, further preferably 6% by mass or less, further more preferably 4.5% by mass or less, in the total composition.

[0196] <17> A skin external application composition as described in any one of <1> to <16> above, wherein the mass ratio (A) / (C) of component (A) to component (C) is preferably 4 or more, more preferably 5 or more, preferably 100 or less, more preferably 50 or less, and even more preferably 34 or less.

[0197] <18> A composition for external use on the skin, comprising the following components (A), (B) and (C), wherein the mass ratio of the component (A) to the component (C) (A) / (C) is 3 to 200,

[0198] (A) 1 to 30% by mass of one or more selected from silicone-modified polynorbornene and silicone-modified pullulan;

[0199] (B) 1 to 98% by mass of a volatile oil having a volatility of 14% or more after drying at 40° C. and 60% RH for 30 minutes under 1 standard atmosphere;

[0200] (C) 0.1 to 20% by mass of polyol.

[0201] <19> A composition for external use on the skin, comprising the following components (A), (B) and (C), wherein the mass ratio of the component (A) to the component (C) (A) / (C) is 3 to 200,

[0202] (A) 1 to 30% by mass of silicone-modified polynorbornene;

[0203] (B) 1 to 98% by mass of a volatile oil having a volatility of 14% or more after drying at 40° C. and 60% RH for 30 minutes under 1 standard atmosphere;

[0204] (C) 0.1 to 20% by mass of polyol.

[0205] <20> A composition for external use on skin comprising the following components (A), (B) and (C), wherein the mass ratio of component (A) to component (C) (A) / (C) is 3 to 100,

[0206] (A) 4 to 20% by mass of one or more selected from silicone-modified polynorbornene and silicone-modified pullulan;

[0207] (B) 70 to 92% by mass of a volatile oil having a volatility of 14% or more after drying at 40°C and 60% RH at 1 standard atmosphere for 30 minutes;

[0208] (C) 0.2 to 10% by mass of polyol.

[0209] <21> A composition for external use on skin comprising the following components (A), (B) and (C), wherein the mass ratio (A) / (C) of the component (A) to the component (C) is 3 to 100,

[0210] (A) 4 to 20% by mass of silicone-modified polynorbornene;

[0211] (B) 70 to 92% by mass of a volatile oil having a volatility of 14% or more after drying at 40°C and 60% RH at 1 standard atmosphere for 30 minutes;

[0212] (C) 0.2 to 10% by mass of polyol.

[0213] <22> The skin external application composition according to any one of <1> to <21>, which preferably further contains a surfactant, more preferably a nonionic surfactant, and even more preferably a nonionic surfactant of HLB 1 to 7.

[0214] <23> The skin external preparation composition as described in <22> above, wherein the content of the nonionic surfactant is preferably 30% by mass or less, more preferably 10% by mass or less, further preferably 5% by mass or less, further more preferably 3% by mass or less, further more preferably 1% by mass or less, in the total composition.

[0215] <24> The skin external application composition as described in any one of <1> to <23> above, which preferably further contains a non-volatile oil, more preferably contains one or more selected from ester oils, hydrocarbon oils, and silicones, further preferably contains at least an ester oil, and further more preferably contains at least a diester oil.

[0216] <25> The skin external preparation composition as described in <24> above, wherein the content of the non-volatile oil is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and 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.

[0217] <26> The skin external preparation composition as described in any one of <1> to <25> above, wherein the water content is preferably 50 mass% or less, more preferably 30 mass% or less, further preferably 10 mass% or less, further more preferably 5 mass% or less, further more preferably 1 mass% or less in the total composition.

[0218] <27> Use of the composition for external use on skin according to any one of <1> to <26> as an agent for improving skin wrinkles.

[0219] [Example]

[0220] The present invention will be further described below by way of examples, but the present invention is not limited to the scope of the examples. In the present examples, various measurements and evaluations were performed by the following methods.

[0221] (Number average molecular weight Mn)

[0222] The number average molecular weight of the polymer was measured by gel filtration chromatography (GPC) using polystyrene as a standard substance under the following conditions.

[0223] Measuring device: HLC-8320GPC (manufactured by Tosoh Corporation)

[0224] Column: K-806L (Shodex), 2 columns connected in series

[0225] Detector: RI

[0226] Eluent: 1mmol / L-Farmin DM20 (manufactured by Kao Corporation) / CHCl 3

[0227] Flow rate: 1.0mL / min

[0228] Column temperature: 40°C

[0229] (Deformation ratio)

[0230] 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 1 (a) A single surface of a polyethylene sheet 1 ("LL Film" manufactured by ENSHU CHEMICAL INDUSTRIES) having a width (W) of 20 mm × a length (L0) of 100 mm × a thickness of 0.03 mm is provided, and a plurality of layers of polyethylene sheet 1 are provided. The plurality of layers of polyethylene sheet 1 are provided with a plurality of layers of polyethylene sheet 1, each of which has a width (W) of 20 mm × a length (L0) of 100 mm × a thickness of 0.03 mm. Figure 1 (a) and dried in a thermostatic oven set at 40°C for 10 minutes. Figure 1 The length of the polyethylene sheet at the portion where the solution was applied in (b)) was set to L1 (50 mm), and the length of the polyethylene sheet at the portion where the shrinkage (curling) occurred after drying was set to L2, and L2 / L1 was calculated and used as the deformation ratio of the polymer. L2 was set to the average value of the values ​​measured on the two long sides of the polyethylene sheet 1.

[0231] (Bending resistance)

[0232] A 30% by mass hexamethyldisiloxane solution of the polymer of component (A) used in each composition was prepared. The solution was applied onto a polyethylene terephthalate film ("Lumirror 100T60" manufactured by Toray Co., Ltd.) having a width of 50 mm×a length of 100 mm×a thickness of 0.1 mm using a 200 μm applicator, and dried in a thermostatic bath set at 40° C. for 120 minutes to prepare a film (test piece) with a polymer film.

[0233] Using the obtained test piece, the bending resistance test was carried out according to the cylindrical mandrel method specified in JIS K5600-5-1:1999. Using a bending test device of type 1 (bending tester manufactured by Erichsen, model 266), the surface of the polymer film side of the test piece was made to be the outside, and cylindrical mandrels with diameters of 32mm, 25mm, 20mm, 16mm, 12mm, 10mm, 8mm, 6mm, 4mm, 3mm, and 2mm were used to carry out the bending resistance test in sequence from the cylindrical mandrel with a larger diameter. The test was terminated at the time when cracks occurred in the polymer film, and the minimum diameter (mm) of the cylindrical mandrel that did not produce cracks was used as the value of bending resistance. The smaller the value, the better the bending resistance.

[0234] (Volatization rate)

[0235] 0.5 g of the sample was placed in a glass dish with a diameter of 40 mm and dried on a hot plate set at 40° C. under 1 standard atmosphere and 60% RH for 30 minutes. The mass of the sample before drying was defined as W. 0 (g), the mass of the sample after drying is set as W 1 (g), {(W 0 -W 1 ) / W 0 The value of}×100 is taken as the volatilization rate (%). The larger the value, the faster the volatilization speed is and the easier it is to dry.

[0236] (Wrinkle improvement effect)

[0237] A team of 5 professional members Figure 2 0.2 g of each composition was applied with fingers on the nasolabial folds of 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 were expressed as the total score of 5 people.

[0238] 5: Wrinkles become very light.

[0239] 4: Wrinkles become lighter.

[0240] 3: Wrinkles are slightly lightened.

[0241] 2: Wrinkles are retained and do not change much.

[0242] 1: No change.

[0243] (Thickness of the coating film after coating and drying)

[0244] After applying each composition to the skin and drying it, five professional panelists conducted sensory evaluation on the thickness of the coating film according to the following criteria. The results are shown as the total score of the five panelists.

[0245] 5: No uneven thickness.

[0246] 4: Almost no uneven thickness.

[0247] 3: The thickness is slightly uneven.

[0248] 2: The thickness is uneven.

[0249] 1: The thickness is obviously uneven.

[0250] (Whitening state during drying after coating)

[0251] Five professional panelists applied each composition to the skin and performed sensory evaluation on the whitening state during drying according to the following criteria. The results are shown as the total score of the five panelists.

[0252] 5: Looks whitish.

[0253] 4: Doesn’t look too whitish.

[0254] 3: A portion looks slightly white.

[0255] 2: Some parts appear whitish.

[0256] 1: The overall appearance is whitish.

[0257] [Examples 1 to 14, Comparative Example 1]

[0258] Skin external preparation compositions (liquid form) having the compositions shown in Table 1 were prepared, and their wrinkle-improving effects, the thickness of the coating film after application and drying, and the whitening state during application and drying were evaluated.

[0259] (Manufacturing method)

[0260] The oil phase component in which the components (A), (B) and (C) are mixed is dispersed using a disperser and then stirred using a homomixer to obtain a composition for external use on skin.

[0261] [Table 1]

[0262]

[0263] In Table 1, *1 to *3 are as follows.

[0264] *1: A solid component obtained by drying under reduced pressure at 50°C for 12 hours "NBN-30-ID" manufactured by Shin-Etsu Chemical Co., Ltd. (an isododecane solution of a norbornene / tris(trimethylsiloxy)silylnorbornene) copolymer with e / f=60 / 40 (mol / mol) and Mn=360,000 in the following formula (6), with an active ingredient concentration of 30% by mass) was used.

[0265]

[0266] *2: A solid component obtained by drying under reduced pressure at 50° C. for 12 hours "TSPL-30-ID" (isododecane solution of tris(trimethylsiloxy)silylpropylcarbamate pullulan, active ingredient concentration: 30% by mass) manufactured by Shin-Etsu Chemical Co., Ltd. was used.

[0267] *3: A solid component obtained by drying "X21-5595" manufactured by Shin-Etsu Chemical Co., Ltd. (isododecane solution of trimethylsiloxysilicic acid, active ingredient concentration: 60% by mass) at 50° C. under reduced pressure for 12 hours was used.

[0268] [Examples 15 to 17]

[0269] In the same manner as in Examples 1 to 14, skin external preparation compositions having the compositions shown in Table 2 were prepared.

[0270] The obtained skin external preparation compositions were all able to improve wrinkles, had no uneven thickness of the coating film, and were able to suppress whitening during drying after application.

[0271] [Table 2]

[0272]

[0273] In Table 2, *4 means as follows.

[0274] *4: A solid component obtained by drying "XS66-B8226" (cyclopentasiloxane solution of trifluoropropyldimethyl / trimethylsiloxysilicic acid, active ingredient concentration: 50 mass %) manufactured by Momentive Performance Materials Japan LLC at 50°C under reduced pressure for 12 hours was used.

[0275] [Examples 18 to 19]

[0276] In the same manner as in Examples 1 to 14, skin external preparation compositions having the compositions shown in Table 3 were prepared.

[0277] The obtained skin external preparation compositions were all able to improve wrinkles, had no uneven thickness of the coating film, and were able to suppress whitening during drying after application.

[0278] [Table 3]

[0279]

[0280] [Example 20]

[0281] A skin external preparation composition (liquid form) having the composition of Example 1 shown in Table 1 was prepared and filled in a spray container. The skin external preparation composition was sprayed from the spray container onto the nasolabial folds and the surrounding areas of the face, and the wrinkle improvement effect after drying, the thickness of the coating film after application and drying, and the whitening state during application and drying were evaluated. As a result, a beautiful film with excellent wrinkle improvement effect, no uneven thickness of the coating film, and completely suppressed whitening was obtained.

Claims

1. A composition for external use on skin, wherein: The invention comprises the following components (A), (B) and (C), wherein the mass ratio (A) / (C) of the component (A) to the component (C) is 4.0 to 92.9, (A) 1 to 30% 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 based on a cylindrical mandrel method performed by the following method (2), the minimum diameter of a cylindrical mandrel on which cracks are not generated in a film of the polymer is 2 mm or more and 25 mm or less, Component (A) is a silicone-modified polynorbornene represented by the following formula (6), In the formula, e and f are the number of repeating units, and are each independently an integer greater than 1; Method (1): Prepare a 10 mass % hexamethyldisiloxane solution of the polymer; 0.005 g of the solution is spread over a width of 20 mm × a length of 100 mm × a thickness of The solution was applied on one side of a 0.03 mm polyethylene sheet from one end of the short side to the length direction in a range of 20 mm in width and 50 mm in length, and dried in a constant temperature bath set at 40° C. for 10 minutes; the length of the polyethylene sheet where the solution was applied was defined as L1, the length of the polyethylene sheet where the solution was deformed due to shrinkage after drying was defined as L2, and the value of L2 / L1 was defined as the deformation ratio; Method (2): preparing a 30 mass % hexamethyldisiloxane solution of the polymer; The solution was applied 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 dried in a thermostatic chamber set at 40° C. for 120 minutes to prepare a test piece; the test piece was subjected to a bending resistance test according to the cylindrical mandrel method specified in JIS K5600-5-1:1999, and the minimum diameter of the cylindrical mandrel that did not cause cracks on the polymer film on the test piece was determined; (B) a volatile oil having a volatility of 14% or more after drying at 40°C and 60% RH for 30 minutes under 1 standard atmosphere, Component (B) is at least one selected from isododecane, hexamethyldisiloxane, methylpolytrimethylsiloxane, and dimethylpolysiloxane having a kinematic viscosity of 2 cSt or less at 25°C; (C) Polyol.

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

3. The composition for external use on skin according to claim 1 or 2, wherein Component (C) is one or more selected from glycol, glycerin and sugar alcohol.

4. The composition for external use on skin according to claim 1 or 2, wherein The content of the component (C) is 0.1 to 20% by mass.

5. The composition for external use on skin according to claim 1 or 2, wherein The mass ratio (A) / (B) of the component (A) to the component (B) is 0.02 to 1.

6. The composition for external use on skin according to claim 1 or 2, wherein Furthermore, it contains (D) a surfactant.

7. The composition for external use on skin according to claim 1 or 2, wherein Furthermore, it contains non-volatile oil.

8. The composition for external use on skin according to claim 1 or 2, wherein Furthermore, it contains water.

9. The composition for external use on skin according to claim 1 or 2, wherein Regarding component (A), in formula (6), the ratio of e to f is e / f = 20 / 80 to 90 / 10 mol / mol.

10. Use of the composition for external application to skin according to any one of claims 1 to 9 for non-therapeutic purposes as an agent for improving skin wrinkles.

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