KR20210028664A - How to improve skin wrinkles - Google Patents

Abstract

A method for improving skin wrinkles, wherein a composition containing the following components (A) and (B) is applied to the skin. (A) As a polymer having a silicone structure, the strain ratio measured by the predetermined method (1) is 0.3 or more and 1 or less, and in the bending resistance test by the cylindrical mandrel method performed by the predetermined method (2), A polymer having a minimum diameter of 2 mm or more and 25 mm or less in a cylindrical mandrel that does not cause cracks in the polymer film (B) Volatile oil with a volatilization rate of 14% or more after drying for 30 minutes at 40°C and 60% RH under 1 atmosphere

Description

How to improve skin wrinkles

The present invention relates to a method for improving skin wrinkles.

As we age, people's skin has more wrinkles. This is part of the aging phenomenon of the skin and depends on a number of factors, such as changes in skin tissue and the effect of UV rays.

Although a technique for making the wrinkles of the skin inconspicuous has been proposed, in the method by cosmetic molding, it is necessary to control the shape by invading the skin. Skin care products that non-invasively improve skin wrinkles are also known, but the improvement effect is very low, and the satisfaction of women suffering from wrinkles has not been obtained.

Therefore, there is a need for a method capable of controlling the shape of the skin in a non-invasive manner and effectively improving wrinkles.

By the way, for the purpose of improving the uniformity of the cosmetic film and the maintenance of the cosmetic, cosmetic compositions containing a film-forming polymer are known. Patent Literature 1 relates to a cosmetic for makeup, which is formulated with a predetermined fructo-oligosaccharide fatty acid ester, a volatile hydrocarbon, and an oil-soluble film-forming resin, and has excellent applicability and uniformity of a cosmetic film. Patent Document 2 relates to a cosmetic composition containing a film-forming polymer in which a predetermined functional group is introduced into the skeleton of a polycycloolefin polymer, and having a good makeup oil and texture.

Japanese Patent Application Laid-Open No. 2008-247761 Japanese Unexamined Patent Publication No. 2012-17317

The present invention relates to the following [1] to [3].

[1] A method for improving skin wrinkles, wherein a composition containing the following component (A) and component (B) is applied to the skin.

(A) As a polymer having a silicone structure, the strain ratio measured by the following method (1) is 0.3 or more and 1 or less, and in the bending resistance test by the cylindrical mandrel method performed by the following method (2), Polymers with a minimum diameter of 2 mm or more and 25 mm or less of a cylindrical mandrel that does not cause cracks in the polymer film

Method (1): A 10 mass% hexamethyldisiloxane solution of the polymer is prepared. 0.005 g of the solution was applied to one side of a polyethylene sheet having a width of 20 mm × a length of 100 mm × a thickness of 0.03 mm, from one end of the short side toward the length direction, in a range of 20 mm in width × 50 mm in length, and set at 40°C. Dry for 10 minutes in a thermostat. The length of the polyethylene sheet coated with the solution is L1, the length of the polyethylene sheet deformed by shrinkage after drying is L2, and the value of L2/L1 is the strain ratio.

Method (2): A 30 mass% hexamethyldisiloxane solution of the polymer is prepared. The solution was applied to a polyethylene terephthalate film having a width of 50 mm × a length of 100 mm × a thickness of 0.1 mm using a 200 μm applicator, and dried for 120 minutes in a thermostat set at 40° C. to prepare a test piece. Using the test piece, a bending resistance test is performed in accordance with the cylindrical mandrel method specified in JIS K5600-5-1:1999, and the minimum diameter of the cylindrical mandrel in which cracks do not occur in the polymer film on the test piece is determined.

(B) Volatile oil having a volatilization rate of 14% or more after drying at 40° C., 60% R. H. for 30 minutes under 1 atm.

[2] A method for improving skin wrinkles, comprising a step of applying a composition containing the following components (A) and (B) to the periphery of the skin wrinkles, and then drying the composition to shrink the component (A) .

(A) As a polymer having a silicone structure, the strain ratio measured by the method (1) is 0.3 or more and 1 or less, and in the bending resistance test by the cylindrical mandrel method performed by the method (2), Polymers with a minimum diameter of 2 mm or more and 25 mm or less of a cylindrical mandrel that does not cause cracks in the polymer film

(B) Volatile oil having a volatilization rate of 14% or more after drying at 40° C., 60% R. H. for 30 minutes under 1 atm.

[3] A method of applying a composition containing the following component (A) and component (B) to the periphery of wrinkles on the skin.

(A) As a polymer having a silicone structure, the strain ratio measured by the method (1) is 0.3 or more and 1 or less, and in the bending resistance test by the cylindrical mandrel method performed by the method (2), Polymers with a minimum diameter of 2 mm or more and 25 mm or less of a cylindrical mandrel that does not cause cracks in the polymer film

(B) Volatile oil having a volatilization rate of 14% or more after drying at 40° C., 60% R. H. for 30 minutes under 1 atm.

1: is explanatory drawing of the evaluation method of the deformation ratio (L2/L1) of a polymer by method (1).
Fig. 2 is an example of a form in which the composition is applied to the skin of the periphery of wrinkles (nasolabial folds) in the form of a plane or band.
3 is an example of a form in which a composition is applied in a line shape to the skin of the periphery of wrinkles (nasolabial folds).
Fig. 4 is an example of a form in which a composition is applied in a dot shape to the skin of the periphery of wrinkles (nasolabial folds).
5 is a photograph showing the wrinkle-improving effect of Example 1. FIG.
6 is a photograph showing the wrinkle-improving effect of Comparative Example 2.

The present invention relates to a method for improving skin wrinkles by applying a composition containing the following component (A) and component (B) to the skin.

In addition, the present invention has a step of applying a composition containing the following component (A) and component (B) to the periphery of the wrinkles of the skin, and then drying the composition to shrink the component (A). It's about how to improve.

(A) As a polymer having a silicone structure, the strain ratio measured by the following method (1) is 0.3 or more and 1 or less, and in the bending resistance test by the cylindrical mandrel method performed by the following method (2), Polymers with a minimum diameter of 2 mm or more and 25 mm or less of a cylindrical mandrel that does not cause cracks in the polymer film

Method (1): A 10 mass% hexamethyldisiloxane solution of the polymer is prepared. 0.005 g of the solution was applied to one side of a polyethylene sheet having a width of 20 mm × a length of 100 mm × a thickness of 0.03 mm, from one end of the short side toward the length direction, in a range of 20 mm in width × 50 mm in length, and set at 40°C. Dry for 10 minutes in a thermostat. The length of the polyethylene sheet coated with the solution is L1, the length of the polyethylene sheet deformed by shrinkage after drying is L2, and the value of L2/L1 is the strain ratio.

Method (2): A 30 mass% hexamethyldisiloxane solution of the polymer is prepared. The solution was applied to a polyethylene terephthalate film having a width of 50 mm × a length of 100 mm × a thickness of 0.1 mm using a 200 μm applicator, and dried for 120 minutes in a thermostat set at 40° C. to prepare a test piece. Using the test piece, a bending resistance test is performed in accordance with the cylindrical mandrel method specified in JIS K5600-5-1:1999, and the minimum diameter of the cylindrical mandrel in which cracks do not occur in the polymer film on the test piece is determined.

(B) Volatile oil having a volatilization rate of 14% or more after drying for 30 minutes at 40°C and 50% R. H. under atmospheric pressure

Hereinafter, these methods are also referred to as "improving methods of the present invention" as appropriate.

Further, the present invention relates to a method of applying the composition containing the component (A) and the component (B) to the periphery of the wrinkles of the skin. Hereinafter, the method is appropriately referred to as "application method of the present invention".

In the present specification, "wrinkles on the skin" mean irregularities and wrinkles appearing on the skin surface. Wrinkles on the skin tend to appear around the mouth, around the eyes, forehead, and neck. Small wrinkles are small wrinkles, large wrinkles are large wrinkles, and large wrinkles occur in the flow of pores such as nasolabial folds and cheeks. The method of the present invention is preferable in that it exhibits an effect of making any wrinkles inconspicuous, and in particular, even large wrinkles such as nasolabial folds can be improved non-invasively.

The inventors of the present invention have a polymer having a silicone structure (hereinafter, also simply referred to as "component (A)"), which has the above-described predetermined strain ratio and bending resistance, and the predetermined volatile oil (hereinafter, also referred to simply as "component (B)"). It was found that by applying a composition containing) to the skin, the shape of the skin can be controlled non-invasively and wrinkles of the skin can be made inconspicuous.

In the present specification, the term "method for improving wrinkles on the skin" means that the skin around the wrinkles is stretched and stretched by the contraction action of the component (A) contained in the composition, as described later, and the shape of the skin is controlled non-invasively. That's how to do it. That is, a method of flattening the uneven shape of the skin surface by physically extending the wrinkles of the skin.For example, a method of filling the unevenness of the skin surface by applying a cosmetic or the like to the skin, or optically making the wrinkles inconspicuous; and Is a different concept.

<Component (A)>

The component (A) used in the present invention is a polymer having a silicone structure, and the deformation ratio measured by the following method (1) is 0.3 or more and 1 or less, and the cylindrical mandrel method performed by the following method (2). In the flexural resistance test by, the minimum diameter of the cylindrical mandrel in which cracks do not occur in the polymer film is 2 mm or more and 25 mm or less.

Method (1): A 10 mass% hexamethyldisiloxane solution of the polymer is prepared. 0.005 g of the solution was applied to one side of a polyethylene sheet having a width of 20 mm × a length of 100 mm × a thickness of 0.03 mm, from one end of the short side toward the length direction, in a range of 20 mm in width × 50 mm in length, and set at 40°C. Dry for 10 minutes in a thermostat. The length of the polyethylene sheet coated with the solution is L1, the length of the polyethylene sheet deformed by shrinkage after drying is L2, and the value of L2/L1 is the strain ratio.

Method (2): A 30 mass% hexamethyldisiloxane solution of the polymer is prepared. The solution was applied to a polyethylene terephthalate film having a width of 50 mm × a length of 100 mm × a thickness of 0.1 mm using a 200 μm applicator, and dried for 120 minutes in a thermostat set at 40° C. to prepare a test piece. Using the test piece, a bending resistance test is performed in accordance with the cylindrical mandrel method specified in JIS K5600-5-1:1999, and the minimum diameter of the cylindrical mandrel in which cracks do not occur in the polymer film on the test piece is determined.

When the component (A) satisfies the above-described deformation ratio measured by the method (1), for example, a composition containing the polymer as component (A) is applied to the skin around the wrinkles, etc., and then the composition is applied. When dried, the film containing the polymer shrinks and the skin surface in close contact with the film shrinks. Due to this action, the skin at the portion where wrinkles are occurring is stretched, so that the wrinkles can be made inconspicuous. Therefore, it is preferable that the improvement method of the present invention has a step of applying the composition to the periphery of the wrinkles of the skin, and then a step of shrinking the component (A) by drying the composition.

A method of evaluating the deformation ratio (L2/L1) of the component (A) by the method (1) will be described with reference to FIG. 1. First, a 10 mass% hexamethyldisiloxane solution of the component (A) used in the composition is prepared. One end of the short side of the polyethylene sheet 1 on one side of the polyethylene sheet 1 having a width (W) of 20 mm × a length (L0) of 100 mm × a thickness of 0.03 mm in which 0.005 g of this solution is shown in FIG. 1(a) From (1a) toward the longitudinal direction, it is applied to a range of 20 mm in width x 50 mm in length (part 2 shown in Fig. 1(a)), and dried in a thermostat set at 40°C for 10 minutes. Fig. 1(b) is a schematic diagram of a polyethylene sheet that is partially deformed (curled) by shrinkage of a polymer, which is a component (A), after drying the polyethylene sheet 1 to which the above solution has been applied.

In the dried polyethylene sheet (Fig. 1(b)), the length of the polyethylene sheet at the portion coated with the solution is L1 (50 mm), the length of the polyethylene sheet at the portion deformed by shrinkage after drying is L2, and L2 /L1 is calculated, and this value is taken as the deformation ratio. L2 is taken as the average of the values measured on the two long sides of the polyethylene sheet 1. The larger the value of L2/L1 is, the larger the shrinkage of the polymer due to drying is, and the upper limit of L2/L1 is 1.

From the viewpoint of elongating the wrinkles of the skin so that it is not conspicuous, the deformation ratio L2/L1 evaluated by the method (1) of the component (A) is 0.3 or more, preferably 0.5 or more, more preferably 0.6 It is more, 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, even more preferably 0.95 or more, and the upper limit is 1.

The said transformation ratio can be specifically evaluated by the method described in an Example.

In addition, component (A) is excellent in bending resistance, and in the bending resistance test by the cylindrical mandrel method carried out by the method (2), the minimum of the cylindrical mandrel in which cracks do not occur in the polymer film as component (A). The diameter is 2 mm or more and 25 mm or less. Thereby, the film formed by the composition containing the component (A) does not easily crack, and it becomes easy to shrink in a state that follows the shape of the skin.

The smaller the minimum diameter of the cylindrical mandrel is, the better the bending resistance is. From the viewpoint of obtaining sufficient adhesion between the film and the skin surface when the film containing the polymer shrinks, the minimum diameter is 25 mm or less, preferably 20 mm or less, more preferably 12 mm or less, even more preferably It is 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 elongate the wrinkles of the skin and make it inconspicuous, the minimum diameter of the cylindrical mandrel in which cracks do not occur is preferably 2 mm or more, more preferably It is 3 mm or more. The specific range of the minimum diameter of the cylindrical mandrel is preferably 2 to 25 mm, more preferably 2 to 20 mm, still more preferably 2 to 12 mm, even more preferably 2 to 8 mm, even more preferably It is preferably 3 to 6 mm, and even more preferably 3 to 5 mm.

The bending resistance can be specifically evaluated by the method described in Examples using a type 1 bending test apparatus specified in JIS K5600-5-1:1999.

In addition, the ratio of the deformation ratio obtained by the method (1) to the minimum diameter (mm) of the mandrel obtained by the method (2) of the component (A) [(strain ratio)/(minimum of the mandrel Diameter)] is preferably 0.01 or more, more preferably 0.02 or more, still more preferably 0.10 or more, even more preferably 0.15 or more, from the viewpoint of the effect of improving wrinkles on the skin. From the viewpoint of imparting sufficient strength and shape control effect in order not to stand out, it is preferably 0.5 or less, and more preferably 0.4 or less. The specific range of the ratio is preferably 0.01 to 0.5, more preferably 0.02 to 0.5, still more preferably 0.10 to 0.5, even more preferably 0.15 to 0.5, and even more preferably 0.15 to 0.4.

In this specification, the "silicon structure" refers to a structure represented by the following general formula (I).

[Formula 1]

In General Formula (I), R ¹ is each independently a hydrocarbon group having 1 or more and 12 or less carbon atoms, and p is an integer of 1 or more. ^{When applied to the present invention, R 1} is preferably from the viewpoint of elongating the wrinkles of the skin to make it inconspicuous, thereby obtaining a sufficient wrinkle improvement effect (hereinafter, also referred to as ``the wrinkle improvement effect of the skin'') and versatility. An alkyl group having 1 or more and 12 or less carbon atoms or an aryl group having 6 or more and 12 or less carbon atoms, more preferably an alkyl group or phenyl group having 1 or more and 12 or less carbon atoms, more preferably an alkyl group having 1 or more and 3 or less carbon atoms, and even more preferably a methyl group to be.

The polymer which is the component (A) may have a silicone structure or may be a polymer consisting only of a silicone structure, but from the viewpoint of making a polymer having the above-described properties, it is preferable that it is a polymer having a silicone structure in part.

In the case of a polymer having a silicone structure in part, the silicone structure may be present in either the main chain or the side chain among the polymers, and from the viewpoint of making a polymer having the prescribed properties, it is preferably present in the side chain. .

When the silicone structure is present in the polymer main chain, there is no particular limitation on its bonding form, for example, the silicone structure may be present at the end of the polymer main chain, and the silicone structure in the polymer main chain is in a block or random form. It may be a copolymerized polymer bonded together. In addition, a polymer graft-modified by a compound having a silicone structure can also be used.

The component (A) used in the present invention is preferably a silicone-modified polymer, and specific examples thereof include silicone-modified silicone-modified polymers containing a norbornane structure such as silicone-modified polynorbornene; Silicon-modified pullulan; Silicone structure-containing silicic acid compounds such as trialkylsiloxysilicic acid, fluorine-modified alkylsiloxysilicic acid, and phenyl-modified alkylsiloxysilicic acid; Silicon dendrimer; And the like.

(Silicon modified polymer containing norbornane structure)

In this specification, the norbornane structure means a structure represented by the following formula. The norbornane structure-containing silicone-modified polymer may be a silicone-modified polymer having a structure represented by the formula at an arbitrary site in the polymer.

[Formula 2]

As the norbornane structure-containing silicone-modified polymer, a polymer having a repeating unit represented by the following general formula (1) or (2) can be mentioned.

[Formula 3]

In the formula, R ² is each independently an alkyl group having 1 or more and 12 or less carbon atoms, and X is a group represented by the following formula (i). a is an integer of 1 or more and 3 or less, and b is an integer of 0 or more and 2 or less.

[Formula 4]

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

[Formula 5]

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.

In the general formula (1), R ² is each independently an alkyl group having 1 or more and 12 or less carbon atoms, and from the viewpoint of skin wrinkle improvement effect and versatility, methyl group, ethyl group, n-propyl group, butyl group, or pentyl A group is preferable and a methyl group is more preferable.

X is a group represented by the above formula (i), and in formula (i), R ¹ is each independently a hydrocarbon group having 1 or more and 12 or less carbon atoms. From the viewpoint of skin wrinkle improvement effect and versatility, R ¹ is preferably an alkyl group having 1 or more and 12 or less carbon atoms or an aryl group having 6 or more and 12 or less carbon atoms, and more preferably an alkyl group or phenyl group having 1 or more and 12 or less carbon atoms. , More preferably, it is a C1-C3 alkyl group, More preferably, it is a methyl group. c is an integer of 1 or more and 5 or less, and c=1 is preferable from the viewpoint of versatility. That is, X is preferably a trimethylsiloxy group.

a is an integer of 1 or more and 3 or less, and may be a polymer in which a repeating unit of a = 2 and a repeating unit of a = 3 are mixed and present, for example. From the viewpoint of versatility, a is preferably 3. b is an integer of 0 or more and 2 or less, from the same viewpoint, preferably 0, 1 or a combination thereof, and 0 is more preferable.

In the general formula (2), R ¹ , R ² and b are the same as described above. d is an integer of 2 or more and 5 or less, and d = 2 is preferable from the viewpoint of versatility. As for the cyclic silicone structure in General Formula (2) ^{, it is preferable that R 1} and R ² are methyl groups and d is 2 or 3 from the same viewpoint. That is, the cyclic silicone structure in the general formula (2) is preferably a structure represented by the following formula (4) or (5).

[Formula 6]

From the viewpoint of the effect of improving wrinkles on the skin, the ratio of the repeating unit represented by the general formula (1) or (2) in the norbornane structure-containing silicone modified polymer is, preferably, 10% of the total number of repeating units in the polymer. It is above, more preferably, it is 30% or more, and still more preferably, it is 50% or more. Moreover, the upper limit is 100%, Preferably it is 95% or less, More preferably, it is 90% or less, More preferably, it is 70% or less. The specific range of the number of repeating units represented by the general formula (1) or (2) in the silicone-modified norbornane structure-containing polymer is preferably 10 to 100%, more preferably, of the total number of repeating units in the polymer. It is 10 to 95%, More preferably, it is 30 to 90%, More preferably, it is 50 to 70%.

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).

[Formula 7]

In the formula, R ³ to R ⁶ are each independently selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, and a halogenated hydrocarbon group. A substituent or an oxetanyl group, an alkoxycarbonyl group, a polyoxyalkylene group, a polyglyceryl group, or an alkoxysilyl group. Two groups selected from R ³ to R ^{6 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 above.

The ratio of the repeating units represented by the general formula (3) in the norbornane structure-containing silicone-modified polymer is preferably 90% or less, more preferably 90% or less of the total number of repeating units in the polymer from the viewpoint of the effect of improving wrinkles on the skin. It is preferably 70% or less, more preferably 50% or less. 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, still more preferably 30% of the total number of repeating units in the polymer. That's it. The specific range of the number of repeating units represented by the general formula (3) in the norbornane structure-containing silicone-modified polymer is preferably 5 to 90%, more preferably 10 to 70% of the total number of repeating units in the polymer. , More preferably, it is 30 to 50%.

The ratio of the repeating units represented by the general formulas (1) to (3) in the norbornane structure-containing silicone-modified polymer ^{can be determined by 1} H-NMR measurement.

As the norbornane structure-containing silicone-modified polymer, silicone-modified polynorbornene is preferred, and more preferably silicone-modified polynorbornene represented by the following formula (6).

[Formula 8]

In the formula, e and f are the number of repeating units, each independently an integer of 1 or more.

From the viewpoint of the effect of improving wrinkles on the skin, the ratio of e and f in the general formula (6) is preferably e/f = 20/80 to 90/10 (mol/mol), more preferably 30/70 to It is 80/20 (mol/mol), More preferably, it is 50/50-70/30 (mol/mol).

The number average molecular weight Mn of the norbornane structure-containing silicone-modified polymer is preferably 50,000 or more, more preferably 100,000 or more, and even more preferably from the viewpoint of achieving both shrinkage and bending resistance, and from the viewpoint of the effect of improving wrinkles on the skin. Preferably it is 200,000 or more, preferably 2 million or less, more preferably 1.5 million or less, still more preferably 800,000 or less, and even more preferably 600,000 or less. The specific range of the number average molecular weight Mn of the norbornane structure-containing silicone-modified polymer is preferably 50,000 to 2 million, more preferably 100,000 to 1.5 million, still more preferably 200,000 to 800,000, even more preferably It is between 200,000 and 600,000.

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

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

For example, if it is a norbornane structure-containing silicone-modified polymer having a repeating unit represented by the general formula (1) or (2), it is obtained by addition polymerization of a cyclic olefin monomer represented by the following general formula (1a) or (2a). I can. Further, you may copolymerize a cyclic olefin monomer represented by the following general formula (3a).

[Formula 9]

In the formula, R ¹ is each independently an alkyl group having 1 or more and 12 or less carbon atoms, and X is a group represented by the following formula (i). a is an integer of 1 or more and 3 or less, and b is an integer of 0 or more and 2 or less.

[Formula 10]

In the formula, R ² is each independently a hydrocarbon group having 1 or more and 12 or less carbon atoms, and c is an integer of 1 or more and 5 or less.

[Formula 11]

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.

[Formula 12]

In the formula, R ³ to R ⁶ are each independently selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, and a halogenated hydrocarbon group. A substituent or an oxetanyl group, an alkoxycarbonyl group, a polyoxyalkylene group, a polyglyceryl group, or an alkoxysilyl group. Two groups selected from R ³ to R ^{6 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 above.

When copolymerizing the cyclic olefin monomer represented by the general formula (3a), the amount used is 100 mol%, preferably 90 mol% or less, of the total monomers used for polymerization from the viewpoint of the effect of improving wrinkles on the skin. , More preferably 70 mol% or less, still more preferably 50 mol% or less, and preferably 5 mol% or more, more preferably 10 mol% or more, still more preferably 30 mol% or more.

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

[Formula 13]

From the viewpoint of the effect of improving wrinkles on the skin, the copolymerization ratio of tris(trimethylsiloxy)silylnorbornene and norbornene is preferably 20/80 to 90/10 (mol/mol), more preferably 30 It is /70 to 80/20 (mol/mol), More preferably, it is 50/50 to 70/30 (mol/mol).

In addition, the repeating units represented in the general formulas (1) to (3) and the formula (6) all represent the 2,3-additional structural units of the cyclic olefin monomer as a raw material monomer, but the cyclic olefin It may contain a 2,7-additional structural unit by addition polymerization of a monomer.

The norbornane structure-containing silicone-modified polymer is preferably a norbornene/tris(trimethylsiloxy)silylnorbornene) copolymer, and the name of INCI (International Cosmetic Ingredient Dictionary and Handbook, 16th Edition, Volume 2, 2016, p. 2274): It is a compound denoted as NORBORNENE/TRIS(TRIMETHYLSILOXY)SILYLNORBORNENE COPOLYMER.

As a commercially available silicone-modified polymer containing a norbornane structure, Shin-Etsu Chemical Co., Ltd. ``NBN-30-ID'' (norbornene/tris(trimethylsiloxy)silylnorbornene) copolymer isododecane solution ) And the like.

(Silicone Modified Pullulan)

Examples of the silicone-modified pullulan include pullulan having a silicone structure in the side chain. Specifically, from the viewpoint of the wrinkle improvement effect and versatility of the skin, at least part of the hydrogen atoms of the OH group in the pullulan are Silicon-modified pullulan substituted with a group represented by the following general formula (7) is preferable.

[Formula 14]

In the formula, Z ¹ is a single bond or a divalent organic group. R 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.

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 is represented by the following general formula (9). A divalent group is more preferable.

[Formula 15]

In the formula, R ¹¹ is an alkylene group having 1 or more and 10 or less carbon atoms, and a methylene group, an ethylene group, a trimethylene group, a propylene group, a butylene group, and the like are exemplified. From the same viewpoint, among these, an ethylene group, a trimethylene group, and a propylene group are preferable, and a trimethylene group or a propylene group is more preferable.

As a commercially available silicone-modified pullulan, Shin-Etsu Chemical Co., Ltd. ``TSPL-30-ID'' (tri(trimethylsiloxy)silylpropylcarbamic acid pullulan isododecane solution), ``TSPL-30- D5" (cyclopentasiloxane solution of pullulan of tri(trimethylsiloxy)silylpropylcarbamic acid), etc. are mentioned.

(Silicone structure containing silicic acid compound)

As the silicone structure-containing silicic acid compound used in the present invention, a silicate compound having a silicone structure at the terminal is exemplified, for example, trialkylsiloxysilicic acid, fluorine-modified alkylsiloxysilicic acid, phenyl-modified alkylsiloxysilicic acid, etc. Can be mentioned.

The alkyl group in the trialkylsiloxysilicic acid is preferably a carbon number of 1 or more and 10 or less, more preferably a carbon number of 1 or more and 4 or less, and still more preferably a methyl group from the viewpoint of skin wrinkle improvement effect and versatility. . As a specific example of trialkylsiloxysilicic acid, trimethylsiloxysilicic acid can be mentioned.

Examples of the fluorine-modified alkylsiloxysilicic acid include compounds in which at least a part of the hydrogen atoms of the alkyl group in the trialkylsiloxysilicic acid are substituted with a fluorine atom. As a specific example, trifluoropropyldimethylsiloxysilicic acid, trifluoropropyldimethyl/trimethylsiloxysilicic acid, etc. are mentioned.

As phenyl-modified alkylsiloxysilicic acid, phenylpropyldimethylsiloxysilicic acid, phenylpropyldimethyl/trimethylsiloxysilicic acid, etc. are mentioned, for example.

Among the silicone structure-containing silicic acid compounds, one or more selected from the group consisting of trialkylsiloxysilicic acid and fluorine-modified alkylsiloxysilicic acid is preferable from the viewpoint of the effect of improving wrinkles on the skin.

As commercially available silicic acid compounds containing a silicon structure, Shin-Etsu Chemical Industries Co., Ltd. "KF-7312J", "KF-7312K", "KF-7312T", "KF-7312L", "X-21-5249", and " X-21-5250", "KF-9021", "X-21-5595", "X-21-5616", "KF-9021L", "X-21-5249L", "X-21-5250L" Trimethylsiloxysilicic acid (solution) such as, Momentive Performance Materials Japan joint company ``XS66-B8226'' (a cyclopentasiloxane solution of trifluoropropyldimethyl/trimethylsiloxysilicic acid), ``XS66-B8636 "(Dimethicone solution of trifluoropropyldimethyl/trimethylsiloxysilicic acid), "SilShine151" (phenylpropyldimethylsiloxysilicic acid), and the like can be used.

(Silicon Dendrimer)

Examples of the silicone dendrimer include vinyl polymers having a siloxane dendrimer structure in the side chain. It is preferable that the siloxane dendrimer structure is a group specifically represented by the following general formula (10) from the viewpoint of the wrinkle improvement effect of the skin and the viewpoint of versatility.

[Formula 16]

In the formula, R ¹ is the same as above. Z ² is a single bond or a divalent organic group. X 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 representing the hierarchy of the group.

[Formula 17]

In the formula, R ¹ is the same as above, and R ¹² is an alkyl group having 1 or more and 10 or less carbon atoms. Z ³ is an alkylene group having 2 or more and 10 or less carbon atoms. X ^{i + 1} is a hydrogen atom, an alkyl group having 1 or more and 10 or less carbon atoms, an aryl group, or a group represented by the general formula (11), and a ⁱ is an integer of 0 or more and 3 or less.

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

[Formula 18]

In the formula, R ¹³ is an alkylene group having 1 or more and 10 or less carbon atoms, and methylene group, ethylene group, trimethylene group, propylene group, butylene group and the like are exemplified, and from the viewpoint of versatility, ethylene group, trimethylene group, or propylene Group is preferred. R ¹⁴ is an alkyl group having 1 or more and 10 or less carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, and a butyl group, and from the same viewpoint, a methyl group is preferable. R ¹⁵ is an alkylene group having 1 or more and 10 or less carbon atoms, methylene group, ethylene group, trimethylene group, propylene group, butylene group and the like are exemplified, and from the same viewpoint, an ethylene group is preferable. q is an integer of 0 or more and 4 or less, and r is 0 or 1.

Examples of the vinyl polymer having the above-described siloxane dendrimer structure in the side chain (hereinafter, also simply referred to as "vinyl polymer") include polymers having repeating units derived from monomers represented by the following general formula (15).

[Formula 19]

In the formula, R ¹ and X ¹ are the same as above. Y is a group containing a vinyl bond, for example, a vinyl group, 2-acryloyloxyethyl group, 3-acryloyloxypropyl group, 2-methacryloyloxyethyl group, 3-methacryloyloxy Propyl 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) ) An ethyl group, an allyl group, and a 5-hexenyl group are mentioned. Among these, from the viewpoint of versatility, preferably a (meth)acryloyl group or a vinyl group, and more preferably a (meth)acryloyl group.

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-based monomer is a monomer other than the monomer having a group containing a vinyl bond and represented by the general formula (15), for example, (meth)acrylic acid, alkyl (meth)acrylate, hydroxyalkyl (meth) ) Acrylate, aromatic ring-containing (meth)acrylate, fatty acid vinyl ester, (meth)acrylamide, styrene or derivatives thereof, and the like, and one or two or more of them may be used. Among these, from the viewpoint of versatility, (meth)acrylic monomers such as (meth)acrylic acid, alkyl (meth)acrylate, hydroxyalkyl (meth)acrylate, and aromatic ring-containing (meth)acrylate are preferable.

In the vinyl polymer, the content of the repeating unit derived from the monomer represented by the general formula (15) is preferably 0.1% by mass or more with respect to the total repeating units in the vinyl polymer, from the viewpoint of the effect of improving wrinkles on the skin, More preferably, it is 10 mass% or more, More preferably, it is 20 mass% or more. In addition, the upper limit is 100 mass%.

It is more preferable that the said vinyl polymer is an acrylic polymer. That is, a preferable silicone dendrimer is an acrylic polymer having a siloxane dendrimer structure in the 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 is derived from a (meth)acrylic monomer other than the monomer represented by the general formula (15). You may further include a repeating unit.

As commercially available silicone dendrimers, Toray Dow Corning Co., Ltd. ``FA 4001 CM Silicone Acrylate'' (cyclopentasiloxane solution of acrylate-polytrimethylsiloxymethacrylate copolymer), ``FA 4002 ID Silicone Acrylate'' ( Acrylic silicon dendrimers, such as an isododecane solution of an acrylate-polytrimethylsiloxy methacrylate copolymer), are mentioned.

Among the above polymers, from the viewpoint of the effect of improving skin wrinkles, it is selected from the group consisting of silicone-modified polynorbornene, silicone-modified pullulan, trimethylsiloxysilicic acid, trifluoropropyldimethyl/trimethylsiloxysilicic acid, and acrylsilicone dendrimer. At least one selected from the group consisting of silicone-modified polynorbornene, silicone-modified pullulan, trimethylsiloxysilicic acid, and trifluoropropyldimethyl/trimethylsiloxysilicic acid is more preferred, From the viewpoint of the anti-wrinkle effect and bending resistance of the skin, at least one selected from the group consisting of silicone-modified polynorbornene and silicone-modified pullulan is more preferred, and silicone-modified polynorbornene is even more preferred.

The content of the component (A) in the composition used in the present invention is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1% by mass or more, from the viewpoint of the effect of improving wrinkles on the skin, Even more preferably, it is 5 mass% or more. In addition, the content of the component (A) in the composition is preferably 30% by mass or less, more preferably 25% by mass or less, from the viewpoint of not giving a feeling of discomfort to the skin after drying, and coating properties of the composition, freedom of prescription, and , More preferably, it is 20 mass% or less, Even more preferably, it is 15 mass% or less. The specific range of the content of the component (A) in the composition is preferably 0.1 to 30 mass%, more preferably 0.5 to 25 mass%, still more preferably 1 to 20 mass%, even more preferably 1 to 15 It is mass %, More preferably, it is 5 to 15 mass %.

<Component (B)>

The composition used in the present invention contains, as component (B), a volatile oil having a volatilization rate of 14% or more after drying for 30 minutes at 40° C. and 60% RH under 1 atmosphere pressure from the viewpoint of enhancing the effect of improving wrinkles on the skin. . When the component (B) is contained, the drying rate of the composition containing the component (A) is improved, thereby accelerating the contraction of the component (A) in the drying process, thereby elongating the wrinkles of the skin by the aforementioned mechanism. The effect of making it inconspicuous is more improved.

From the viewpoint of obtaining the above effect, the component (B) has a volatilization rate after drying for 30 minutes at 40° C. and 60% RH under 1 atmosphere, preferably 18% or more, more preferably 25% or more, further preferably Is 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. In addition, the upper limit is 100%.

The volatilization rate of the component (B) was obtained by placing 0.5 g of a sample in a glass chalet having a diameter of 40 mm, allowing it to stand at 40°C for 30 minutes under an atmosphere of 60% RH under 1 atmosphere, and dried, and the sample before drying. Assuming that the mass is W ₀ (g) and the mass of the sample after drying is W ₁ (g), it is determined as a value of _{{(W 0} -W ₁ )/W _{0 }×100.} The larger this value, the faster the volatilization rate, which means that it is easier to dry.

Moreover, you may use 2 or more types of volatile oils as a component (B).

Specifically, the volatilization rate can be measured by the method described in Examples.

Preferred specific examples of the component (B) include an oil agent having at least one selected from the group consisting of hydrocarbon oils and silicone oils, and having a volatilization rate within the above range from the viewpoint of enhancing the effect of improving wrinkles on the skin. Among these, 1 selected from the group consisting of isododecane (volatility 33%), hexamethyldisiloxane (volatility 100%), methyltrimethicone, and dimethylpolysiloxane having a kinematic viscosity at 25°C of 2 cSt or less. More than a species is preferable. Further, the kinematic viscosity can be measured using, for example, an Uberode viscometer.

From the viewpoint of enhancing the effect of improving wrinkles on the skin, component (B) is more preferably 1 selected from the group consisting of isododecane, hexamethyldisiloxane, and dimethylpolysiloxane having a kinematic viscosity at 25° C. of 1.5 cSt or less. And more preferably hexamethyldisiloxane, and at least one selected from the group consisting of dimethylpolysiloxane having a kinematic viscosity at 25° C. of 1 cSt or less, and even more preferably hexamethyldisiloxane.

As commercial products of hexamethyldisiloxane and dimethylpolysiloxane having a kinematic viscosity of 2 cSt or less at 25°C, "KF-96L-0.65cs" (hexamethyldisiloxane) manufactured by Shin-Etsu Chemical Co., Ltd., and "TMF1. 5", "KF-96L-1cs" (octamethyltrisiloxane), "KF-96L-1.5cs", "KF-96L-2cs", "SH200C Fluid 1cs" manufactured by Toray Dow Corning, " SH200C Fluid 1.5cs", "TSF451-0.65" manufactured by Momentive Performance Materials Japan Joint Stock Company, "BELSIL DM0.65" manufactured by Asahi Kasei Barker Silicone Co., Ltd., and the like.

The content of the component (B) in the composition used in the present invention is preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more from the viewpoint of enhancing the effect of improving skin wrinkles. , Even more preferably 20% by mass or more, even more preferably 25% by mass or more, even more preferably 35% by mass or more, even more preferably 45% by mass or more, even more preferably 50% by mass or more , Even more preferably 60% by mass or more, even more preferably 70% by mass or more, even more preferably 80% by mass or more, and from the viewpoint of enhancing the wrinkle-improving effect of the skin and the degree of freedom of prescription, preferably Is 99.9% by mass or less, more preferably 99.5% by mass or less, still more preferably 99% by mass or less, even more preferably 97% by mass or less, and even more preferably 95% by mass or less. The specific range of the content of the component (B) in the composition is preferably 1 to 99.9 mass%, more preferably 5 to 99.9 mass%, still more preferably 5 to 99.5 mass%, even more preferably 10 to 99.5. Mass%, still more preferably 20 to 99.5 mass%, even more preferably 25 to 99.5 mass%, still more preferably 35 to 99.5 mass%, still more preferably 35 to 99 mass%, even more preferably Preferably, 45 to 99% by mass, even more preferably 50 to 99% by mass, even more preferably 60 to 99% by mass, even more preferably 70 to 99% by mass, even more preferably 80 to 99% by mass %, even more preferably 80 to 97 mass%, even more preferably 80 to 95 mass%.

In addition, from the viewpoint of enhancing the effect of improving wrinkles on the skin, the product of the product of the volatilization rate (%) of the component (B) and the content (mass%) of the component (B) in the composition is divided by 100 [Volatilization rate (%) × content (Mass%)/100] is preferably 5 or more, preferably 20 or more, preferably 35 or more, more preferably 40 or more, even more preferably 45 or more, still more preferably 60 or more, more More preferably, it is 70 or more. [Volatilization (%) x content (mass%)/100] is preferably 99.9 or less.

<Other ingredients>

In addition to the above components, the composition used in the present invention may appropriately contain other components conventionally blended in cosmetics or the like within a range that does not impair the object of the present invention. Examples of such components include surfactants, water-soluble polymers, antioxidants, ultraviolet absorbers, vitamins, preservatives, pH adjusters, fragrances, plant extracts, moisturizers, coloring agents, cooling agents, restrictors, fungicides, skin activators, etc. Can be mentioned.

The form of the composition used in the present invention may be a form applicable to the skin by application or the like, and examples thereof include forms such as solutions, emulsions, creams, lotions, gels, packs, sheets, and foams.

The composition used in the present invention is preferably liquid when applied to the skin from the viewpoint of exerting an effect of reducing wrinkles on the skin by shrinking the component (A) by applying it to the skin and then drying the composition. And it is more preferable that it is liquid in 25 degreeC.

In addition, the composition used in the present invention is applied by applying it to the skin, and then, from the viewpoint of accelerating the contraction of the component (A) in the step of drying the composition, thereby enhancing the effect of improving the wrinkles of the skin, the content of water is low. It is desirable. The content of water in the composition is preferably 15% by mass or less, more preferably 10% by mass or less, still more preferably 5% by mass or less, even more preferably 2% by mass or less, and even more preferably 1% by mass. % Or less, even more preferably 0.5% by mass or less, and even more preferably 0.1% by mass or less.

In the skin wrinkle improvement method of the present invention, specifically, it is preferable to apply the composition by applying the composition to the periphery of the skin wrinkles or the like.

In addition, in the application method of the present invention, it is applied by, for example, applying the composition to the periphery of wrinkles. According to the application method, the shape of the skin can be controlled non-invasively by the above-described action mechanism, and wrinkles of the skin can be made inconspicuous.

In the present specification, "the periphery of the wrinkle of the skin" is distinguished from the inside of the wrinkle, that is, the concave portion of the skin surface or the concave portion of the wrinkle. In the present invention, by applying the composition to the skin around the wrinkles, when the composition is dried, the film containing the component (A) contracts and the skin surface around the wrinkles contracts, and the skin in the area causing the wrinkles is stretched. It means that the wrinkles become inconspicuous. In addition, in the improvement method of the present invention and the application method of the present invention, as long as the effect of the present invention is obtained, the composition is not limited only to the periphery of the wrinkles of the skin and does not interfere with application to the inside of the wrinkles.

From the viewpoint of obtaining the above effect, it is preferable to include at least a part of a region intersecting the direction of the wrinkle as a region to which the composition is applied among the wrinkles periphery. The direction of wrinkles refers to the direction in which the wrinkles are stretched. This is because by applying the composition to an area that intersects the direction of the wrinkles, the skin in the area where the wrinkles are occurring is stretched and the wrinkles become inconspicuous.

As the area intersecting with the direction of the wrinkle, it is preferable that it is a region along the direction of the wrinkle, and the region may be only one side or both sides of the wrinkle. In particular, it is more preferable to apply the composition to both sides with the wrinkles interposed therebetween. This is because the wrinkles can be made more inconspicuous by stretching the skin of the wrinkle-producing portion from both sides of the wrinkle.

As a form of applying the composition to an area along the direction of wrinkles, for example, a form in which the composition is applied to the area in a plane, strip, line, or dot form, and specifically, FIG. 2 to be described later. The form shown in-FIG. 4 can be illustrated.

In addition, when the direction of the wrinkles is not parallel to the direction of gravity, such as, for example, nasolabial folds, it is preferable that the area to which the composition is applied (the area intersecting the direction of the wrinkles) includes the area on the upper side of the wrinkles. Do. The term "gravity direction" as used herein refers to a direction in which gravity acts when a person is standing upright, and the term "upper side" refers to a direction opposite to the direction of gravity. By applying the composition to at least the area on the upper side of the wrinkles, the skin of the area causing the wrinkles is stretched upward, so that the wrinkles can be made more inconspicuous. From the same point of view as above, when the direction of the wrinkles is not parallel to the direction of gravity, the area to which the composition is applied is the upper and lower regions with the wrinkles interposed therebetween, and the upper region of the wrinkles is It is more preferable that it is a wider range than the lower region.

An example of the form in which the composition is applied in the method of the present invention is shown in FIGS. 2 to 4.

Figure 2 is a form in which the composition is applied to the skin of the periphery of wrinkles (nasolabial folds) in a plane or band, Figure 2(a) is an area on the upper side of wrinkles, and Figure 2(b)(c) is The composition was applied to the upper and lower regions, respectively. From the viewpoint of making the wrinkles less conspicuous, as shown in Fig. 2(c), the area to which the composition is applied is the upper and lower regions with the wrinkles interposed therebetween, and the upper region of the wrinkle is the lower region of the wrinkle. A wider one is more preferable.

Fig. 3(a)(b)(c) is a form in which the composition is applied in a line to the skin around the wrinkles (nasolabial folds), and Fig. 4(a)(b) is the skin around the wrinkles (nasolabial folds). It is a form in which the composition is applied in a dot shape. As shown in Figs. 3 and 4, even when the composition is applied in a line or dot shape, from the viewpoint of evenly stretching the skin from both sides of the wrinkles, the composition is applied to the upper and lower regions between the wrinkles. It is desirable.

In the application method of the present invention, the amount of the composition used is not particularly limited as long as it can exhibit the effect of making wrinkles inconspicuous, but for nasolabial folds, for example, 0.01 g or more and 10 g or less to be.

In the application method of the present invention, it is preferable to have a step of applying the composition to the periphery of the wrinkles of the skin and applying it, and then drying the composition to shrink the component (A). By the drying, the component (A) in the composition applied to the skin contracts, and this contraction action stretches and stretches the skin around the wrinkles, thereby flattening the uneven shape of the skin surface, and furthermore, the wrinkles are not conspicuous. It exerts an effect that prevents it.

After drying, you may remove the said composition as needed. Alternatively, the composition may be applied to the skin and then dried, and then makeup may be applied from above without removing the composition.

Regarding the above-described embodiments, the present invention further discloses the following embodiments.

<1>

A method for improving skin wrinkles, wherein a composition containing the following components (A) and (B) is applied to the skin.

(A) As a polymer having a silicone structure, the strain ratio measured by the following method (1) is 0.3 or more and 1 or less, and in the bending resistance test by the cylindrical mandrel method performed by the following method (2), Polymers with a minimum diameter of 2 mm or more and 25 mm or less of a cylindrical mandrel that does not cause cracks in the polymer film

Method (1): A 10 mass% hexamethyldisiloxane solution of the polymer is prepared. 0.005 g of the solution was applied to one side of a polyethylene sheet having a width of 20 mm × a length of 100 mm × a thickness of 0.03 mm, from one end of the short side toward the length direction, in a range of 20 mm in width × 50 mm in length, and set at 40°C. Dry for 10 minutes in a thermostat. The length of the polyethylene sheet coated with the solution is L1, the length of the polyethylene sheet deformed by shrinkage after drying is L2, and the value of L2/L1 is the strain ratio.

Method (2): A 30 mass% hexamethyldisiloxane solution of the polymer is prepared. The solution was applied to a polyethylene terephthalate film having a width of 50 mm × a length of 100 mm × a thickness of 0.1 mm using a 200 μm applicator, and dried for 120 minutes in a thermostat set at 40° C. to prepare a test piece. Using the test piece, a bending resistance test is performed in accordance with the cylindrical mandrel method specified in JIS K5600-5-1:1999, and the minimum diameter of the cylindrical mandrel in which cracks do not occur in the polymer film on the test piece is determined.

(B) Volatile oil having a volatilization rate of 14% or more after drying at 40° C., 60% R. H. for 30 minutes under 1 atm.

<2>

A method for improving skin wrinkles, comprising a step of applying a composition containing the following components (A) and (B) to the periphery of the skin wrinkles, and then drying the composition to shrink the component (A).

(A) As a polymer having a silicone structure, the strain ratio measured by the method (1) is 0.3 or more and 1 or less, and in the bending resistance test by the cylindrical mandrel method performed by the method (2), Polymers with a minimum diameter of 2 mm or more and 25 mm or less of a cylindrical mandrel that does not cause cracks in the polymer film

(B) Volatile oil having a volatilization rate of 14% or more after drying at 40° C., 60% R. H. for 30 minutes under 1 atm.

<3>

Component (A) is at least one selected from the group consisting of a norbornane structure-containing silicone-modified polymer, a silicone-modified pullulan, a silicone structure-containing silicic acid compound, and a silicone dendrimer,

The strain rate measured by the method (1) is 0.5 or more and 1 or less,

The content of the component (A) in the composition is 0.1% by mass or more and 30% by mass or less,

Component (B) is at least one selected from the group consisting of hydrocarbon oils and silicone oils,

The volatilization rate of component (B) is 30% or more,

The method according to <1> or <2>, wherein the content of the component (B) in the composition is 1% by mass or more and 99.9% by mass or less.

<4>

Any of <1> to <3>, wherein the component (B) is at least one selected from the group consisting of isododecane, hexamethyldisiloxane, methyltrimethicone, and dimethylpolysiloxane having a kinematic viscosity at 25°C of 2 cSt or less. The method described in one.

<5>

The method according to any one of <1> to <4>, wherein the content of the component (B) in the composition is 5% by mass or more and 99.5% by mass or less.

<6>

A value obtained by dividing the product of the volatilization rate (%) of the component (B) and the content (mass%) of the component (B) in the composition by 100 [volatilization rate (%) × content (mass%)/100] is 5 The above method according to any one of <1> to <5>.

<7>

The ratio of the deformation ratio obtained by the method (1) to the minimum diameter (mm) of the mandrel obtained by the method (2) [(strain ratio)/(minimum diameter of the mandrel)] is 0.01 or more and 0.5 or less , The method according to any one of <1> to <6>.

<8>

The method according to any one of <1> to <7>, wherein the content of the component (A) in the composition is 1% by mass or more and 20% by mass or less.

<9>

The method according to any one of <1> to <8>, wherein the volatilization rate of the component (B) is 45% or more.

<10>

The method according to any one of <1> to <9>, wherein the component (B) is at least one selected from the group consisting of hexamethyldisiloxane and dimethylpolysiloxane having a kinematic viscosity at 25°C of 1 cSt or less.

<11>

The method according to any one of <1> to <10>, wherein the content of the component (B) in the composition is 20% by mass or more and 99.5% by mass or less.

<12>

A value obtained by dividing the product of the volatilization rate (%) of the component (B) and the content (mass%) of the component (B) in the composition by 100 [volatilization rate (%) × content (mass%)/100] is 20 or more , The method according to any one of <1> to <11>.

<13>

The method according to any one of <1> to <12>, wherein the component (A) is at least one selected from the group consisting of a norbornane structure-containing silicone-modified polymer and a silicone-modified pullulan.

<14>

In the bending resistance test by the cylindrical mandrel method carried out by the method (2), the minimum diameter of the cylindrical mandrel in which cracks do not occur in the polymer film is 2 mm or more and 12 mm or less, <1> to <13>. The method according to any one of.

<15>

The method according to any one of <1> to <14>, wherein the strain ratio measured by the method (1) is 0.85 or more and 1 or less.

<16>

The ratio of the deformation ratio obtained by the method (1) to the minimum diameter (mm) of the mandrel obtained by the method (2) [(strain ratio)/(minimum diameter of the mandrel)] is 0.10 or more and 0.5 or less , The method according to any one of <1> to <15>.

<17>

The method according to any one of <1> to <16>, wherein the volatilization rate of the component (B) is 80% or more.

<18>

The method according to any one of <1> to <17>, in which the component (B) is hexamethyldisiloxane.

<19>

The method according to any one of <1> to <18>, wherein the content of the component (B) in the composition is 35% by mass or more and 99% by mass or less.

<20>

A value obtained by dividing the product of the volatilization rate (%) of the component (B) and the content (mass%) of the component (B) in the composition by 100 [volatilization rate (%) × content (mass%)/100] is 45 The above method according to any one of <1> to <19>.

<21>

The method according to any one of <1> to <20>, in which the component (A) is a norbornane structure-containing silicone-modified polymer.

<22>

The method according to <21>, wherein the norbornane structure-containing silicone-modified polymer is a silicone-modified polynorbornene represented by the following formula (6).

[Formula 20]

In the formula, e and f are the number of repeating units, each independently an integer of 1 or more.

<23>

The method according to <22>, wherein the ratio of e and f in the formula (6) is e/f = 20/80 to 90/10 (mol/mol).

<24>

In the bending resistance test by the cylindrical mandrel method performed by the method (2), the minimum diameter of the cylindrical mandrel in which cracks do not occur in the polymer film is 3 mm or more and 5 mm or less, <1> to <23>. The method according to any one of.

<25>

The method according to any one of <1> to <24>, wherein the strain ratio measured by the method (1) is 0.95 or more and 1 or less.

<26>

The ratio of the deformation ratio obtained by the method (1) to the minimum diameter (mm) of the mandrel obtained by the method (2) [(strain ratio)/(minimum diameter of the mandrel)] is 0.15 or more and 0.4 or less , The method according to any one of <1> to <25>.

<27>

Component (A) is at least one member selected from the group consisting of a norbornane structure-containing silicone-modified polymer and a silicone-modified pullulan,

The strain rate measured by the method (1) is 0.85 or more and 1 or less,

In the bending resistance test by the cylindrical mandrel method carried out by the method (2), the minimum diameter of the cylindrical mandrel in which cracks do not occur in the polymer film is 2 mm or more and 12 mm or less,

The ratio of the deformation ratio obtained by the method (1) to the minimum diameter (mm) of the mandrel obtained by the method (2) [(strain ratio)/(minimum diameter of the mandrel)] is 0.10 or more and 0.5 or less ego,

The content of the component (A) in the composition is 1% by mass or more and 20% by mass or less,

Component (B) is at least one selected from the group consisting of hexamethyldisiloxane and dimethylpolysiloxane having a kinematic viscosity at 25° C. of 1 cSt or less,

The volatilization rate of component (B) is 45% or more,

The method according to any one of <1> to <3>, wherein the content of the component (B) in the composition is 20% by mass or more and 99% by mass or less.

<28>

Component (A) is at least one member selected from the group consisting of a norbornane structure-containing silicone-modified polymer and a silicone-modified pullulan,

The strain rate measured by the method (1) is 0.85 or more and 1 or less,

In the bending resistance test by the cylindrical mandrel method carried out by the method (2), the minimum diameter of the cylindrical mandrel in which cracks do not occur in the polymer film is 2 mm or more and 12 mm or less,

The content of the component (A) in the composition is 1% by mass or more and 20% by mass or less,

Component (B) is at least one selected from the group consisting of hexamethyldisiloxane and dimethylpolysiloxane having a kinematic viscosity at 25° C. of 1 cSt or less,

The volatilization rate of component (B) is 45% or more,

The content of the component (B) in the composition is 20% by mass or more and 99% by mass or less,

A value obtained by dividing the product of the volatilization rate (%) of the component (B) and the content (mass%) of the component (B) in the composition by 100 [volatilization rate (%) × content (mass%)/100] is 20 or more , The method according to any one of <1> to <3>.

<29>

Component (A) is at least one member selected from the group consisting of a norbornane structure-containing silicone-modified polymer and a silicone-modified pullulan,

The strain rate measured by the method (1) is 0.85 or more and 1 or less,

In the bending resistance test by the cylindrical mandrel method carried out by the method (2), the minimum diameter of the cylindrical mandrel in which cracks do not occur in the polymer film is 2 mm or more and 12 mm or less,

The ratio of the deformation ratio obtained by the method (1) to the minimum diameter (mm) of the mandrel obtained by the method (2) [(strain ratio)/(minimum diameter of the mandrel)] is 0.10 or more and 0.5 or less ego,

The content of the component (A) in the composition is 1% by mass or more and 20% by mass or less,

Component (B) is at least one selected from the group consisting of hexamethyldisiloxane and dimethylpolysiloxane having a kinematic viscosity at 25° C. of 1 cSt or less,

The volatilization rate of component (B) is 45% or more,

The content of the component (B) in the composition is 20% by mass or more and 99% by mass or less,

A value obtained by dividing the product of the volatilization rate (%) of the component (B) and the content (mass%) of the component (B) in the composition by 100 [volatilization rate (%) × content (mass%)/100] is 20 or more , The method according to any one of <1> to <3>.

<30>

Component (A) is a silicone-modified polymer containing a norbornane structure,

The strain rate measured by the method (1) is 0.95 or more and 1 or less,

In the bending resistance test by the cylindrical mandrel method carried out by the method (2), the minimum diameter of the cylindrical mandrel in which cracks do not occur in the polymer film is 3 mm or more and 5 mm or less,

The ratio of the deformation ratio obtained by the method (1) to the minimum diameter (mm) of the mandrel obtained by the method (2) [(strain ratio)/(minimum diameter of the mandrel)] is 0.15 or more and 0.4 or less ego,

The content of the component (A) in the composition is 1% by mass or more and 20% by mass or less,

Component (B) is hexamethyldisiloxane,

The method according to any one of <1> to <3>, wherein the content of the component (B) in the composition is 35% by mass or more and 99% by mass or less.

<31>

Component (A) is a silicone-modified polymer containing a norbornane structure,

The strain rate measured by the method (1) is 0.95 or more and 1 or less,

In the bending resistance test by the cylindrical mandrel method carried out by the method (2), the minimum diameter of the cylindrical mandrel in which cracks do not occur in the polymer film is 3 mm or more and 5 mm or less,

The content of the component (A) in the composition is 1% by mass or more and 20% by mass or less,

Component (B) is hexamethyldisiloxane,

The content of the component (B) in the composition is 35% by mass or more and 99% by mass or less,

A value obtained by dividing the product of the volatilization rate (%) of the component (B) and the content (mass%) of the component (B) in the composition by 100 [volatilization rate (%) × content (mass%)/100] is 45 or more , The method according to any one of <1> to <3>.

<32>

Component (A) is a silicone-modified polymer containing a norbornane structure,

The strain rate measured by the method (1) is 0.95 or more and 1 or less,

In the bending resistance test by the cylindrical mandrel method carried out by the method (2), the minimum diameter of the cylindrical mandrel in which cracks do not occur in the polymer film is 3 mm or more and 5 mm or less,

The ratio of the deformation ratio obtained by the method (1) to the minimum diameter (mm) of the mandrel obtained by the method (2) [(strain ratio)/(minimum diameter of the mandrel)] is 0.15 or more and 0.4 or less ego,

The content of the component (A) in the composition is 1% by mass or more and 20% by mass or less,

Component (B) is hexamethyldisiloxane,

The content of the component (B) in the composition is 35% by mass or more and 99% by mass or less,

A value obtained by dividing the product of the volatilization rate (%) of the component (B) and the content (mass%) of the component (B) in the composition by 100 [volatilization rate (%) × content (mass%)/100] is 45 or more , The method according to any one of <1> to <3>.

<33>

The method according to any one of <1> to <32>, in which the composition is liquid at 25°C.

<34>

The method according to any one of <1> to <33>, wherein the content of water in the composition is 5% by mass or less.

<35>

Any one of <1> to <34>, wherein the composition is applied to the periphery of the wrinkles of the skin, wherein the area to which the composition is applied in the periphery of the wrinkles includes at least a part of the area intersecting the direction of the wrinkles The method described in.

<36>

The method according to <35>, wherein the area is an area along the direction of a wrinkle.

<37>

The method according to <35> or <36>, in which the region is both sides sandwiching a wrinkle.

<38>

The method according to any one of <35> to <37>, wherein the composition is applied to the region in a planar shape, a strip shape, a line shape, or a dot shape.

<39>

The method according to any one of <1> to <38>, wherein the wrinkle improvement method is a method in which the skin around the wrinkles is stretched and elongated by the contraction action of the component (A) to control the shape of the skin non-invasively. .

Example

Hereinafter, the present invention will be described by way of examples, but the present invention is not limited to the scope of the examples. In addition, in this Example, various measurements and evaluation were performed by the following method.

(Number average molecular weight Mn)

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

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

Column: K-806L (manufactured by Shodex), 2 in series

Detector: RI

Eluent: 1 mmol/ℓ-Pamine DM20 (manufactured by Kao Co., Ltd.)/CHCl ₃

Flow rate: 1.0 ml/min

Column temperature: 40 °C

(Transformation ratio)

A 10 mass% hexamethyldisiloxane solution of the polymer used in the composition of each example was prepared. 0.005 g of this solution is shown in Fig. 1(a), a polyethylene sheet 1 having a width (W) of 20 mm × a length (L0) of 100 mm × a thickness of 0.03 mm ("LL film" manufactured by Enshu Chemical Industry Co., Ltd.) On one side of the polyethylene sheet 1, from one end 1a of the short side of the polyethylene sheet 1 toward the length direction, it was applied to a range of 20 mm in width x 50 mm in length (part 2 shown in Fig. 1(a)), and set to 40°C. It was dried for 10 minutes in one thermostat. In the dried polyethylene sheet (Fig. 1(b)), the length of the polyethylene sheet at the portion coated with the solution is L1 (50 mm), and the length of the polyethylene sheet at the portion deformed (curled) by shrinkage after drying is L2. , L2/L1 was calculated, and this value was taken as the deformation ratio of the polymer. L2 was taken as the average of the values measured on two long sides of the polyethylene sheet 1.

(Flexibility resistance)

A 30 mass% hexamethyldisiloxane solution of the polymer used in the composition of each example was prepared. This solution was applied to a polyethylene terephthalate film having a width of 50 mm × a length of 100 mm × a thickness of 0.1 mm using an applicator of 200 μm (“Lumorah 100 T60” manufactured by Toray Co., Ltd.), and a thermostat set at 40°C. It dried for 120 minutes in the inside, and the film (test piece) with a polymer film was produced.

Using the obtained test piece, a bending resistance test was performed in accordance with the cylindrical mandrel method specified in JIS K5600-5-1:1999. Using a type 1 bending test apparatus (Bending Tester manufactured by Ericsen, Model 266), the surface of the polymer film side of the test piece was made to be outside, and diameters 32 mm, 25 mm, 20 mm, 16 mm, 12 mm, 10 mm , 8 mm, 6 mm, 4 mm, 3 mm, and 2 mm cylindrical mandrels were sequentially subjected to a bending resistance test from a cylindrical mandrel having a large diameter. The test was terminated when a crack occurred in the polymer film, and the minimum diameter (mm) of a cylindrical mandrel in which no crack occurred was taken as the value of the bending resistance. The smaller this value is, the better the bending resistance is.

(Volatilization rate)

0.5 g of a sample was placed in a glass dish having a diameter of 40 mm, and left to stand for 30 minutes on a hot plate set at 40° C. in an environment of 60% RH under 1 atmosphere and dried. The mass of the sample before drying was W ₀ (g), the mass of the sample after drying was W ₁ (g), and the value of {(W ₀ -W ₁ )/W ₀ }×100 was taken as the volatilization rate (%). The larger this value, the faster the volatilization rate, which means that it is easier to dry.

(Wrinkle improvement effect)

In the form of Fig. 2(c), 0.2 g of the composition of each example was applied with a finger so that the nasolabial folds of the mouth on the half of the subject's face were interposed. After drying for 10 minutes at room temperature (25° C.), a professional evaluator evaluated the wrinkle improvement effect based on the following 5 steps.

5: wrinkles became considerably softer

4: wrinkles became softer

3: Wrinkles were slightly softened.

2: Wrinkles remained and did not change much

1: no change

Examples 1 to 16, Comparative Examples 1 and 2 (Preparation and evaluation of the composition)

All the components shown in Table 1 were blended, and uniformly mixed with a disper, and the composition shown in Table 1 was prepared. Using the obtained composition, the skin wrinkle improvement evaluation was performed by the above method. Table 1 shows the results. In addition, the compounding amount shown in Table 1 is the amount of the active ingredient (mass %) of each component.

The compounding components in Table 1 are as follows.

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

[Formula 21]

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

*3: Momentive Performance Materials Japan joint company "XS66-B8226" (cyclopentasiloxane solution of trifluoropropyldimethyl/trimethylsiloxysilicic acid, active ingredient concentration: 50% by mass) at 50°C. It dried under reduced pressure for 12 hours, and the obtained solid content was used.

*4: Shin-Etsu Chemical Co., Ltd. product "X21-5595" (trimethylsiloxysilicic acid isododecane solution, active ingredient concentration: 60 mass%) was dried under reduced pressure at 50° C. for 12 hours, and the obtained solid content was used.

*5: Shin-Etsu Chemical Co., Ltd. "KP-550" (isododecane solution of a graft copolymer composed of acrylic polymer and dimethylpolysiloxane, active ingredient concentration: 40 mass%) was dried under reduced pressure at 50° C. for 12 hours, The obtained solid content was used.

*6: Shin-Etsu Chemical Co., Ltd., 「KF-96L-0.65cs」, hexamethyldisiloxane

*7: Shin-Etsu Chemical Co., Ltd., 「KF-96L-1cs」, octamethyltrisiloxane

*8: Shin-Etsu Chemical Co., Ltd., 「KF-995」, decamethylcyclopentasiloxane

*9: The volatilization rate (%) described in Comparative Example 1 is the volatilization rate of decamethylcyclopentasiloxane which is a volatile oil other than component (B).

Regarding the wrinkle improvement effect, the results of Example 1 are shown in Fig. 5 and the results of Comparative Example 2 are shown in Fig. 6. 5(a) and 6(a) are photographs of the periphery of the nasolabial fold before applying the composition, and FIGS. 5(b) and 6(b) are photographs of the periphery of the nasolabial folds after applying the composition. As shown in FIG. 5, according to the method of Example 1, the nasolabial folds and the minor diameters of the periphery were not conspicuous, whereas the improvement effect was not observed in Comparative Example 2 shown in FIG. 6.

Industrial applicability

According to the method of the present invention, by controlling the shape of the skin non-invasively, it is possible to make the wrinkles of the skin inconspicuous.

One ; Polyethylene sheet
1a; One end of the short side of the polyethylene sheet 1
2 ; Part where polymer solution is applied

Claims (12)

A method for improving skin wrinkles, wherein a composition containing the following components (A) and (B) is applied to the skin.
(A) As a polymer having a silicone structure, the strain ratio measured by the following method (1) is 0.3 or more and 1 or less, and in the bending resistance test by the cylindrical mandrel method performed by the following method (2), Polymers with a minimum diameter of 2 mm or more and 25 mm or less of a cylindrical mandrel that does not cause cracks in the polymer film
Method (1): A 10 mass% hexamethyldisiloxane solution of the polymer is prepared. 0.005 g of the solution was applied to one side of a polyethylene sheet having a width of 20 mm × a length of 100 mm × a thickness of 0.03 mm, from one end of the short side toward the length direction, in a range of 20 mm in width × 50 mm in length, and set at 40°C. Dry for 10 minutes in a thermostat. The length of the polyethylene sheet coated with the solution is L1, the length of the polyethylene sheet deformed by shrinkage after drying is L2, and the value of L2/L1 is the strain ratio.
Method (2): A 30 mass% hexamethyldisiloxane solution of the polymer is prepared. The solution was applied to a polyethylene terephthalate film having a width of 50 mm × a length of 100 mm × a thickness of 0.1 mm using a 200 μm applicator, and dried for 120 minutes in a thermostat set at 40° C. to prepare a test piece. Using the test piece, a bending resistance test is performed in accordance with the cylindrical mandrel method specified in JIS K5600-5-1:1999, and the minimum diameter of the cylindrical mandrel in which cracks do not occur in the polymer film on the test piece is determined.
(B) Volatile oil having a volatilization rate of 14% or more after drying for 30 minutes at 40° C. and 60% RH under 1 atm. A method for improving skin wrinkles, comprising a step of applying a composition containing the following components (A) and (B) to the periphery of the skin wrinkles, and then drying the composition to shrink the component (A).
(A) As a polymer having a silicone structure, the strain ratio measured by the following method (1) is 0.3 or more and 1 or less, and in the bending resistance test by the cylindrical mandrel method performed by the following method (2), Polymers with a minimum diameter of 2 mm or more and 25 mm or less of a cylindrical mandrel that does not cause cracks in the polymer film
Method (1): A 10 mass% hexamethyldisiloxane solution of the polymer is prepared. 0.005 g of the solution was applied to one side of a polyethylene sheet having a width of 20 mm × a length of 100 mm × a thickness of 0.03 mm, from one end of the short side toward the length direction, in a range of 20 mm in width × 50 mm in length, and set at 40°C. Dry for 10 minutes in a thermostat. The length of the polyethylene sheet coated with the solution is L1, the length of the polyethylene sheet deformed by shrinkage after drying is L2, and the value of L2/L1 is the strain ratio.
Method (2): A 30 mass% hexamethyldisiloxane solution of the polymer is prepared. The solution was applied to a polyethylene terephthalate film having a width of 50 mm × a length of 100 mm × a thickness of 0.1 mm using a 200 μm applicator, and dried for 120 minutes in a thermostat set at 40° C. to prepare a test piece. Using the test piece, a bending resistance test is performed in accordance with the cylindrical mandrel method specified in JIS K5600-5-1:1999, and the minimum diameter of the cylindrical mandrel in which cracks do not occur in the polymer film on the test piece is determined.
(B) Volatile oil having a volatilization rate of 14% or more after drying for 30 minutes at 40° C. and 60% RH under 1 atm. A method of applying a composition containing the following components (A) and (B) to the periphery of wrinkles on the skin.
(A) As a polymer having a silicone structure, the strain ratio measured by the following method (1) is 0.3 or more and 1 or less, and in the bending resistance test by the cylindrical mandrel method performed by the following method (2), Polymers with a minimum diameter of 2 mm or more and 25 mm or less of a cylindrical mandrel that does not cause cracks in the polymer film
Method (1): A 10 mass% hexamethyldisiloxane solution of the polymer is prepared. 0.005 g of the solution was applied to one side of a polyethylene sheet having a width of 20 mm × a length of 100 mm × a thickness of 0.03 mm, from one end of the short side toward the length direction, in a range of 20 mm in width × 50 mm in length, and set at 40°C. Dry for 10 minutes in a thermostat. The length of the polyethylene sheet coated with the solution is L1, the length of the polyethylene sheet deformed by shrinkage after drying is L2, and the value of L2/L1 is the strain ratio.
Method (2): A 30 mass% hexamethyldisiloxane solution of the polymer is prepared. The solution was applied to a polyethylene terephthalate film having a width of 50 mm × a length of 100 mm × a thickness of 0.1 mm using a 200 μm applicator, and dried for 120 minutes in a thermostat set at 40° C. to prepare a test piece. Using the test piece, a bending resistance test is performed in accordance with the cylindrical mandrel method specified in JIS K5600-5-1:1999, and the minimum diameter of the cylindrical mandrel in which cracks do not occur in the polymer film on the test piece is determined.
(B) Volatile oil having a volatilization rate of 14% or more after drying for 30 minutes at 40° C. and 60% RH under 1 atm. The method according to claim 2 or 3,
In the periphery of the wrinkle, the area to which the composition is applied includes at least a portion of an area that intersects the direction of the wrinkle. The method of claim 4,
The method wherein the area is an area along the direction of the wrinkle. The method according to claim 4 or 5,
The method in which the area is on both sides with a wrinkle interposed therebetween. The method according to any one of claims 1 to 6,
The method in which the component (B) is at least one selected from the group consisting of hydrocarbon oils and silicone oils. The method according to any one of claims 1 to 7,
The method wherein the component (B) is at least one selected from the group consisting of isododecane, hexamethyldisiloxane, methyltrimethicone, and dimethylpolysiloxane having a kinematic viscosity of 2 cSt or less at 25°C. The method according to any one of claims 1 to 8,
The method in which the content of the component (B) in the composition is 1% by mass or more and 99.9% by mass or less. The method according to any one of claims 1 to 9,
The method, wherein the component (A) is at least one selected from the group consisting of silicone-modified polynorbornene, silicone-modified pullulan, trimethylsiloxysilicic acid, trifluoropropyldimethyl/trimethylsiloxysilicic acid, and acrylsilicone dendrimer. The method according to any one of claims 1 to 10,
The ratio of the deformation ratio obtained by the method (1) to the minimum diameter (mm) of the mandrel obtained by the method (2) [(strain ratio)/(minimum diameter of the mandrel)] is 0.01 or more and 0.5 or less , Way. The method according to any one of claims 1 to 11,
The method, wherein the content of the component (A) in the composition is 0.1% by mass or more and 30% by mass or less.

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