JPWO2020067358A1 - How to improve skin wrinkles - Google Patents

Abstract

A method for improving skin wrinkles in which a composition containing a polymer having a silicone structure is applied to the skin, wherein the deformation ratio evaluated by the predetermined method (1) is 0.3 or more and 1 or less. Moreover, in the bending resistance test by the cylindrical mandrel method performed by the predetermined method (2), the minimum diameter of the cylindrical mandrel at which cracks do not occur in the polymer film is 2 mm or more and 25 mm or less.

Description

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

With aging, human skin becomes more wrinkled. This is part of the skin aging phenomenon and is subject to multiple factors such as changes in skin tissue and the effects of exposure to UV light.
Techniques for making wrinkles on the skin inconspicuous have been proposed, but in the cosmetic shaping method, it was necessary to control the shape by invading the skin. Skin care products that non-invasively improve wrinkles on the skin are also known, but the improvement effect is extremely low, and the satisfaction of women suffering from wrinkles has not been obtained.
Therefore, a method that can control the shape of the skin non-invasively and effectively improve wrinkles is desired.

By the way, cosmetics containing a film-forming polymer are known for the purpose of improving the uniformity of the cosmetic film and the retention of the cosmetic film. Patent Document 1 relates to a cosmetic for make-up, which contains a predetermined fructooligosaccharide fatty acid ester, a volatile hydrocarbon, and an oil-soluble film-forming resin, and has excellent coatability and uniformity of a cosmetic film. Patent Document 2 relates to a cosmetic containing a film-forming polymer in which a predetermined functional group is introduced into the skeleton of a polycycloolefin polymer, and has a good cosmetic feel and feel.

Japanese Unexamined Patent Publication 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, in which a composition containing a polymer having a silicone structure is applied to the skin, wherein the deformation ratio measured by the following method (1) is 0.3 or more and 1 or less. A method in which the minimum diameter of a cylindrical mandrel that does not cause cracks in the polymer film is 2 mm or more and 25 mm or less in a bending resistance test by the cylindrical mandrel method performed by the following method (2).
Method (1): A 10% by 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, and a thickness of 0.03 mm in a range of 20 mm in width and 50 mm in length from one end of a short side in the length direction. Dry for 10 minutes in a constant temperature bath set at ° C. The length of the polyethylene sheet of the portion coated with the solution is L1, the length of the polyethylene sheet of the portion deformed by shrinkage after drying is L2, and the value of L2 / L1 is defined as the deformation ratio.
Method (2): A 30% by mass hexamethyldisiloxane solution of the polymer is prepared. The solution is applied to a polyethylene terephthalate film having a width of 50 mm, a length of 100 mm and a thickness of 0.1 mm using a 200 μm applicator, and dried in a constant temperature bath set at 40 ° C. for 120 minutes to prepare a test piece. The test piece is used to perform a bending resistance test in accordance with the cylindrical mandrel method specified in JIS K5600-5: 1: 1999, and the minimum diameter of the cylindrical mandrel at which the polymer film on the test piece does not crack. Ask for.
[2] A method for improving skin wrinkles, which comprises a step of applying a composition containing a polymer having a silicone structure to the periphery of wrinkles of the skin, and then a step of drying the composition to shrink the polymer. In the bending resistance test by the cylindrical mandrel method performed by the method (2), the polymer has a deformation ratio of 0.3 or more and 1 or less as measured by the method (1). A method in which the minimum diameter of a cylindrical mandrel that does not cause cracks in the film is 2 mm or more and 25 mm or less.
[3] A method of applying a composition containing a polymer having a silicone structure to the periphery of wrinkles on the skin, wherein the deformation ratio of the polymer measured by the method (1) is 0.3 or more and 1 or less. A method in which the minimum diameter of a cylindrical mandrel that does not cause cracks in the polymer film in the bending resistance test by the cylindrical mandrel method performed by the method (2) is 2 mm or more and 25 mm or less.

Detailed description of the invention

The present invention is a method of applying a composition containing a polymer having a silicone structure to the periphery of wrinkles on the skin, wherein the deformation ratio of the polymer measured by the following method (1) is 0.3 or more and 1 or less. The present invention relates to a method in which the minimum diameter of the cylindrical mandrel at which cracks do not occur in the polymer film is 2 mm or more and 25 mm or less in the bending resistance test by the cylindrical mandrel method performed by the following method (2).
Further, the present invention is a method for improving wrinkles on the skin, which comprises a step of applying a composition containing a polymer having a silicone structure to the periphery of wrinkles on the skin, and then a step of drying the composition to shrink the polymer. Therefore, the polymer has a deformation ratio of 0.3 or more and 1 or less measured by the following method (1), and is said to have been subjected to a bending resistance test by the cylindrical mandrel method performed by the following method (2). The present invention relates to a method in which the minimum diameter of a cylindrical mandrel that does not cause cracks in a polymer film is 2 mm or more and 25 mm or less.
Hereinafter, these methods are also appropriately referred to as "improvement methods of the present invention".
Method (1): A 10% by 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, and a thickness of 0.03 mm in a range of 20 mm in width and 50 mm in length from one end of a short side in the length direction. Dry for 10 minutes in a constant temperature bath set at ° C. The length of the polyethylene sheet of the portion coated with the solution is L1, the length of the polyethylene sheet of the portion deformed by shrinkage after drying is L2, and the value of L2 / L1 is defined as the deformation ratio.
Method (2): A 30% by mass hexamethyldisiloxane solution of the polymer is prepared. The solution is applied to a polyethylene terephthalate film having a width of 50 mm, a length of 100 mm and a thickness of 0.1 mm using a 200 μm applicator, and dried in a constant temperature bath set at 40 ° C. for 120 minutes to prepare a test piece. The test piece is used to perform a bending resistance test in accordance with the cylindrical mandrel method specified in JIS K5600-5: 1: 1999, and the minimum diameter of the cylindrical mandrel at which the polymer film on the test piece does not crack. Ask for.

Further, the present invention is a method of applying a composition containing a polymer having a silicone structure to the periphery of wrinkles on the skin, wherein the deformation ratio of the polymer measured by the method (1) is 0.3 or more. The present invention relates to a method in which the minimum diameter of the cylindrical mandrel in which cracks do not occur in the polymer film in the bending resistance test by the cylindrical mandrel method performed by the method (2) is 2 mm or more and 25 mm or less. Hereinafter, the method is also appropriately referred to as "the application method of the present invention".

As used herein, the term "skin wrinkles" means irregularities and streaks appearing on the surface of the skin. Wrinkles on the skin tend to appear around the mouth, around the eyes, forehead, neck, etc. Small streaks are small wrinkles, large streaks are large wrinkles, and large wrinkles occur in the pore flow of the law line, cheeks, etc. The improvement method of the present invention has the effect of making all wrinkles inconspicuous, and is particularly preferable in that even large wrinkles such as those on the law line can be improved non-invasively.

The present inventor applies a composition containing a polymer having a silicone structure (hereinafter, also simply referred to as “polymer”) having the predetermined deformation rate and bending resistance to the skin, thereby making the skin non-invasive. We have found that the shape can be controlled and wrinkles on the skin can be made less noticeable.
As described later, the term "skin wrinkle improving method" as used herein refers to a non-invasive method of controlling the shape of the skin by pulling and stretching the skin around the wrinkles by the contraction action of the polymer contained in the composition. The method. That is, it is a method of physically smoothing out wrinkles on the skin to flatten the uneven shape of the skin surface. For example, a cosmetic or the like is applied to the skin to fill the unevenness on the skin surface or optically make the wrinkles inconspicuous. It is a concept different from the method.

<Polymer with silicone structure>
The polymer having a silicone structure used in the present invention has a deformation ratio of 0.3 or more and 1 or less measured by the following method (1), and has bending resistance by the cylindrical mandrel method performed by the following method (2). In the test, the minimum diameter of the cylindrical mandrel that does not cause cracks in the polymer film is 2 mm or more and 25 mm or less.
Method (1): A 10% by 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, and a thickness of 0.03 mm in a range of 20 mm in width and 50 mm in length from one end of a short side in the length direction. Dry for 10 minutes in a constant temperature bath set at ° C. The length of the polyethylene sheet of the portion coated with the solution is L1, the length of the polyethylene sheet of the portion deformed by shrinkage after drying is L2, and the value of L2 / L1 is defined as the deformation ratio.
Method (2): A 30% by mass hexamethyldisiloxane solution of the polymer is prepared. The solution is applied to a polyethylene terephthalate film having a width of 50 mm, a length of 100 mm and a thickness of 0.1 mm using a 200 μm applicator, and dried in a constant temperature bath set at 40 ° C. for 120 minutes to prepare a test piece. The test piece is used to perform a bending resistance test in accordance with the cylindrical mandrel method specified in JIS K5600-5: 1: 1999, and the minimum diameter of the cylindrical mandrel at which the polymer film on the test piece does not crack. Ask for.

By satisfying the above-mentioned deformation ratio measured by the method (1), a polymer having a silicone structure is applied, for example, by applying a composition containing the polymer to the skin around wrinkles, and then applying the composition. When dried, the skin surface in close contact with the polymer shrinks as the film containing the polymer shrinks. By this action, the skin of the wrinkled portion is stretched, so that the wrinkles can be made inconspicuous. Therefore, the improvement method of the present invention preferably includes a step of applying the composition to the wrinkle peripheral portion of the skin, and then a step of drying the composition to shrink the polymer.

The method for evaluating the deformation ratio (L2 / L1) of the polymer by the method (1) will be described with reference to FIG. First, a 10% by mass hexamethyldisiloxane solution of the polymer used in the composition is prepared. 0.005 g of this solution is applied to 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, as shown in FIG. It is applied to a range of 20 mm in width × 50 mm in length (part 2 shown in FIG. 1 (a)) in the direction from the beginning to the length, and dried in a constant temperature bath set at 40 ° C. for 10 minutes. FIG. 1B is a schematic view of a polyethylene sheet to which the solution-coated polyethylene sheet 1 is dried and then a part of the polyethylene sheet is deformed (curled) by shrinkage of the polymer.
In the dried polyethylene sheet (FIG. 1 (b)), the length of the polyethylene sheet in the portion coated with the solution is L1 (50 mm), and the length of the polyethylene sheet deformed by shrinkage after drying is L2. L1 is calculated and this value is used as the deformation ratio. L2 is the average value of the values measured on the two long sides of the polyethylene sheet 1. The larger the value of L2 / L1, the larger the amount of shrinkage of the polymer due to drying, and the upper limit of L2 / L1 is 1.

From the viewpoint of smoothing out wrinkles on the skin and making them inconspicuous, the deformation ratio L2 / L1 evaluated by the method (1) is 0.3 or more, preferably 0.5 or more, more preferably 0.6 or more. It is even more preferably 0.7 or more, even more preferably 0.8 or more, even more preferably 0.85 or more, even more preferably 0.9 or more, even more preferably 0.95 or more, with an upper limit of 1. be.
Specifically, the deformation ratio can be evaluated by the method described in Examples.

Further, the polymer used in the present invention has excellent bending resistance, and in the bending resistance test by the cylindrical mandrel method performed by the method (2), the minimum diameter of the cylindrical mandrel at which cracks do not occur in the film of the polymer is 2 mm or more. It is 25 mm or less. As a result, the film containing the polymer is less likely to crack and is more likely to shrink while following the skin shape.
The smaller the minimum diameter of the cylindrical mandrel, the better the bending resistance. The minimum diameter is 25 mm or less, preferably 20 mm or less, more preferably 12 mm or less, still more preferably 8 mm or less, from the viewpoint of obtaining sufficient adhesion between the film and the skin surface when the film containing the polymer shrinks. It is even more preferably 6 mm or less, and even more preferably 5 mm or less. On the other hand, from the viewpoint of imparting sufficient strength and shape control effect to smooth out wrinkles on the skin and make them inconspicuous, the minimum diameter of the cylindrical mandrel that does not generate cracks is preferably 2 mm or more, more preferably 3 mm or more. be. The specific range of the minimum diameter of the cylindrical mandrel is preferably 2-25 mm, more preferably 2-20 mm, even more preferably 2-12 mm, even more preferably 2-8 mm, even more preferably 3-6 mm, more. More preferably, it is 3 to 5 mm.
The bending resistance can be evaluated by using the type 1 bending test apparatus specified in JIS K5600-5-1: 1999, specifically by the method described in Examples.

Further, the ratio of the deformation ratio of the polymer having the silicone structure used in the present invention to the minimum diameter (mm) of the mandrel obtained by the method (2) [(deformation ratio) / (mandrel). The minimum diameter)] is preferably 0.01 or more, more preferably 0.02 or more, still more preferably 0.10 or more, still more preferably 0.15 or more, from the viewpoint of the effect of improving skin wrinkles. It is preferably 0.5 or less, more preferably 0.4 or less, from the viewpoint of imparting sufficient strength and shape control effect to smooth out and make the wrinkles inconspicuous. 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, still more preferably 0.15 to 0. 5, and even more preferably 0.15 to 0.4.

一般式（Ｉ）中、Ｒ^１はそれぞれ独立に炭素数１以上１２以下の炭化水素基であり、ｐは１以上の整数である。本発明に適用した際に皮膚のシワを伸ばして目立たなくさせ、十分なシワ改善効果を得る観点（以下、「皮膚のシワ改善効果」ともいう）及び汎用性の観点から、Ｒ^１は好ましくは炭素数１以上１２以下のアルキル基又は炭素数６以上１２以下のアリール基であり、より好ましくは炭素数１以上１２以下のアルキル基又はフェニル基、更に好ましくは炭素数１以上３以下のアルキル基、より更に好ましくはメチル基である。As used herein, the term "silicone structure" refers to a structure represented by the following general formula (I).

In the general formula (I), R ¹ is an independently 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 preferable from the viewpoint of extending the wrinkles of the skin to make them inconspicuous and obtaining a sufficient wrinkle improving effect (hereinafter, also referred to as “skin wrinkle improving effect”) and versatility. 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, and further preferably an alkyl group having 1 to 3 carbon atoms. , More preferably a methyl group.

The polymer may have a silicone structure as long as it has a silicone structure, and may be a polymer having only a silicone structure. However, from the viewpoint of forming a polymer having the predetermined characteristics, a polymer having a partially silicone structure is preferable.
In the case of a polymer having a partially silicone structure, the silicone structure may be present in either the main chain or the side chain in the polymer, and is present in the side chain from the viewpoint of making the polymer having the predetermined characteristics. It is preferable to do so.
When the silicone structure is present in the polymer main chain, the bonding form thereof is not particularly limited. For example, the silicone structure may be present at the end of the polymer main chain, or the silicone structure is block-shaped in the polymer main chain. Alternatively, it may be a randomly bonded copolymer polymer. Further, a polymer graft-modified with a compound having a silicone structure can also be used.

As the polymer used in the present invention, a silicone-modified polymer is preferable, and specific examples thereof include a norbornan structure-containing silicone-modified polymer such as silicone-modified polynorbornene; silicone-modified purulan; trialkylsiloxysilicic acid, fluorine-modified alkylsiloxysilicic acid, and the like. Examples thereof include silicone structure-containing silicic acid compounds such as phenyl-modified alkylsiloxysilicic acid; silicone dendrimers; and the like.

ノルボルナン構造含有シリコーン変性ポリマーとしては、下記一般式（１）又は（２）で表される繰り返し単位を有するポリマーが挙げられる。

式中、Ｒ^２はそれぞれ独立に炭素数１以上１２以下のアルキル基であり、Ｘは下記式（ｉ）で表される基である。ａは１以上３以下の整数であり、ｂは０以上２以下の整数である。

式中、Ｒ^１は前記と同じであり、ｃは１以上５以下の整数である。

式中、Ｒ^１、Ｒ^２及びｂは前記と同じであり、ｄは２以上５以下の整数である。(Silicon modified polymer containing norbornane structure)
In the present specification, the norbornane structure means a structure represented by the following formula. The norbornane structure-containing silicone-modified polymer may be any silicone-modified polymer having a structure represented by the formula at any site in the polymer.

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

In the formula, R ² is an alkyl group having 1 to 12 carbon atoms independently, 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.

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

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

In the general formula (1), R ² is an alkyl group having 1 or more and 12 or less carbon atoms independently, and is a methyl group, an ethyl group, or an n-propyl group from the viewpoint of the effect of improving wrinkles on the skin and the viewpoint of versatility. , Butyl group, or pentyl group is preferable, and methyl group is more preferable.
X is a group represented by the above formula (i), and in the formula (i), R ¹ is an independently hydrocarbon group having 1 to 12 carbon atoms. From the viewpoint of skin wrinkle improving effect and versatility, R ¹ is preferably an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms, and more preferably 1 to 12 carbon atoms. Alkyl group or phenyl group, more preferably an alkyl group having 1 or more and 3 or less carbon atoms, and even more preferably 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, for example, a polymer in which a repeating unit of a = 2 and a repeating unit of a = 3 are mixed and exist. From the viewpoint of versatility, a is preferably 3. b is an integer of 0 or more and 2 or less, and from the same viewpoint, 0, 1 or a combination thereof is preferable, 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. Cyclic silicones structure in the general formula (2), from the same viewpoint, R ¹ and R ² are methyl groups, it is preferably 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).

From the viewpoint of the effect of improving skin wrinkles, the ratio of the repeating units represented by the general formula (1) or (2) in the norbornane structure-containing silicone-modified polymer is preferably the total number of repeating units in the polymer. It is 10% or more, more preferably 30% or more, still more preferably 50% or more. 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 norbornane structure-containing silicone-modified polymer is preferably 10 to 100% of the total number of repeating units in the polymer. It is preferably 10 to 95%, more preferably 30 to 90%, and even more preferably 50 to 70%.

式中、Ｒ^３〜Ｒ^６はそれぞれ独立に、水素原子、ハロゲン原子、炭素数１以上１０以下の、アルキル基、アルケニル基、シクロアルキル基、アリール基、アルコキシ基、アリールオキシ基及びハロゲン化炭化水素基から選ばれる置換基、又は、オキセタニル基、アルコキシカルボニル基、ポリオキシアルキレン基、ポリグリセリル基、又はアルコキシシリル基である。Ｒ^３〜Ｒ^６から選ばれる２つの基は、互いに結合して脂環構造、芳香環構造、カルボイミド基又は酸無水物基を形成していてもよい。ｂは前記と同じである。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).

In the formula, R ^{3 to} R ⁶ are independently hydrogen atom, halogen atom, alkyl group, alkenyl group, cycloalkyl group, aryl group, alkoxy group, aryloxy group and halogenated carbide having 1 or more and 10 or less carbon atoms. It is a substituent selected from a hydrogen group, or an oxetanyl group, an alkoxycarbonyl group, a polyoxyalkylene group, a polyglyceryl group, or an alkoxysilyl group. The ^{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 described above.

The ratio of the repeating units represented by the above general formula (3) in the norbornane structure-containing silicone-modified polymer is preferably 90% or less of the total number of repeating units in the polymer from the viewpoint of the effect of improving skin wrinkles. It is more preferably 70% or less, still more preferably 50% or less. When the repeating unit represented by the general formula (3) is included, the ratio thereof 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 is all. 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 10% of the total number of repeating units in the polymer. It is 70%, more preferably 30 to 50%.
The ratio of the repeating units represented by the above general formulas (1) to (3) in the norbornane structure-containing silicone-modified polymer ^{can be determined by 1 1} H-NMR measurement.

式中、ｅ、ｆは繰り返し単位数であり、それぞれ独立に１以上の整数である。
皮膚のシワ改善効果の観点から、一般式（６）中のｅとｆの割合は、好ましくはｅ／ｆ＝２０／８０〜９０／１０（ｍｏｌ／ｍｏｌ）、より好ましくは３０／７０〜８０／２０（ｍｏｌ／ｍｏｌ）であり、更に好ましくは５０／５０〜７０／３０（ｍｏｌ／ｍｏｌ）である。As the norbornane structure-containing silicone-modified polymer, silicone-modified polynorbornene is preferable, and silicone-modified polynorbornene represented by the following formula (6) is more preferable.

In the formula, e and f are the number of repeating units, and each is an integer of 1 or more independently.
From the viewpoint of the effect of improving skin wrinkles, 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 80. It is / 20 (mol / mol), more preferably 50/50 to 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, still more preferably 100,000 or more, from the viewpoint of achieving both shrinkage and bending resistance and the effect of improving skin wrinkles. 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, still 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, still more preferably 200,000 to 200,000. It is 600,000.
The number average molecular weight Mn of the polymer can be measured by a gel permeation chromatography (GPC) method using polystyrene as a standard substance, and specifically, can be measured by the method described in Examples.

式中、Ｒ^１はそれぞれ独立に炭素数１以上１２以下のアルキル基であり、Ｘは下記式（ｉ）で表される基である。ａは１以上３以下の整数であり、ｂは０以上２以下の整数である。

式中、Ｒ^２はそれぞれ独立に炭素数１以上１２以下の炭化水素基であり、ｃは１以上５以下の整数である。

式中、Ｒ^１、Ｒ^２及びｂは前記と同じであり、ｄは２以上５以下の整数である。

式中、Ｒ^３〜Ｒ^６はそれぞれ独立に、水素原子、ハロゲン原子、炭素数１以上１０以下の、アルキル基、アルケニル基、シクロアルキル基、アリール基、アルコキシ基、アリールオキシ基及びハロゲン化炭化水素基から選ばれる置換基、又は、オキセタニル基、アルコキシカルボニル基、ポリオキシアルキレン基、ポリグリセリル基、又はアルコキシシリル基である。Ｒ^３〜Ｒ^６から選ばれる２つの基は、互いに結合して脂環構造、芳香環構造、カルボイミド基又は酸無水物基を形成していてもよい。ｂは前記と同じである。The norbornane structure-containing silicone-modified polymer 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.
For example, in the case of a norbornane structure-containing silicone-modified polymer having a repeating unit represented by the general formula (1) or (2), the cyclic olefin monomer represented by the following general formula (1a) or (2a) is addition-polymerized. Can be obtained. Further, in the addition polymerization, the cyclic olefin monomer represented by the following general formula (3a) may be copolymerized.

In the formula, R ¹ is an alkyl group having 1 to 12 carbon atoms independently, 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.

In the formula, R ² is an independently 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.

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

In the formula, R ^{3 to} R ⁶ are independently hydrogen atom, halogen atom, alkyl group, alkenyl group, cycloalkyl group, aryl group, alkoxy group, aryloxy group and halogenated carbide having 1 or more and 10 or less carbon atoms. It is a substituent selected from a hydrogen group, or an oxetanyl group, an alkoxycarbonyl group, a polyoxyalkylene group, a polyglyceryl group, or an alkoxysilyl group. The ^{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 described above.

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

皮膚のシワ改善効果の観点から、トリス（トリメチルシロキシ）シリルノルボルネンと、ノルボルネンとの共重合比は、好ましくは２０／８０〜９０／１０（ｍｏｌ／ｍｏｌ）、より好ましくは３０／７０〜８０／２０（ｍｏｌ／ｍｏｌ）であり、更に好ましくは５０／５０〜７０／３０（ｍｏｌ／ｍｏｌ）である。The silicone-modified polynorbornene represented by the formula (6) can be obtained by addition polymerization of tris (trimethylsiloxy) silylnorbornene represented by the following formula (6a) and norbornene.

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

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

As the norbornene structure-containing silicone-modified polymer, a norbornene / tris (trimethylsiloxy) silylnorbornene) copolymer is preferable, and the INCI name (International Nomenclature Ingredient Compound Handbook, 16th edition, Vol. 2, 2016, p.2274): NORBORN / TRIS (TRIMETHYLSILOXY) SILYLNORBORNENE COPOLYMER is a compound.
Examples of commercially available norbornane structure-containing silicone-modified polymers include "NBN-30-ID" (norbornene / tris (trimethylsiloxy) silylnorbornene) copolymer isododecane solution manufactured by Shin-Etsu Chemical Co., Ltd.).

式中、Ｚ^１は単結合又は２価の有機基である。Ｒ^２、Ｘ、ａは前記と同じであり、同様の観点から、Ｘは好ましくはトリメチルシロキシ基、ａは好ましくは３である。(Silicone modified pullulan)
Examples of the silicone-modified pullulan include pullulan having a silicone structure in the side chain. Specifically, from the viewpoint of skin wrinkle improving effect and versatility, at least a part of the hydrogen atoms of the OH group in pullulan is present. Silicone-modified pullulan substituted with a group represented by the following general formula (7) is preferable.

In the formula, Z ¹ is a single bond or a divalent organic group. R ^{2, X,} a is the same as defined above, from the same viewpoint, X is preferably trimethylsiloxy radical, a is preferably 3.

式中、Ｒ^１１は炭素数１以上１０以下のアルキレン基であり、メチレン基、エチレン基、トリメチレン基、プロピレン基、ブチレン基等が例示される。同様の観点から、これらの中でもエチレン基、トリメチレン基、プロピレン基が好ましく、トリメチレン基又はプロピレン基がより好ましい。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 the following general. A divalent group represented by the formula (9) is more preferable.

In the formula, R ¹¹ is an alkylene group having 1 or more and 10 or less carbon atoms, and examples thereof include a methylene group, an ethylene group, a trimethylene group, a propylene group and a butylene group. 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.

Commercially available silicone-modified pullulan includes "TSPL-30-ID" (isododecane solution of tri (trimethylsiloxy) pullulan silylpropylcarbamide) and "TSPL-30-D5" (tri (trimethylsiloxy)) manufactured by Shin-Etsu Chemical Co., Ltd. ) Cyclopentasiloxane solution of pullulan silylpropylcarbamide) and the like.

(Silicic acid compound containing silicone structure)
Examples of the silicone structure-containing silicic acid compound used in the present invention include silicate compounds having a silicone structure at the end, and examples thereof include trialkylsiloxysilicic acid, fluorine-modified alkylsiloxysilicic acid, and phenyl-modified alkylsiloxysilicic acid. Be done.
The alkyl group in trialkylsiloxysilicic acid preferably has 1 or more and 10 or less carbon atoms, more preferably 1 or more and 4 or less carbon atoms, and further preferably a methyl group, from the viewpoint of the effect of improving skin wrinkles and versatility. Is. Specific examples of trialkylsiloxysilicic acid include trimethylsiloxysilicic acid.
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 replaced with fluorine atoms. Specific examples thereof include trifluoropropyldimethylsiloxysilicic acid, trifluoropropyldimethyl / trimethylsiloxysilicic acid and the like.
Examples of the phenyl-modified alkylsiloxysilicic acid include phenylpropyldimethylsiloxysilicic acid and phenylpropyldimethyl / trimethylsiloxysilicic acid.

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 skin wrinkles.

Examples of commercially available silicone structure-containing silicic acid compounds include "KF-7312J", "KF-7312K", "KF-7312T", "KF-7312L", and "X-21-5249" manufactured by Shin-Etsu Chemical Industry Co., Ltd. "X-21-5250", "KF-9021", "X-21-5595", "X-21-5616", "KF-9021L", "X-21-5249L", "X-21-5250L" Trimethylsiloxysilicic acid (solution), "XS66-B8226" (cyclopentasiloxane solution of trifluoropropyldimethyl / trimethylsiloxysilicic acid) manufactured by Momentive Performance Materials Japan LLC, "XS66-B8636" ( A dimethicone solution of trifluoropropyldimethyl / trimethylsiloxysilicic acid), "Silicine 151" (phenylpropyldimethylsiloxysilicic acid) and the like can be used.

式中、Ｒ^１は前記と同じである。Ｚ^２は単結合又は２価の有機基である。Ｘ^１はｉ＝１とした場合の下記一般式（１１）で表される基であり、ｉは該基の階層を示す１以上１０以下の整数である。

式中、Ｒ^１は前記と同じであり、Ｒ^１２は炭素数１以上１０以下のアルキル基である。Ｚ^３は炭素数２以上１０以下のアルキレン基である。Ｘ^ｉ+１は水素原子、炭素数１以上１０以下のアルキル基、アリール基又は一般式（１１）で表される基であり、ａ^ｉは０以上３以下の整数である。(Silicone dendrimer)
Examples of the silicone dendrimer include a vinyl polymer having a siloxane dendrimer structure in the side chain. The siloxane dendrimer structure is preferably a group represented by the following general formula (10) from the viewpoint of skin wrinkle improving effect and versatility.

In the formula, R ¹ is the same as described above. Z ² is a single bond or 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 indicating the hierarchy of the group.

In the formula, R ¹ is the same as described above, and R ¹² is an alkyl group having 1 or more carbon atoms 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.

式中、Ｒ^１３は炭素数１以上１０以下のアルキレン基であり、メチレン基、エチレン基、トリメチレン基、プロピレン基、ブチレン基等が例示され、汎用性の観点から、エチレン基、トリメチレン基、又はプロピレン基が好ましい。Ｒ^１４は炭素数１以上１０以下のアルキル基であり、メチル基、エチル基、プロピル基、ブチル基が例示され、同様の観点から、メチル基が好ましい。Ｒ^１５は炭素数１以上１０以下のアルキレン基であり、メチレン基、エチレン基、トリメチレン基、プロピレン基、ブチレン基等が例示され、同様の観点から、エチレン基が好ましい。ｑは０以上４以下の整数であり、ｒは０又は１である。In the general formula (10), Z ² is a single bond or a divalent organic group, preferably a divalent organic group from the viewpoint of versatility, and the following general formulas (12), (13) or ( The divalent group represented by 14) is more preferable.

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

式中、Ｒ^１及びＸ^１は前記と同じである。Ｙはビニル結合を含む基であり、例えば、ビニル基、２−アクリロイルオキシエチル基、３−アクリロイルオキシプロピル基、２−メタクリロイルオキシエチル基、３−メタクリロイルオキシプロピル基、４−ビニルフェニル基、３−ビニルフェニル基、４−（２−プロペニル）フェニル基、３−（２−プロペニル）フェニル基、２−（４−ビニルフェニル）エチル基、２−（３−ビニルフェニル）エチル基、アリル基、５−ヘキセニル基が挙げられる。これらのうち、汎用性の観点から、好ましくは（メタ）アクリロイル基又はビニル基、より好ましくは（メタ）アクリロイル基である。Examples of the vinyl-based polymer having the above-mentioned siloxane dendrimer structure in the side chain (hereinafter, also simply referred to as “vinyl-based polymer”) include a polymer having a repeating unit derived from a monomer represented by the following general formula (15). Be done.

In the formula, R ¹ and X ¹ are the same as described above. Y is a group containing a vinyl bond, for example, a vinyl group, a 2-acryloyloxyethyl group, a 3-acryloyloxypropyl group, a 2-methacryloyloxyethyl group, a 3-methacryloyloxypropyl group, a 4-vinylphenyl group, 3 -Vinylphenyl group, 4- (2-propenyl) phenyl group, 3- (2-propenyl) phenyl group, 2- (4-vinylphenyl) ethyl group, 2- (3-vinylphenyl) ethyl group, allyl group, Examples include 5-hexenyl groups. Of these, from the viewpoint of versatility, a (meth) acryloyl group or a vinyl group is preferable, and a (meth) acryloyl group is more preferable.

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

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

The vinyl polymer is more preferably 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) acroyl group in the general formula (15), and is a polymer other than the monomer represented by the general formula (15). Meta) It may further contain a repeating unit derived from an acrylic monomer.

Commercially available silicone dendrimers include "FA 4001 CM Silicone Acrylate" (cyclopentasiloxane solution of acrylate-polytrimethylsiloxymethacrylate copolymer) and "FA 4002 ID Silicone Acrylate" (acrylate-poly) manufactured by Toray Dow Corning Co., Ltd. Acrylic silicone dendrimers such as isododecane solution of trimethylsiloxymethacrylate copolymer) can be mentioned.

Among the above polymers, from the viewpoint of the effect of improving wrinkles on the skin, it is selected from the group consisting of silicone-modified polynorbornene, silicone-modified purulan, trimethylsiloxysilicic acid, trifluoropropyldimethyl / trimethylsiloxysilicic acid, and acrylic silicone dendrimer. More than one species is preferable, and one or more species selected from the group consisting of silicone-modified polynorbornene, silicone-modified purulan, trimethylsiloxysilicic acid, and trifluoropropyldimethyl / trimethylsiloxysilicic acid are more preferable, and the effect of improving wrinkles on the skin and bending resistance are more preferable. From the viewpoint of properties, one or more selected from the group consisting of silicone-modified polynorbornene and silicone-modified purulan is more preferable, and silicone-modified polynorbornen is even more preferable.

The content of the polymer 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 skin wrinkles. , More preferably 5% by mass or more. The content of the polymer in the composition is preferably 30% by mass or less, more preferably 25% by mass, from the viewpoints of applicability of the composition, flexibility of formulation, and no discomfort to the skin after drying. Below, it is more preferably 20% by mass or less, and even more preferably 15% by mass or less. The specific range of the content of the polymer in the composition is preferably 0.1 to 30% by mass, more preferably 0.5 to 25% by mass, still more preferably 1 to 20% by mass, still more preferably 1. It is ~ 15% by mass, more preferably 5 to 15% by mass.

<Volatile oil>
The composition used in the present invention further enhances the effect of improving skin wrinkles at 40 ° C. and 60% R.I. H. It can contain a volatile oil having a volatility of 14% or more after drying for 30 minutes. When the volatile oil is contained, the drying rate of the composition containing the polymer is improved, so that the shrinkage of the polymer in the drying process is accelerated, and the effect of smoothing and making the wrinkles of the skin inconspicuous by the above-mentioned mechanism of action is achieved. Is improved.
From the viewpoint of obtaining the above effects, the volatile oil is prepared at 40 ° C. and 60% R. under 1 atm. H. The volatilization rate after drying for 30 minutes is preferably 18% or more, more preferably 25% or more, further preferably 30% or more, still more preferably 45% or more, still more preferably 65% or more, still more preferably. It is 80% or more, more preferably 95% or more. The upper limit is 100%.
The volatility of the volatile oil was 60% R.I. H. In the environment of, let stand at 40 ° C. for 30 minutes to dry, and set the sample mass before drying to W ₀ (g) and the sample mass after drying to W ₁ (g), and {(W _0- W). ₁ ) / W ₀ } × 100.
Two or more types of volatile oil can be used.

Preferred specific examples of the volatile oil include an oil agent which is one or more selected from the group consisting of hydrocarbon oil and silicone oil and whose volatility is in the above range. Among these volatile oils, it is selected from the group consisting of isododecane (volatility 33%), hexamethyldisiloxane (volatility 100%), methyltrimethicone, and dimethylpolysiloxane having a kinematic viscosity of 2 cSt or less at 25 ° C. One or more is preferable. The kinematic viscosity can be measured using, for example, an Ubbelohde viscometer.
The volatile oil is more preferably one or more selected from the group consisting of isododecane and hexamethyldisiloxane, and even more preferably hexamethyldisiloxane.

The content of the volatile oil 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 further 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, still more preferably 45% by mass or more, still more preferably 50% by mass or more, still more preferably 60. It is preferably 7% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and preferably 99.9% by mass or less from the viewpoint of enhancing the effect of improving skin wrinkles and the degree of freedom of formulation. It is more preferably 99.5% by mass or less, still more preferably 99% by mass or less, still more preferably 97% by mass or less, still more preferably 95% by mass or less. The specific range of the content of the volatile oil in the composition is preferably 1 to 99.9% by mass, more preferably 5 to 99.5% by mass, still more preferably 10 to 99.5% by mass, still more. It is preferably 20 to 99.5% by mass, more preferably 25 to 99.5% by mass, still more preferably 35 to 99.5% by mass, still more preferably 35 to 99% by mass, and even more preferably 45 to 99.5% by mass. 99% by mass, more preferably 50 to 99% by mass, still more preferably 60 to 99% by mass, still more preferably 70 to 99% by mass, still more preferably 80 to 99% by mass, still more preferably 80 to 80 to It is 97% by mass, more preferably 80 to 95% by mass.

<Other ingredients>
In addition to the above-mentioned components, the composition used in the present invention may appropriately contain other components usually blended in cosmetics and the like as long as the object of the present invention is not impaired. Examples of the component include surfactants, water-soluble polymers, antioxidants, UV absorbers, vitamins, preservatives, pH adjusters, fragrances, plant extracts, moisturizers, colorants, and cold sensants. Antiperspirants, bactericides, skin activators and the like can be mentioned.

The form of the composition used in the present invention may be any form that can be applied 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 liquid when applied to the skin from the viewpoint of applying the composition to the skin or the like and then drying the composition to shrink the polymer and exert an effect of improving wrinkles on the skin. It is preferable, and it is more preferable that it is liquid at 25 ° C.

Further, the composition used in the present invention has a water content from the viewpoint of accelerating the shrinkage of the polymer in the step of applying the composition to the skin and then drying the composition and enhancing the effect of improving the wrinkles of the skin. Less is preferable. 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, still more preferably 2% by mass or less, still more preferably 1% by mass. Hereinafter, it is even more preferably 0.5% by mass or less, and even more preferably 0.1% by mass or less.

In the method for improving skin wrinkles of the present invention, specifically, it is preferable to apply the composition by applying the composition to the periphery of the skin wrinkles.
Further, in the application method of the present invention, for example, the composition is applied to the peripheral portion of wrinkles. According to the application method, the shape of the skin can be controlled non-invasively by the above-mentioned mechanism of action, and wrinkles on the skin can be made inconspicuous.

The "periphery of wrinkles on the skin" in the present specification is distinguished from the inside of wrinkles, that is, the recesses on the surface of the skin and the recesses on the streaks. In the present invention, by applying the composition containing the polymer to the skin around the wrinkles, when the composition is dried, the skin surface around the wrinkles shrinks along with the shrinkage of the film containing the polymer to cause wrinkles. The skin in the area where it is formed is pulled and wrinkles become less noticeable. 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 can be obtained, it does not prevent the composition from being applied not only to the peripheral part of the skin wrinkles but also to the inside of the wrinkles.

From the viewpoint of obtaining the above effect, it is preferable that the region to which the composition is applied includes at least a part of the region intersecting the direction of the wrinkles in the wrinkle peripheral portion. The direction of wrinkles is the direction in which the streaks run. This is because by applying the composition to the region intersecting the direction of wrinkles, the skin of the wrinkled portion is stretched and the wrinkles become inconspicuous.
The region intersecting the direction of the wrinkles is preferably a region along the direction of the wrinkles, and the region may be only one side of the wrinkles or both sides. In particular, it is more preferable to apply the composition on both sides of the wrinkle. This is because the wrinkles can be made less noticeable by pulling the skin of the wrinkled portion from both sides of the wrinkles.
Examples of the form in which the composition is applied to a region along the direction of wrinkles include a form in which the composition is applied to the region in a planar, band-like, linear or dot shape, and specifics thereof will be described later. Examples of the forms shown in FIGS. 2 to 4 can be illustrated.

Further, when the direction of wrinkles is not parallel to the direction of gravity, for example, as in the law line, it is preferable that the region to which the composition is applied (the region intersecting the direction of wrinkles) includes the region above the wrinkles. The "gravity direction" here means a direction in which gravity acts when a person is upright, and the "upper side" means a direction opposite to the above-mentioned gravity direction. By applying the composition to at least the area above the wrinkles, the skin of the wrinkled portion can be pulled upward to make the wrinkles less noticeable. From the same viewpoint as above, when the direction of the wrinkles is not parallel to the direction of gravity, the region to which the composition is applied is the upper and lower regions sandwiching the wrinkles, and the region above the wrinkles. Is more preferably a wider area than the area under the wrinkles.

An example of a form in which the composition is applied in the application method of the present invention is shown in FIGS. 2 to 4.
FIG. 2 shows a form in which the composition is applied to the skin around the wrinkles (law line) in a planar or band shape, FIG. 2 (a) is an area above the wrinkles, and FIGS. 2 (b) and 2 (c) are wrinkles. The composition is applied to the upper and lower regions sandwiching the above. From the viewpoint of making wrinkles less noticeable, as shown in FIG. 2C, the region to which the composition is applied is the upper and lower regions sandwiching the wrinkles, and the upper region of the wrinkles is the wrinkle. More preferably, it is wider than the lower area.
3 (a), (b) and (c) show the form in which the composition is linearly applied to the skin around the wrinkles (law line), and FIGS. 4 (a) and 4 (b) show the wrinkles (law line). It is a form in which the composition is applied in dots to the surrounding skin. As shown in FIGS. 3 and 4, even when the composition is applied in a linear or dot shape, the composition is applied to the upper and lower regions sandwiching the wrinkles from the viewpoint of evenly pulling the skin from both sides of the wrinkles. It is preferable to apply.

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 is, for example, 0.01 g or more and 10 g or less.

In the application method of the present invention, it is preferable to have a step of applying the composition to the periphery of wrinkles of the skin and the like, and then a step of drying the composition to shrink the polymer. The drying causes the polymer in the composition applied to the skin to shrink, and the shrinking action pulls and stretches the skin around the wrinkles to flatten the uneven shape of the skin surface and make the wrinkles inconspicuous. It works.
After drying, the composition may be removed if necessary. Alternatively, the composition may be applied to the skin and then dried, and then the composition may not be removed and makeup may be applied over the composition.

式中、ｅ、ｆは繰り返し単位数であり、それぞれ独立に１以上の整数である。
＜１２＞
前記式（６）中のｅとｆの割合が、ｅ／ｆ＝２０／８０〜９０／１０（ｍｏｌ／ｍｏｌ）である、＜１１＞に記載の方法。With respect to the above embodiments, the present invention further discloses the following embodiments.
<1>
A method for improving skin wrinkles, in which a composition containing a polymer having a silicone structure is applied to the skin.
The polymer has a deformation ratio of 0.3 or more and 1 or less measured by the following method (1), and is a film of the polymer in a bending resistance test by the cylindrical mandrel method performed by the following method (2). A method in which the minimum diameter of a cylindrical mandrel that does not cause cracks is 2 mm or more and 25 mm or less.
Method (1): A 10% by 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, and a thickness of 0.03 mm in a range of 20 mm in width and 50 mm in length from one end of a short side in the length direction. Dry for 10 minutes in a constant temperature bath set at ° C. The length of the polyethylene sheet of the portion coated with the solution is L1, the length of the polyethylene sheet of the portion deformed by shrinkage after drying is L2, and the value of L2 / L1 is defined as the deformation ratio.
Method (2): A 30% by mass hexamethyldisiloxane solution of the polymer is prepared. The solution is applied to a polyethylene terephthalate film having a width of 50 mm, a length of 100 mm and a thickness of 0.1 mm using a 200 μm applicator, and dried in a constant temperature bath set at 40 ° C. for 120 minutes to prepare a test piece. The test piece is used to perform a bending resistance test in accordance with the cylindrical mandrel method specified in JIS K5600-5: 1: 1999, and the minimum diameter of the cylindrical mandrel at which the polymer film on the test piece does not crack. Ask for.
<2>
A method for improving skin wrinkles, which comprises a step of applying a composition containing a polymer having a silicone structure to a wrinkle peripheral portion of the skin, and then a step of drying the composition to shrink the polymer.
The polymer has a deformation ratio of 0.3 or more and 1 or less measured by the method (1), and is a film of the polymer in a bending resistance test by the cylindrical mandrel method performed by the method (2). A method in which the minimum diameter of a cylindrical mandrel that does not cause cracks is 2 mm or more and 25 mm or less.
<3>
The polymer is one or more selected from the group consisting of a norbornan structure-containing silicone-modified polymer, a silicone-modified pullulan, a silicone structure-containing silicic acid compound, and a silicone dendrimer, and the content of the polymer in the composition is 0.1. The method according to <1> or <2>, wherein the deformation ratio is 0.5 or more and 30% by mass or less and the deformation ratio measured by the method (1) is 0.5 or more and 1 or less.
<4>
The ratio of the deformation ratio determined by the method (1) to the minimum mandrel diameter (mm) obtained by the method (2) [(deformation ratio) / (minimum diameter of the mandrel)] is 0.01 or more and 0.5. The method for improving skin wrinkles according to any one of <1> to <3>, which is described below.
<5>
The method according to any one of <1> to <4>, wherein the content of the polymer in the composition is 1% by mass or more and 20% by mass or less.
<6>
The method according to any one of <1> to <5>, wherein the polymer is at least one selected from the group consisting of a norbornane structure-containing silicone-modified polymer and silicone-modified pullulan.
<7>
In the bending resistance test by the cylindrical mandrel method performed by the method (2), the minimum diameter of the cylindrical mandrel that does not cause cracks in the polymer film is 2 mm or more and 12 mm or less. The method according to any one.
<8>
The method according to any one of <1> to <7>, wherein the deformation ratio measured by the method (1) is 0.85 or more and 1 or less.
<9>
The ratio of the deformation ratio determined by the method (1) to the minimum mandrel diameter (mm) obtained by the method (2) [(deformation ratio) / (minimum diameter of the mandrel)] is 0.10 or more and 0.5. The method according to any one of <1> to <8>, which is described below.
<10>
The method according to any one of <1> to <9>, wherein the polymer is a norbornane structure-containing silicone-modified polymer.
<11>
The method according to <10>, wherein the norbornane structure-containing silicone-modified polymer is a silicone-modified polynorbornene represented by the following formula (6).

In the formula, e and f are the number of repeating units, and each is an integer of 1 or more independently.
<12>
The method according to <11>, wherein the ratio of e and f in the formula (6) is e / f = 20/80 to 90/10 (mol / mol).

式中、ｅ、ｆは繰り返し単位数であり、それぞれ独立に１以上の整数である。
＜２１＞
前記式（６）中のｅとｆの割合が、ｅ／ｆ＝２０／８０〜９０／１０（ｍｏｌ／ｍｏｌ）である、＜２０＞に記載の方法。
＜２２＞
前記ポリマーが下記式（６）で表されるシリコーン変性ポリノルボルネンであり、前記組成物中の該ポリマーの含有量が１質量％以上２０質量％以下であり、前記方法（１）により測定される変形割合が０．９５以上１以下であり、前記方法（２）により行われる円筒形マンドレル法による耐屈曲性試験において、該ポリマーの膜にクラックが発生しない円筒形マンドレルの最小直径が３ｍｍ以上５ｍｍ以下であり、前記方法（２）により求められるマンドレルの最小直径（ｍｍ）に対する、前記方法（１）により求められる変形割合の比率［（変形割合）／（マンドレルの最小直径）］が０．１５以上０．４以下である、＜１＞〜＜３＞のいずれか１に記載の方法。

式中、ｅ、ｆは繰り返し単位数であり、それぞれ独立に１以上の整数である。
＜２３＞
前記式（６）中のｅとｆの割合が、ｅ／ｆ＝２０／８０〜９０／１０（ｍｏｌ／ｍｏｌ）である、＜２２＞に記載の方法。
＜２４＞
前記組成物がさらに１気圧下、４０℃、６０％Ｒ．Ｈ．で３０分乾燥後の揮発率が１４％以上である揮発性油を含有する、＜１＞〜＜２３＞のいずれか１に記載の方法。
＜２５＞
前記組成物中の揮発性油の含有量が４５質量％以上９９質量％以下である、＜２４＞に記載の方法。
＜２６＞
前記組成物が２５℃において液状である、＜１＞〜＜２５＞のいずれか１に記載の方法。
＜２７＞
前記組成物中の水の含有量が５質量％以下である、＜１＞〜＜２６＞のいずれか１に記載の方法。
＜２８＞
前記組成物を皮膚のシワ周辺部に適用する方法であり、該シワ周辺部において該組成物を適用する領域が、シワの方向と交差する領域の少なくとも一部を含む、＜１＞〜＜２７＞のいずれか１に記載の方法。<13>
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 <12>. The method according to any one.
<14>
The method according to any one of <1> to <13>, wherein the deformation ratio measured by the method (1) is 0.95 or more and 1 or less.
<15>
The ratio of the deformation ratio obtained by the method (1) to the minimum diameter (mm) of the mandrel obtained by the method (2) [(deformation ratio) / (minimum diameter of the mandrel)] is 0.15 or more and 0.4. The method according to any one of <1> to <14>, which is as follows.
<16>
The polymer is one or more selected from the group consisting of a norbornan structure-containing silicone-modified polymer and silicone-modified pullulan, and the content of the polymer in the composition is 1% by mass or more and 20% by mass or less. The deformation ratio of the cylindrical mandrel measured by 1) is 0.85 or more and 1 or less, and in the bending resistance test by the cylindrical mandrel method performed by the method (2), the polymer film does not crack. The method according to any one of <1> to <3>, wherein the minimum diameter is 2 mm or more and 12 mm or less.
<17>
The polymer is one or more selected from the group consisting of norbornan structure-containing silicone-modified polymers and silicone-modified pullulan, and the content of the polymer in the composition is 1% by mass or more and 20% by mass or less. The deformation ratio of the cylindrical mandrel measured by 1) is 0.85 or more and 1 or less, and in the bending resistance test by the cylindrical mandrel method performed by the method (2), the polymer film does not crack. The minimum diameter is 2 mm or more and 12 mm or less, and the ratio of the deformation ratio obtained by the method (1) to the minimum diameter (mm) of the mandrel obtained by the method (2) [(deformation ratio) / (minimum diameter of the mandrel). )] Is 0.10 or more and 0.5 or less, according to any one of <1> to <3>.
<18>
The polymer is a norbornan structure-containing silicone-modified polymer, the content of the polymer in the composition is 1% by mass or more and 20% by mass or less, and the deformation ratio measured by the method (1) is 0.95 or more. 1 or less, and 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>. The method according to any one of ~ <3>.
<19>
The polymer is a norbornan structure-containing silicone-modified polymer, the content of the polymer in the composition is 1% by mass or more and 20% by mass or less, and the deformation ratio measured by the method (1) is 0.95 or more. 1 or less, and 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, and the above method ( The ratio of the deformation ratio obtained by the method (1) to the minimum mandrel diameter (mm) obtained by 2) [(deformation ratio) / (minimum diameter of mandrel)] is 0.15 or more and 0.4 or less. , The method according to any one of <1> to <3>.
<20>
The polymer is a silicone-modified polynorbornene represented by the following formula (6), and the content of the polymer in the composition is 1% by mass or more and 20% by mass or less, and is measured by the method (1). In the bending resistance test by the cylindrical mandrel method performed by the method (2) above, the deformation ratio is 0.95 or more and 1 or less, and 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. The method according to any one of <1> to <3>, which is described below.

In the formula, e and f are the number of repeating units, and each is an integer of 1 or more independently.
<21>
The method according to <20>, wherein the ratio of e and f in the formula (6) is e / f = 20/80 to 90/10 (mol / mol).
<22>
The polymer is a silicone-modified polynorbornene represented by the following formula (6), and the content of the polymer in the composition is 1% by mass or more and 20% by mass or less, and is measured by the method (1). In the bending resistance test by the cylindrical mandrel method performed by the method (2) above, the deformation ratio is 0.95 or more and 1 or less, and 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. The ratio of the deformation ratio obtained by the method (1) to the minimum diameter (mm) of the mandrel obtained by the method (2) [(deformation ratio) / (minimum diameter of the mandrel)] is 0.15. The method according to any one of <1> to <3>, which is 0.4 or less.

In the formula, e and f are the number of repeating units, and each is an integer of 1 or more independently.
<23>
The method according to <22>, wherein the ratio of e to f in the formula (6) is e / f = 20/80 to 90/10 (mol / mol).
<24>
The composition was further subjected to 1 atm, 40 ° C., 60% R. et al. H. The method according to any one of <1> to <23>, which contains a volatile oil having a volatility of 14% or more after drying for 30 minutes.
<25>
The method according to <24>, wherein the content of the volatile oil in the composition is 45% by mass or more and 99% by mass or less.
<26>
The method according to any one of <1> to <25>, wherein the composition is liquid at 25 ° C.
<27>
The method according to any one of <1> to <26>, wherein the content of water in the composition is 5% by mass or less.
<28>
A method of applying the composition to the wrinkle peripheral portion of the skin, wherein the region to which the composition is applied in the wrinkle peripheral portion includes at least a part of a region intersecting the direction of the wrinkles, <1> to <27. > The method according to any one of 1.

<29>
The method according to <28>, wherein the region is a region along the direction of wrinkles.
<30>
The method according to <28> or <29>, wherein the region is on both sides of the wrinkle.
<31>
The method according to any one of <27> to <30>, wherein the composition is applied to the region in a planar shape, a strip shape, a linear shape, or a dot shape.
<32>
The method according to any one of <1> to <31>, wherein the wrinkle improving method is a method of pulling and stretching the skin around the wrinkles by the contraction action of the polymer to control the shape of the skin non-invasively. ..

Hereinafter, the present invention will be described with reference to Examples, but the present invention is not limited to the scope of the Examples. In this example, various measurements and evaluations were carried out by the following methods.

(Number average molecular weight Mn)
The number average molecular weight of the polymer was measured by a gel permeation chromatography (GPC) method using polystyrene as a standard substance under the following conditions.
Measuring device: HLC-8320GPC (manufactured by Tosoh Corporation)
Column: K-806L (manufactured by Shodex), 2 series detector: RI
Eluent: 1 mmol / L-Farmin DM20 (manufactured by Kao Corporation) / CHCl ₃
Flow rate: 1.0 mL / min
Column temperature: 40 ° C

(Deformation rate)
A 10 mass% hexamethyldisiloxane solution of the polymer used in the composition of each example was prepared. 0.005 g of this solution is added to 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 Kasei Kogyo Co., Ltd.) as shown in FIG. 1 (a). A constant temperature set at 40 ° C. was applied to one side of the polyethylene sheet 1 in a range of 20 mm in width × 50 mm in length (part 2 shown in FIG. 1 (a)) from one end 1a of the short side of the polyethylene sheet 1 in the length direction. It was dried in the tank for 10 minutes. In the dried polyethylene sheet (FIG. 1 (b)), the length of the polyethylene sheet in the portion coated with the solution is L1 (50 mm), and the length of the polyethylene sheet deformed (curled) by shrinkage after drying is L2. L2 / L1 was calculated, and this value was used as the deformation ratio of the polymer. L2 was the average value of the values measured on the two long sides of the polyethylene sheet 1.

(Bending 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 (“Lumilar 100T60” manufactured by Toray Industries, Inc.) having a width of 50 mm, a length of 100 mm, and a thickness of 0.1 mm using a 200 μm applicator, and in a constant temperature bath set at 40 ° C. The film was dried for 120 minutes to prepare a film with a polymer film (test piece).
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 tester (Mandrel 266, a bending tester manufactured by Ericssen), the diameter of the test piece is 32 mm, 25 mm, 20 mm, 16 mm, 12 mm, 10 mm, so that the surface of the test piece on the polymer film side is on the outside. Bending resistance tests were carried out sequentially from the cylindrical mandrel having the largest diameter using the cylindrical mandrel of 8 mm, 6 mm, 4 mm, 3 mm, and 2 mm. The test was terminated when cracks were generated in the polymer film, and the minimum diameter (mm) of the cylindrical mandrel in which no cracks were generated was defined as the bending resistance value. The smaller this value is, the better the bending resistance is.

(Wrinkle improvement effect)
In the form of FIG. 2C, 0.2 g of the composition of each example was applied with a finger so as to sandwich the law line at the mouth on one side of the subject's face. After drying at room temperature (25 ° C.) for 10 minutes, a professional evaluator evaluated the wrinkle improving effect according to the following five criteria.
5: Wrinkles have become considerably thinner 4: Wrinkles have become thinner 3: Wrinkles have become slightly thinner 2: Wrinkles remain and do not change much 1: No change

Examples 1-7, Comparative Example 1 (Production and Evaluation of Composition)
All the components shown in Table 1 were blended and mixed uniformly with a disper to prepare the composition shown in Table 1. Using the obtained composition, the skin wrinkle improvement evaluation was carried out by the above method. The results are shown in Table 1. The blending amount shown in Table 1 is the amount of the active ingredient (mass%) of each component.

The ingredients in Table 1 are as follows.
* 1: "NBN-30-ID" manufactured by Shin-Etsu Chemical Co., Ltd. (in the following formula (6), e / f = 60/40 (mol / mol), Mn = 360,000 norbornene / tris (trimethylsiloxy) silyl A solution of norbornene) copolymer in isododecane, effective concentration: 30% by mass) was dried under reduced pressure at 50 ° C. for 12 hours, and the obtained solid content was used.

* 2: "TSPL-30-ID" manufactured by Shin-Etsu Chemical Co., Ltd. (isododecane solution of tri (trimethylsiloxy) pullulan silylpropylcarbamide, effective concentration: 30% by mass) was dried under reduced pressure at 50 ° C. for 12 hours. The obtained solid content was used.
* 3: Depressurize "XS66-B8226" (cyclopentasiloxane solution of trifluoropropyldimethyl / trimethylsiloxysilicic acid, effective concentration: 50% by mass) manufactured by Momentive Performance Materials Japan LLC at 50 ° C for 12 hours. It was dried and the obtained solid content was used.
* 4: "X21-5595" manufactured by Shin-Etsu Chemical Co., Ltd. (isododecan solution of trimethylsiloxysilicic acid, effective concentration: 60% by mass) was dried under reduced pressure at 50 ° C. for 12 hours, and the obtained solid content was used. ..
* 5: "FA 4002 ID Silicone Acrylate" manufactured by Toray Dow Corning Co., Ltd. (isododecane solution of acrylate-polytrimethylsiloxymethacrylate copolymer, effective concentration: 40% by mass) was dried under reduced pressure at 50 ° C. for 12 hours. The obtained solid content was used.
* 6: "KP-550" manufactured by Shin-Etsu Chemical Co., Ltd. (isododecane solution of graft copolymer composed of acrylic polymer and dimethylpolysiloxane, effective concentration: 40% by mass) was dried under reduced pressure at 50 ° C. for 12 hours. The obtained solid content was used.
* 7: "KF-96L-0.65cs" manufactured by Shin-Etsu Chemical Co., Ltd., hexamethyldisiloxane

Regarding the wrinkle improving effect, the result of Example 1 is shown in FIG. 5, and the result of Comparative Example 1 is shown in FIG. 5 (a) and 6 (a) are photographs of the periphery of the law line before the composition is applied, and FIGS. 5 (b) and 6 (b) are the periphery of the law line after the composition is applied. This is a picture of the club. As shown in FIG. 5, according to the method of Example 1, the fine wrinkles on the law line and its peripheral portion became inconspicuous, whereas in Comparative Example 1 shown in FIG. 6, no improvement effect was observed.

According to the method of the present invention, the shape of the skin can be controlled non-invasively and the wrinkles of the skin can be made inconspicuous.

It is explanatory drawing of the evaluation method of the deformation ratio (L2 / L1) of a polymer by the method (1). This is an example of a form in which the composition is applied in a planar or band shape to the skin around the wrinkles (law line). This is an example of a form in which the composition is linearly applied to the skin around the wrinkles (law line). This is an example of a form in which the composition is applied in dots to the skin around the wrinkles (law line). It is a photograph which shows the wrinkle improvement effect of Example 1. FIG. It is a photograph which shows the wrinkle improvement effect of the comparative example 1.

1 Polyethylene sheet
1a One end of the short side of the polyethylene sheet 1 2 The portion coated with the polymer solution

Claims (9)

A method for improving skin wrinkles, in which a composition containing a polymer having a silicone structure is applied to the skin.
The polymer has a deformation ratio of 0.3 or more and 1 or less measured by the following method (1), and is a film of the polymer in a bending resistance test by the cylindrical mandrel method performed by the following method (2). A method in which the minimum diameter of a cylindrical mandrel that does not cause cracks is 2 mm or more and 25 mm or less.
Method (1): A 10% by 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, and a thickness of 0.03 mm in a range of 20 mm in width and 50 mm in length from one end of a short side in the length direction. Dry for 10 minutes in a constant temperature bath set at ° C. The length of the polyethylene sheet of the portion coated with the solution is L1, the length of the polyethylene sheet of the portion deformed by shrinkage after drying is L2, and the value of L2 / L1 is defined as the deformation ratio.
Method (2): A 30% by mass hexamethyldisiloxane solution of the polymer is prepared. The solution is applied to a polyethylene terephthalate film having a width of 50 mm, a length of 100 mm and a thickness of 0.1 mm using a 200 μm applicator, and dried in a constant temperature bath set at 40 ° C. for 120 minutes to prepare a test piece. The test piece is used to perform a bending resistance test in accordance with the cylindrical mandrel method specified in JIS K5600-5: 1: 1999, and the minimum diameter of the cylindrical mandrel at which the polymer film on the test piece does not crack. Ask for. A method for improving skin wrinkles, which comprises a step of applying a composition containing a polymer having a silicone structure to a wrinkle peripheral portion of the skin, and then a step of drying the composition to shrink the polymer.
The polymer has a deformation ratio of 0.3 or more and 1 or less measured by the following method (1), and is a film of the polymer in a bending resistance test by the cylindrical mandrel method performed by the following method (2). A method in which the minimum diameter of a cylindrical mandrel that does not cause cracks is 2 mm or more and 25 mm or less.
Method (1): A 10% by 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, and a thickness of 0.03 mm in a range of 20 mm in width and 50 mm in length from one end of a short side in the length direction. Dry for 10 minutes in a constant temperature bath set at ° C. The length of the polyethylene sheet of the portion coated with the solution is L1, the length of the polyethylene sheet of the portion deformed by shrinkage after drying is L2, and the value of L2 / L1 is defined as the deformation ratio.
Method (2): A 30% by mass hexamethyldisiloxane solution of the polymer is prepared. The solution is applied to a polyethylene terephthalate film having a width of 50 mm, a length of 100 mm and a thickness of 0.1 mm using a 200 μm applicator, and dried in a constant temperature bath set at 40 ° C. for 120 minutes to prepare a test piece. The test piece is used to perform a bending resistance test in accordance with the cylindrical mandrel method specified in JIS K5600-5: 1: 1999, and the minimum diameter of the cylindrical mandrel at which the polymer film on the test piece does not crack. Ask for. A method of applying a composition containing a polymer having a silicone structure to the area around wrinkles on the skin.
The polymer has a deformation ratio of 0.3 or more and 1 or less measured by the following method (1), and is a film of the polymer in a bending resistance test by the cylindrical mandrel method performed by the following method (2). A method in which the minimum diameter of a cylindrical mandrel that does not cause cracks is 2 mm or more and 25 mm or less.
Method (1): A 10% by 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, and a thickness of 0.03 mm in a range of 20 mm in width and 50 mm in length from one end of a short side in the length direction. Dry for 10 minutes in a constant temperature bath set at ° C. The length of the polyethylene sheet of the portion coated with the solution is L1, the length of the polyethylene sheet of the portion deformed by shrinkage after drying is L2, and the value of L2 / L1 is defined as the deformation ratio.
Method (2): A 30% by mass hexamethyldisiloxane solution of the polymer is prepared. The solution is applied to a polyethylene terephthalate film having a width of 50 mm, a length of 100 mm and a thickness of 0.1 mm using a 200 μm applicator, and dried in a constant temperature bath set at 40 ° C. for 120 minutes to prepare a test piece. The test piece is used to perform a bending resistance test in accordance with the cylindrical mandrel method specified in JIS K5600-5: 1: 1999, and the minimum diameter of the cylindrical mandrel at which the polymer film on the test piece does not crack. Ask for. The method according to claim 2 or 3, wherein the region to which the composition is applied in the wrinkle peripheral portion includes at least a part of the region intersecting the direction of the wrinkles. The method according to claim 4, wherein the region is a region along the direction of wrinkles. The method according to claim 4 or 5, wherein the region is on both sides of the wrinkle. The method according to any one of claims 1 to 6, wherein the content of the polymer in the composition is 0.1% by mass or more and 30% by mass or less. Any of claims 1 to 7, wherein the polymer is at least one selected from the group consisting of silicone-modified polynorbornene, silicone-modified pullulan, trimethylsiloxysilicic acid, trifluoropropyldimethyl / trimethylsiloxysilicic acid, and acrylic silicone dendrimers. The method according to item 1. The ratio of the deformation ratio determined by the method (1) to the minimum mandrel diameter (mm) obtained by the method (2) [(deformation ratio) / (minimum diameter of the mandrel)] is 0.01 or more and 0.5. The method according to any one of claims 1 to 8 below.

Images