TW202034897A - Method for reducing skin wrinkles - Google Patents

Abstract

This method for reducing skin wrinkles involves applying to the skin a composition that contains a polymer having a silicone structure. Said polymer has a deformation ratio of 0.3-1, evaluated with a prescribed method (1), and, in a cylindrical mandrel bend test performed with a prescribed method (2), the minimum diameter of the cylindrical mandrel at which cracks do not occur in a film of said polymer is 2-25 mm.

Description

How to improve skin wrinkles

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

With the increase of age, the wrinkles of human skin increase. This is part of the skin aging phenomenon, which is affected by multiple factors such as changes in skin tissues and the effects of UV exposure.

There have been proposed techniques for making skin wrinkles inconspicuous, but the method performed by cosmetic plastic surgery must use skin penetration to control the shape. There are also known skin care products that non-invasively improve skin wrinkles, but the improvement effect is extremely low, and the satisfaction of women who are worried about wrinkles cannot be obtained.

Therefore, it is desired to control the skin shape non-invasively and effectively improve wrinkles.

However, for the purpose of improving the uniformity of the cosmetic film or the durability of the cosmetic, there are known cosmetics prepared with a film-forming polymer. Patent Document 1 relates to a cosmetic for color cosmetics, which is formulated with a predetermined fructooligosaccharide fatty acid ester, volatile hydrocarbon, and oil-soluble film-forming resin, and has excellent coating properties and uniformity of the cosmetic film. Patent Document 2 relates to a cosmetic that contains a film-forming polymer in which a predetermined functional group is introduced into the skeleton of a polycycloolefin polymer, and has good cosmetic durability and good touch.

[Prior Technical Literature] [Patent Literature]

Patent Document 1: Japanese Patent Laid-Open No. 2008-247761

Patent Document 2: Japanese Patent Laid-Open No. 2012-17317

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

[1] A method for improving skin wrinkles by applying a composition containing a polymer with a silicone structure to the skin, wherein the polymer has a deformation ratio of 0.3 or more as measured by the following method (1) And 1 or less, and in the bending resistance test of the cylindrical mandrel method by the following method (2), the minimum diameter of the cylindrical mandrel without cracking of the polymer film is 2mm or more and Below 25mm.

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

Method (2): Prepare a 30% by mass hexamethyldisiloxane solution of the above polymer. 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 coater, and dried in a thermostat set at 40° C. for 120 minutes to prepare a test piece. Using this test piece, the bending resistance test was carried out according to the cylindrical mandrel method specified in JIS K5600-5-1:1999, and the minimum diameter of the cylindrical mandrel without cracks in the polymer film on the test piece was obtained. .

[2] A method for improving skin wrinkles, comprising the steps of: applying a composition containing a polymer with a silicone structure to the wrinkle periphery of the skin; and The step of drying the composition to shrink the polymer; wherein the polymer has a deformation ratio determined by the above method (1) of 0.3 or more and 1 or less, and the circle performed by the method (2) In the bending resistance test by the cylindrical mandrel method, the minimum diameter of the cylindrical mandrel without cracking of the polymer 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 of the skin, wherein the polymer has a deformation ratio of 0.3 or more and 1 or less as measured by the above method (1) And in the bending resistance test of the cylindrical mandrel method by the above method (2), the minimum diameter of the cylindrical mandrel without cracking of the polymer film is 2mm or more and 25mm or less.

1‧‧‧Polyethylene sheet

1a‧‧‧One end of the short side of polyethylene sheet 1

2‧‧‧The part coated with polymer solution

Figure 1 (a) and (b) are explanatory diagrams of the evaluation method of the polymer deformation ratio (L2/L1) in the method (1).

Fig. 2 (a) to (c) is an example of a form in which the composition is applied to the skin around the wrinkle (rule wrinkle) in a flat or band shape.

Fig. 3 (a) to (c) are examples of the form in which the composition is applied to the skin around wrinkles (rule lines) in a linear shape.

Fig. 4 (a) and (b) are an example of a form in which the composition is applied in dots to the skin around wrinkles (rule lines).

5(a) and (b) are photographs showing the wrinkle improvement effect of Example 1. FIG.

6(a) and (b) are photographs showing the wrinkle improvement effect of Comparative Example 1. FIG.

The present invention relates to a method for applying a composition containing a polymer having a silicone structure to the periphery of the wrinkles of the skin. The deformation ratio of the polymer measured by the following method (1) is 0.3 or more and 1 or less, And the cylinder made by the following method (2) In the bending resistance test of the centripetal mandrel method, the minimum diameter of the cylindrical mandrel without cracking of the polymer film is 2 mm or more and 25 mm or less.

Furthermore, the present invention relates to a method for improving skin wrinkles, which has the steps of: applying a composition containing a polymer having a silicone structure to the wrinkle periphery of the skin; and then drying the composition to polymerize the composition The step of shrinkage of the polymer; the deformation ratio of the polymer is 0.3 or more and 1 or less as measured by the following method (1), and the bending resistance test of the cylindrical mandrel method by the following method (2) Among them, the minimum diameter of the cylindrical mandrel without cracking of the 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): Prepare a 10% by mass hexamethyldisiloxane solution of the above polymer. On one side of a polyethylene sheet with a width of 20 mm × a length of 100 mm × a thickness of 0.03 mm, 0.005 g of the solution was applied to a range of width 20 mm × length 50 mm from one end of the short side toward the length direction, and set it at 40°C. Dry in a constant temperature bath for 10 minutes. The length of the polyethylene sheet of the portion coated with the above solution is set to L1, the length of the polyethylene sheet of the portion deformed by shrinkage after drying is set to L2, and the value of L2/L1 is used as the deformation ratio.

Method (2): Prepare a 30% by mass hexamethyldisiloxane solution of the above polymer. 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 coater, and dried in a thermostat set at 40° C. for 120 minutes to prepare a test piece. Using this test piece, the bending resistance test was carried out according to the cylindrical mandrel method specified in JIS K5600-5-1:1999, and the minimum diameter of the cylindrical mandrel without cracks in the polymer film on the test piece was obtained. .

Furthermore, the present invention relates to a method for applying a composition containing a polymer having a silicone structure to the periphery of the wrinkles of the skin, the polymer having a deformation ratio measured by the above method (1) of 0.3 or more and 1 Below, and by the above method (2) In the bending resistance test of the conventional cylindrical mandrel method, the minimum diameter of the cylindrical mandrel without cracks in the polymer film is 2 mm or more and 25 mm or less. Hereinafter, this method is also appropriately referred to as the "application method of the present invention".

The so-called "skin wrinkles" in this manual refers to the unevenness and lines that appear on the surface of the skin. Skin wrinkles are prone to appear around the mouth, eyes, forehead, and neck. Small lines are small wrinkles, large lines are large wrinkles, and large wrinkles occur due to the distribution of pores such as nasolabial lines and cheeks. The improvement method of the present invention exerts the effect of making any type of wrinkles inconspicuous, especially in terms of non-invasive improvement of even large wrinkles like nasolabial folds.

The inventors of the present case found that by applying a composition containing a polymer (hereinafter also referred to as "polymer") with the aforementioned predetermined deformation ratio and bending resistance, and having a silicone structure, to the skin, it can be non-invasive The formula controls the shape of the skin and makes skin wrinkles less obvious.

The "method for improving skin wrinkles" in this specification refers to a method that stretches and stretches the skin around the wrinkles by the shrinking action of the polymer contained in the above composition, and controls the skin shape in a non-invasive manner. method. That is, it is a method of physically stretching the skin wrinkles to flatten the uneven shape of the skin surface, and for example, applying cosmetics to the skin to cover the unevenness of the skin surface, or optically making the wrinkles inconspicuous Different concepts.

<Polymer with silicone structure>

The polymer with silicone structure used in the present invention is a cylindrical mandrel with a deformation ratio of 0.3 or more and 1 or less as measured by the following method (1) and performed by the following method (2) In the bending resistance test of the method, the polymer film does not crack the cylindrical center The minimum shaft diameter is 2mm or more and 25mm or less.

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

Method (2): Prepare a 30% by mass hexamethyldisiloxane solution of the above polymer. 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 coater, and dried in a thermostat set at 40° C. for 120 minutes to prepare a test piece. Using this test piece, the bending resistance test was carried out according to the cylindrical mandrel method specified in JIS K5600-5-1:1999, and the minimum diameter of the cylindrical mandrel without cracks in the polymer film on the test piece was obtained. .

Since a polymer with a polysiloxane structure satisfies the aforementioned deformation ratio measured by method (1), for example, a composition containing the polymer is applied to the skin around wrinkles, and then the composition is dried When the film containing the polymer shrinks, the surface of the skin closely adhered to the film shrinks. With this action, the skin of the part where wrinkles occur is stretched, so wrinkles can be made inconspicuous. Therefore, the improvement method of the present invention preferably includes a step of applying the composition to the periphery of wrinkles of the skin; and then a step of drying the composition to shrink the polymer.

The evaluation method of the polymer deformation ratio (L2/L1) in the above method (1) is explained with reference to FIG. 1. First, a 10% by mass hexamethyldisiloxane solution of the polymer used in the composition is prepared. On one side of the polyethylene sheet 1 with a width (W) of 20 mm × a length (L0) of 100 mm × a thickness of 0.03 mm as shown in Figure 1 (a), 0.005 g of the solution is made of the polyethylene sheet 1. One end 1a of the short side is applied to the range of width 20mm×length 50mm from the length direction (the part of 2 shown in Figure 1(a)), and it is dried in a constant temperature bath set at 40°C for 10 minutes. Fig. 1(b) is a schematic diagram of a polyethylene sheet in which a part of the polyethylene sheet 1 coated with the above solution is dried and deformed (curled) due to polymer shrinkage.

On the dried polyethylene sheet (Figure 1(b)), set the length of the polyethylene sheet coated with the solution to L1 (50mm), and set the polyethylene sheet deformed by shrinkage after drying Set the length to L2, calculate L2/L1 and use this value 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 greater the shrinkage of the polymer caused by drying. The upper limit of L2/L1 is 1.

From the viewpoint of stretching skin wrinkles to make them inconspicuous, the deformation ratio L2/L1 evaluated by the above method (1) is 0.3 or more, preferably 0.5 or more, more preferably 0.6 or more, and even more preferably 0.7 or more , And more preferably 0.8 or more, particularly preferably 0.85 or more, even more preferably 0.9 or more, most preferably 0.95 or more, and the upper limit is 1.

Specifically, the deformation ratio can be evaluated by the method described in the examples.

In addition, the polymer used in the present invention has excellent bending resistance. In the bending resistance test of the cylindrical mandrel method performed by the above method (2), the polymer film is not cracked. The minimum diameter of the mandrel is 2mm or more and 25mm or less. Thereby, the film containing the polymer is not easy to be broken, and is easy to shrink in accordance with the state of following the skin shape.

The smaller the minimum diameter of the cylindrical mandrel, the better the bending resistance. From the viewpoint of obtaining sufficient adhesion between the film and the skin surface when the film containing the above-mentioned polymer is shrunk, the minimum diameter is 25mm or less, preferably 20mm or less, more preferably 12mm or less, and even more preferably 8mm Or less, more preferably 6 mm or less, particularly preferably 5 mm or less. On the other hand, in order to stretch the skin wrinkles and make them From the viewpoint of strength and shape control effect, the minimum diameter of the cylindrical mandrel that does not cause cracks is preferably 2 mm or more, more preferably 3 mm or more. The specific range of the minimum diameter of the cylindrical mandrel is preferably 2~25mm, more preferably 2~20mm, still more preferably 2~12mm, still more preferably 2~8mm, particularly preferably 3~6mm, most preferably Preferably it is 3~5mm.

The bending resistance can be evaluated using the type 1 bending test device specified in JIS K5600-5-1: 1999, specifically, according to the method described in the examples.

In addition, in the polymer with a silicone structure used in the present invention, the ratio of the deformation ratio obtained by the above method (1) to the minimum diameter of the mandrel (mm) obtained by the above method (2) [(Deformation ratio)/(minimum diameter of mandrel)], from the viewpoint of the skin wrinkle improvement effect, it is preferably 0.01 or more, more preferably 0.02 or more, still more preferably 0.10 or more, and still more preferably 0.15 As described above, from the viewpoint of imparting sufficient strength and shape control effects in order to stretch skin wrinkles so as to be inconspicuous, it is preferably 0.5 or less, more preferably 0.4 or less. The specific range of the above ratio is preferably 0.01 to 0.5, more preferably 0.02 to 0.5, still more preferably 0.10 to 0.5, still more preferably 0.15 to 0.5, particularly preferably 0.15 to 0.4.

The "polysiloxane structure" in this specification refers to the structure represented by the following general formula (I).

In general formula (I), R ^{1 is} each independently a hydrocarbon group having a carbon number of 1 or more and 12 or less, and p is an integer of 1 or more. When applied to the present invention, skin wrinkles are stretched to make them inconspicuous and sufficient wrinkle improvement effects are obtained (hereinafter also referred to as "skin wrinkle improvement effects") and from the viewpoint of versatility, R ^{1 is} preferably carbon An alkyl group having a number of 1 or more and 12 or less or an aryl group having a carbon number of 6 or more and 12 or less, more preferably an alkyl group or phenyl group having a carbon number of 1 or more and 12 or less, and still more preferably a carbon number of 1 or more and 3 or less The alkyl group is more preferably a methyl group.

The polymer may have a silicone structure as long as it has a silicone structure alone. However, from the viewpoint of making a polymer with the above-mentioned predetermined characteristics, it is preferable to partially have a silicone structure Of polymers.

In the case of a polymer having a polysiloxane structure partially, the polysiloxane structure may exist in either the main chain or the side chain in the polymer. From the viewpoint of making a polymer with the above-mentioned predetermined characteristics, It is preferably present in the side chain.

In the case that the silicone structure exists in the polymer main chain, the bonding form is not particularly limited. For example, the silicone structure can exist at the end of the polymer main chain, or the polysiloxane structure can be in block or A copolymer that is randomly bonded to the polymer backbone. In addition, a polymer modified by grafting a compound having a silicone structure can also be used.

烯等之含降

烷構造的聚矽氧改質聚合物；聚矽氧改質聚三葡萄糖(pullulan)；三烷基矽氧基矽酸、氟改質烷基矽氧基矽酸、苯基改質烷基矽氧基矽酸等之含聚矽氧構造的矽酸化合物；聚矽氧樹枝狀聚合物；等。 As the polymer used in the present invention, polysiloxane-modified polymer is preferred, and specific examples thereof include: polysiloxane-modified polymer

Alkene

Alkyl structure modified polysiloxane polymer; polysiloxane modified polytriglucose (pullulan); trialkylsiloxy silicic acid, fluorine modified alkyl siloxy silicic acid, phenyl modified alkyl silicon Silicic acid compounds containing polysiloxane structure such as oxysilicic acid; polysiloxane dendrimers; etc.

(Including drop

(Polysiloxane modified polymer with alkane structure)

烷構造，意指下述式所示構造。含降

烷構造的聚矽氧改質聚合物若為於聚合物中任意部位具有該式所示構造的聚矽氧改質聚合物即可。 The so-called drop in this manual

The alkane structure means a structure represented by the following formula. With drop

The polysiloxane-modified polymer having an alkane structure may be a polysiloxane-modified polymer having a structure represented by the formula in any part of the polymer.

[化2]

烷構造的聚矽氧改質聚合物，可舉例如具有下述一般式(1)或(2)所示重複單位的聚合物。 As containing drop

Examples of polysiloxane-modified polymers having an alkane structure include polymers having repeating units represented by the following general formula (1) or (2).

In the formula, R ^{2 is} each independently an alkyl group having a carbon number of 1 or more and 12 or less, 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.

[化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 above general formula (1), R ^{2 is} each independently an alkyl group having a carbon number of 1 or more and 12 or less. From the viewpoint of the skin wrinkle improvement effect and the versatility, methyl, ethyl, or normal Propyl, butyl or pentyl, more preferably methyl.

X is a group represented by the above formula (i). In the formula (i), R ^{1 is} each independently a hydrocarbon group having 1 to 12 carbon atoms. From the viewpoint of skin wrinkle improvement 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 a carbon number of 1 or more. The alkyl group or phenyl group of 12 or less is more preferably an alkyl group having 1 to 3 carbon atoms, and still more preferably a methyl group. c is an integer of 1 to 5, and from the viewpoint of versatility, c=1 is preferred. That is, X is preferably trimethylsiloxy.

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

In the above general formula (2), R ¹ , R ² and b are the same as above. d is an integer of 2 or more and 5 or less, and from the viewpoint of versatility, d=2 is preferable. For the cyclic polysiloxane structure in general formula (2), from the same viewpoint, it is preferable that R ¹ and R ² are methyl groups, and d is 2 or 3. That is, the cyclic polysiloxane structure in the general formula (2) is preferably the structure shown in the following formula (4) or (5).

烷構造的聚矽氧改質聚合物中上述一般式(1)或(2)所示重複單位的比例，係於該聚合物中之總重複單位數中，較佳為10%以上、更佳為30%以上、又更佳為50%以上。又，上限為100%、較佳為95%以下、更佳為90%以下、又更佳為70%以下。含降

烷構造的聚矽氧改質聚合物中上述一般式(1)或(2)所示重複單位數的具體範圍，係於該聚合物中之總重複單位數中，較佳為10~100%、更佳為10~95%、又更佳為30~90%、再更佳為50~70%。 From the point of view of skin wrinkle improvement effect, containing

The proportion of repeating units represented by the above general formula (1) or (2) in the polysiloxane modified polymer with alkane structure is based on the total number of repeating units in the polymer, preferably 10% or more, more preferably It is 30% or more, and more preferably 50% or more. Moreover, the upper limit is 100%, preferably 95% or less, more preferably 90% or less, and still more preferably 70% or less. With drop

The specific range of the number of repeating units shown in the above general formula (1) or (2) in the polysiloxane-modified polymer of alkane structure is based on the total number of repeating units in the polymer, preferably 10-100% , More preferably 10~95%, still more preferably 30~90%, still more preferably 50~70%.

烷構造的聚矽氧改質聚合物中，除了上述一般式(1)或(2)所示重複單位之外，亦可具有下述一般式(3)所示重複單位。 With drop

In addition to the repeating unit represented by the above general formula (1) or (2), the polysiloxane-modified polymer having an alkane structure may have a repeating unit represented by the following general formula (3).

[化7]

In the formula, R ³ to R ⁶ are each independently selected from a hydrogen atom, a halogen atom, and a C 1 to 10 alkyl group, alkenyl group, cycloalkyl group, aryl group, alkoxy group, aryloxy group, and halogenated hydrocarbon group The substituents of, or oxetanyl, alkoxycarbonyl, polyoxyalkylene, polyglyceryl, or alkoxysilyl. Two groups selected from R ³ to R ⁶ may also be bonded to each other to form an alicyclic structure, aromatic ring structure, carbamido group or anhydride group. The b system is the same as above.

烷構造的聚矽氧改質聚合物中上述一般式(3)所示重複單位的比例，係由皮膚之皺紋改善效果的觀點而言，係於該聚合物中之總重複單位數中，較佳為90%以下、更佳為70%以下、又更佳為50%以下。又，於含有上述一般式(3)所示重複單位的情況，其比例係於該聚合物中之總重複單位數中，較佳為5%以上、更佳為10%以上、又更佳為30%以上。含降

烷構造的聚矽氧改質聚合物中上述一般式(3)所示重複單位數的具體範圍，係於該聚合物中之總重複單位數中，較佳為5~90%、更佳為10~70%、又更佳為30~50%。 With drop

The proportion of repeating units shown in the above general formula (3) in the polysiloxane-modified polymer with alkane structure is based on the wrinkle improvement effect of the skin, and is based on the total number of repeating units in the polymer. It is preferably 90% or less, more preferably 70% or less, and still more preferably 50% or less. In addition, in the case of containing the repeating unit represented by the above general formula (3), the ratio is based on the total number of repeating units in the polymer, preferably 5% or more, more preferably 10% or more, and still more preferably More than 30%. With drop

The specific range of the number of repeating units shown in the above general formula (3) in the polysiloxane-modified polymer with alkane structure is based on the total number of repeating units in the polymer, preferably 5 to 90%, more preferably 10~70%, more preferably 30~50%.

烷構造的聚矽氧改質聚合物中上述一般式(1)~(3)所示重複單位的比例，可藉由¹H-NMR測定求得。 With drop

The ratio of the repeating units represented by the above general formulas (1) to (3) in the polysiloxane-modified polymer with an alkane structure can be determined by ¹ H-NMR measurement.

烷構造的聚矽氧改質聚合物，較佳為聚矽氧改質聚降

烯，更佳係下述式(6)所示之聚矽氧改質聚降

烯。 As containing drop

Polysiloxane modified polymer with alkane structure, preferably polysiloxane modified polymer

Alkene, more preferably a polysiloxane modified polysiloxane represented by the following formula (6)

Ene.

[化8]

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

From the viewpoint of skin wrinkle improvement effect, the ratio of e to f in general formula (6) is preferably e/f=20/80~90/10 (mol/mol), more preferably e/f= 30/70~80/20(mol/mol), and more preferably e/f=50/50~70/30(mol/mol).

烷構造的聚矽氧改質聚合物之數量平均分子量Mn，係由兼顧收縮性與耐彎曲性的觀點及皮膚之皺紋改善效果的觀點而言，較佳為5萬以上、更佳為10萬以上、又更佳為20萬以上，且較佳為200萬以下、更佳為150萬以下、又更佳為80萬以下、再更佳為60萬以下。含降

烷構造的聚矽氧改質聚合物之數量平均分子量Mn的具體範圍，較佳為5萬~200萬、更佳為10萬~150萬、又更佳為20萬~80萬、再更佳為20萬~60萬。 With drop

The number average molecular weight Mn of the polysiloxane-modified polymer with alkane structure is from the viewpoint of both shrinkage and bending resistance and the effect of improving skin wrinkles, and is preferably 50,000 or more, more preferably 100,000 Above, more preferably 200,000 or more, and 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. With drop

The specific range of the number average molecular weight Mn of the polysiloxane modified polymer with alkane structure is preferably 50,000 to 2 million, more preferably 100,000 to 1.5 million, more preferably 200,000 to 800,000, and even more preferably 200,000 to 600,000.

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

烷構造的聚矽氧改質聚合物係例如使含有降

烷構造或可形成降

烷構造之聚矽氧改質環狀烯烴單體依公知方法加成聚合而獲得。 With drop

The polysiloxane modified polymer with alkane structure, for example, reduces the content

Alkane structure may form a drop

The polysiloxane-modified cyclic olefin monomer with alkane structure is obtained by addition polymerization according to a known method.

烷構造的聚矽氧改質聚合物，則可使下述一般式(1a)或(2a)所示環狀烯烴 單體加成聚合而獲得。再者，於加成聚合中，亦可使下述一般式(3a)所示環狀烯烴單體進行共聚合。 If it is, for example, the content of the repeating unit shown in the above general formula (1) or (2)

The polysiloxane modified polymer with an alkane structure can be obtained by addition polymerization of a cyclic olefin monomer represented by the following general formula (1a) or (2a). In addition, in addition polymerization, a cyclic olefin monomer represented by the following general formula (3a) may also be copolymerized.

In the formula, R ^{1 is} each independently an alkyl group having a carbon number of 1 or more and 12 or less, 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} each independently a hydrocarbon group having a carbon number of 1 or more and 12 or less, and c is an integer of 1 or more and 5 or less.

[化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.

In the formula, R ³ to R ⁶ are each independently selected from a hydrogen atom, a halogen atom, and a C 1 to 10 alkyl group, alkenyl group, cycloalkyl group, aryl group, alkoxy group, aryloxy group, and halogenated hydrocarbon group The substituents of, or oxetanyl, alkoxycarbonyl, polyoxyalkylene, polyglyceryl, or alkoxysilyl. Two groups selected from R ³ to R ⁶ may also be bonded to each other to form an alicyclic structure, aromatic ring structure, carbamido group or anhydride group. The b system is the same as above.

When the cyclic olefin monomer represented by the general formula (3a) is copolymerized, the amount used is based on the skin wrinkle improving effect, when the total monomer used in the polymerization is set to 100 mol% , It is preferably 90 mol% or less, more preferably 70 mol% or less, still more preferably 50 mol% or less, and preferably 5 mol% or more, It is more preferably 10 mol% or more, and still more preferably 30 mol% or more.

烯可使下述式(6a)所示參(三甲基矽氧基)矽基降

烯、與降

烯進行加成聚合而獲得。 The polysiloxy modified polysiloxane shown in the above formula (6)

The ene can reduce the silyl group represented by the following formula (6a) (trimethylsiloxy)

Ene, and drop

The olefin is obtained by addition polymerization.

烯、與降

烯之共聚合比較佳為20/80~90/10(mol/mol)、更佳為30/70~80/20(mol/mol)、又更佳為50/50~70/30(mol/mol)。 From the viewpoint of skin wrinkle improvement effect, ginseng (trimethylsiloxy) silyl reduces

Ene, and drop

The copolymerization of olefin is preferably 20/80~90/10 (mol/mol), more preferably 30/70~80/20 (mol/mol), and even more preferably 50/50~70/30 (mol/mol) mol).

In addition, the repeating units shown in the above general formulas (1) to (3) and the above formula (6) all represent the 2,3-addition structural unit of the cyclic olefin monomer which is the raw material monomer, but It may also contain the 2,7-addition structural unit caused by the addition polymerization of the cyclic olefin monomer.

烷構造的聚矽氧改質聚合物，較佳為降

烯/參(三甲基矽氧基)矽基降

烯)共聚物，由INCI名(International Cosmetic Ingredient Dictionary and Handbook，第16版，第2卷，2016年，p.2274)：NORBORNENE/TRIS(TRIMETHYLSILOXY)SILYLNORBORNENE COPOLYMER所記載之化合物。 As containing drop

Polysiloxane modified polymer with alkane structure, preferably

Ene / ginseng (trimethylsiloxy) silyl drop

Olefin) copolymer, a compound described by INCI name (International Cosmetic Ingredient Dictionary and Handbook, 16th edition, Vol. 2, 2016, p. 2274): NORBORNENE/TRIS (TRIMETHYLSILOXY) SILYLNORBORNENE COPOLYMER.

烷構造的聚矽氧改質聚合物，可舉例如信越化學工業(股)製「NBN-30-ID」(降

烯/參(三甲基矽氧基)矽基降

烯)共聚物之異十二烷溶液)等。 As a commercially available drop

The polysiloxane modified polymer with alkane structure, for example, "NBN-30-ID" manufactured by Shin-Etsu Chemical Co., Ltd.

Ene / ginseng (trimethylsiloxy) silyl drop

Olefin) copolymer in isododecane solution) and so on.

(Polysiloxane modified polytriglucose)

Examples of the polysiloxane-modified triglucose include triglucose having a polysiloxane structure in the side chain. Specifically, from the viewpoint of the skin wrinkle improvement effect and the versatility, polytriglucose is preferred. Triglucosamine modified polytriglucose is modified by polysiloxy substituted with at least part of the hydrogen atoms of the OH group in the following general formula (7).

[化14]-Z ¹ -SiX _a R ² _3-a (7)

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

In 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 more preferably the following The divalent group represented by general formula (9).

In the formula, R ¹¹ is an alkylene group having a carbon number of 1 to 10, and examples thereof include methylene, ethylene, trimethylene, propylene, and butylene. From the same viewpoint, among these, ethylene, trimethylene, and propylene are preferable, and trimethylene or propylene is more preferable.

As commercially available polysiloxane-modified triglucosamine, for example, "TSPL-30-ID" (tris(trimethylsiloxy) silylpropyl urethane triglucose) manufactured by Shin-Etsu Chemical Co., Ltd. Isododecane solution), "TSPL-30-D5" (tris (trimethylsiloxy) silylpropyl urethane triglucose cyclopentasiloxane solution), etc.

(Silicic acid compound containing polysiloxane structure)

As the silicic acid compound containing a polysiloxane structure used in the present invention, for example, a silicic acid compound having a polysiloxane structure at the end can be mentioned, for example, trialkylsiloxysilicic acid, fluorine-modified alkylsilicic acid Alkylsilicic acid, phenyl modified alkylsiloxysilicic acid, etc.

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

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 fluorine atoms. As specific examples thereof, for example, trifluoropropyldimethylsiloxysilicic acid, trifluoropropyldimethyl/trimethylsiloxysilicic acid, etc. may be mentioned.

Examples of phenyl-modified alkylsiloxysilicic acid include phenylpropyldimethylsiloxysilicic acid, phenylpropyldimethyl/trimethylsiloxysilicic acid, and the like.

Among the silicic acid compounds containing polysiloxane structure, from the viewpoint of the skin wrinkle improvement effect, it is preferably selected from the group consisting of trialkylsiloxysilicic acid and fluorine-modified alkylsiloxysilicic acid More than one.

As commercially available silicic acid compounds containing polysiloxane structure, Shin-Etsu Chemical Co., Ltd. products "KF-7312J", "KF-7312K", "KF-7312T", "KF-7312L", and "X- 21-5249", "X-21-5250", "KF-9021", "X-21-5595", "X-21-5616", "KF-9021L", "X-21-5249L", " X-21-5250L" and other trimethylsiloxysilicic acid (solution), manufactured by Momentive Performance Materials Japan contract company "XS66-B8226" (trifluoropropyldimethyl/trimethylsiloxysilicic acid Cyclopentasiloxane solution), "XS66-B8636" (three Polydimethylsiloxane solution of fluoropropyldimethyl/trimethylsiloxysilicic acid), "SilShinel51" (phenylpropyldimethylsiloxysilicic acid), etc.

(Polysiloxy dendrimer)

Examples of the polysiloxane dendrimer include vinyl polymers having a silicone dendrimer structure in the side chain. The silicone dendrimer structure is based on the viewpoint of the skin wrinkle improvement effect and the versatility. Specifically, it is preferably a group represented by the following general formula (10).

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 base represented by the following general formula (11) when i=1, and i is an integer from 1 to 10 that represents the level of the base.

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

In general formula (10), Z ² is a single bond or a divalent organic group. From the viewpoint of versatility, it is preferably a divalent organic group, and more preferably the following general formulas (12), (13) or ( 14) The divalent base shown.

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

As the above-mentioned vinyl polymer having a silicone dendrimer structure in the side chain (hereinafter also referred to as "vinyl polymer"), for example, a monomer represented by the following general formula (15) Derivative polymer of repeating units.

In the formula, R ¹ and X ¹ are the same as above. Y is a group containing a vinyl bond, and examples thereof include vinyl, 2-propenyloxyethyl, 3-propenyloxypropyl, 2-methacryloyloxyethyl, and 3-methacryloyloxyethyl. Oxypropyl, 4-vinylphenyl, 3-vinylphenyl, 4-(2-propenyl)phenyl, 3-(2-propenyl)phenyl, 2-(4-vinylphenyl) ) Ethyl, 2-(3-vinylphenyl)ethyl, allyl, 5-hexenyl. Among these, from the viewpoint of versatility, a (meth)acryloyl group or a vinyl group is preferred, and a (meth)acryloyl group is more preferred.

The vinyl polymer may further contain a repeating unit derived from a vinyl monomer other than the monomer represented by the above general formula (15). The vinyl-based monomer is a monomer other than the monomer represented by the general formula (15) having a vinyl bond-containing group, and examples thereof include (meth)acrylic acid, alkyl (meth)acrylate, Hydroxyalkyl (meth)acrylate, aromatic ring-containing (meth)acrylate, fatty acid vinyl ester, (meth)acrylamide, styrene or its derivatives, etc., one or two of these can be used More than species. Among these, from the viewpoint of versatility, preferred are (meth)acrylic acid, alkyl (meth)acrylate, hydroxyalkyl (meth)acrylate, and aromatic ring-containing (meth)acrylic acid. (Meth)acrylic monomers such as esters.

In the vinyl polymer, the content of the repeating unit derived from the monomer represented by the general formula (15) is based on the skin wrinkle improving effect, relative to the total repeating unit in the vinyl polymer , Preferably 0.1% by mass or more, more preferably 10% by mass or more, and still more preferably 20% by mass or more. In addition, the upper limit is 100% by mass.

The above-mentioned vinyl polymer is more preferably an acrylic polymer. That is, as a preferable polysiloxane dendrimer, it is an acrylic polymer having a silicone dendrimer structure in the side chain (hereinafter also referred to as "acrylic polysiloxane dendrimer"). Compound"). Acrylic polysiloxane dendrimers are polymers having repeating units derived from monomers in which Y is a (meth)acryloyl group in the above general formula (15), and may further contain those derived from the general formula (15) Shows repeating units derived from (meth)acrylic monomers other than monomers.

Commercially available polysiloxane dendrimers include, for example, "FA 4001 CM Silicone Acrylate" manufactured by Toray Dow Corning Co., Ltd. (Cyclopentasiloxane of acrylate-polytrimethylsiloxy methacrylate copolymer) Oxane solution), "FA 4002 ID Silicone Acrylate" (isododecane solution of acrylate-polytrimethylsiloxy methacrylate copolymer) and other acrylic polysiloxane dendrimers.

烯、聚矽氧改質聚三葡萄糖、三甲基矽氧基矽酸、三氟丙基二甲基/三甲基矽氧基矽酸、及丙烯酸系聚矽氧樹枝狀聚合物所構成群的1種以上，更佳為選自由聚矽氧改質聚降

烯、聚矽氧改質聚三葡萄糖、三甲基矽氧基矽酸及三氟丙基二甲基/三甲基矽氧基矽酸所構成群的1種以上；由皮膚之皺紋改善效果及耐彎曲性的觀點而言，又更佳為選自由聚矽氧改質聚降

烯及聚矽氧改質聚三葡萄糖所構成群的1種以上，再更佳為聚矽氧改質聚降

烯。 Among the above polymers, from the viewpoint of the effect of improving skin wrinkles, it is preferably selected from the group consisting of polysiloxane modified polymer

A group consisting of olefin, polysiloxane modified polytriglucose, trimethylsiloxysilicic acid, trifluoropropyl dimethyl/trimethylsiloxysilicic acid, and acrylic-based polysiloxy dendrimer 1 or more of, it is better to choose from polysilicone modified polymer

One or more of the group consisting of olefin, polysiloxane modified polyglucose, trimethylsiloxysilicic acid and trifluoropropyldimethyl/trimethylsiloxysilicic acid; the effect of improving wrinkles on the skin From the viewpoint of bending resistance, it is better to choose from

One or more of the group consisting of polytriglucose modified by olefin and polysiloxane, and more preferably modified by polysiloxane.

Ene.

The content of the above-mentioned 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, and still more preferably 1% by mass or more from the viewpoint of skin wrinkle improvement effect , And more preferably 5 mass% or more. In addition, from the viewpoints of coating properties of the composition, freedom of formulation, and no discomfort to the skin after drying, the content of the polymer in the composition is preferably 30% by mass or less, more preferably 25% by mass Or less, more preferably 20% by mass or less, still more preferably 15% by mass the following. The specific range of the content of the above-mentioned polymer in the composition is preferably 0.1-30% by mass, more preferably 0.5-25% by mass, still more preferably 1-20% by mass, and still more preferably 1-15% by mass , Especially preferred is 5-15% by mass.

<Volatile Oil>

The composition used in the present invention, from the viewpoint of further improving the effect of improving skin wrinkles, may further contain volatility with a volatilization rate of 14% or more after drying at 1 atmosphere, 40°C, and 60%RH for 30 minutes oil. If the volatile oil is contained, the drying speed of the composition containing the polymer is increased, and the shrinkage of the polymer during the drying process is accelerated, and the effect of stretching the skin wrinkles by the above-mentioned action mechanism is further improved.

From the viewpoint of obtaining the above effects, the volatilization rate of the volatile oil after drying for 30 minutes at 1 atmosphere, 40°C, and 60%RH is preferably 18% or more, more preferably 25% or more, and even more preferably 30% Above, more preferably 45% or more, still more preferably 65% or more, particularly preferably 80% or more, and most preferably 95% or more. Also, the upper limit is 100%.

The volatilization rate of the volatile oil is to put 0.5g of the sample into a glass dish with a diameter of 40mm, and let it dry at 40℃ for 30 minutes under 1 atmospheric pressure and 60%RH. The mass of the sample before drying Set as W ₀ (g) and the mass of the sample after drying as W ₁ (g), which is calculated by {(W ₀ -W ₁ )/W ₀ }×100.

Moreover, two or more types of volatile oils can be used.

Preferred specific examples of volatile oils include, for example, one or more oils selected from the group consisting of hydrocarbon oils and silicone oils and having a volatility rate in the above-mentioned range. Among these volatile oils, preferably selected from isododecane (33% volatility), hexamethyldisiloxane (100% volatility), methyl trimethylsiloxane, 25°C The dynamic viscosity is below 2cSt One or more of the following dimethyl polysiloxane groups. In addition, the dynamic viscosity can be measured using, for example, a Ubbelohde viscometer.

As the volatile oil, more preferably one or more selected from the group consisting of isododecane and hexamethyldisiloxane, and still more preferably hexamethyldisiloxane.

The content of the volatile oil in the composition used in the present invention, from the viewpoint of improving the effect of improving skin wrinkles, is preferably 1% by mass or more, more preferably 5% by mass or more, and still more preferably 10 % By mass, still more preferably 20% by mass or more, more preferably 25% by mass or more, still more preferably 35% by mass or more, still more preferably 45% by mass or more, more preferably 50% by mass or more, and more preferably 60% by mass or more, more preferably 70% by mass or more, and still more preferably 80% by mass or more; from the viewpoint of improving the wrinkle improvement effect of the skin and the degree of freedom of formulation, it is preferably 99.9% by mass Or less, more preferably 99.5% by mass or less, still more preferably 99% by mass or less, still more preferably 97% by mass or less, and 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 preferably 20 to 99.5% by mass , More preferably 25~99.5% by mass, still more preferably 35~99.5% by mass, still more preferably 35~99% by mass, more preferably 45~99% by mass, still more preferably 50~99% by mass, and still more It is preferably 60 to 99% by mass, more preferably 70 to 99% by mass, still more preferably 80 to 99% by mass, still more preferably 80 to 97% by mass, and still 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 normally formulated such as cosmetics within a range that does not impair the purpose of the present invention. Examples of the component include surfactants, water-soluble polymers, antioxidants, and ultraviolet rays. Absorbents, vitamins, preservatives, pH adjusters, fragrances, plant extracts, moisturizers, colorants, cooling agents, perspirants, antiseptics, skin active agents, etc.

The form of the composition used in the present invention may be a form that can be applied to the skin by coating or the like, and examples include solutions, emulsions, creams, emulsions, gels, films, sheets, foams, etc. The form.

From the viewpoint that the composition used in the present invention is applied to the skin by coating, etc., and then the composition is dried to shrink the polymer to exert the effect of improving skin wrinkles, it is preferably applied to the skin When it is liquid, it is more preferably liquid at 25°C.

In addition, the composition used in the present invention is preferable from the viewpoint of accelerating the shrinkage of the polymer and improving the effect of improving skin wrinkles in the step of applying the composition to the skin and then drying the composition The water content is less. 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, more preferably 1% by mass or less, It is still more preferably 0.5% by mass or less, and still 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 above-mentioned composition to the periphery of wrinkles of the skin.

In the application method of the present invention, for example, it is applied by coating the above-mentioned composition on the periphery of wrinkles. With this application method, the above-mentioned action mechanism can be used to non-invasively control the skin shape and make skin wrinkles less obvious.

The "peripheral part of skin wrinkles" in this manual is different from the inner part of wrinkles, that is, the concave parts of the skin surface or the concave parts of the lines. In the present invention, by applying the polymer-containing composition to the skin around wrinkles, when the composition is dried, the polymer-containing film shrinks and the skin surface at the wrinkle periphery also shrinks. Shrink, the skin where wrinkles occur is stretched and wrinkles become inconspicuous. Furthermore, the improvement method of the present invention and the application method of the present invention are not limited to the periphery of wrinkles of the skin before the effects of the present invention can be obtained, and the above composition can also be applied to the inside of wrinkles.

From the viewpoint of obtaining the above-mentioned effect, it is preferable that the wrinkle peripheral portion includes at least a part of the region intersecting the wrinkle direction as the region to which the composition is applied. The so-called wrinkle direction is the direction in which the fingerprint path extends. This is due to the fact that by applying the above composition to the area intersecting with the wrinkle direction, the skin where the wrinkle occurs is stretched and the wrinkle becomes inconspicuous.

The area intersecting the wrinkle direction is preferably an area along the wrinkle direction, and the area may be only one side of the wrinkle or both sides. In particular, it is more preferable to apply the above-mentioned composition on both sides of the wrinkles. This is because the wrinkles can be made more inconspicuous by stretching the wrinkled skin from both sides of the wrinkles.

As a form in which the composition is applied to the area along the wrinkle direction, for example, a form in which the composition is applied to the area in the form of a surface, a band, a line, or a dot. Specifically, FIG. 2 described later can be illustrated. ~ The shape shown in Figure 4.

In addition, in the case where the wrinkle direction is not parallel to the direction of gravity, such as a nasolabial fold, the area where the composition is applied (the area intersecting the wrinkle direction) preferably includes the area above the wrinkle. The so-called "direction of gravity" here refers to the direction of gravity when a person stands upright. The so-called "upper side" means the direction opposite to the above-mentioned gravity direction. By applying the above composition at least on the area above the wrinkles, the skin where the wrinkles occur is stretched upward, making the wrinkles more inconspicuous. From the same point of view as above, when the wrinkle direction is not parallel to the direction of gravity, the area where the composition is applied is the area above and below the wrinkle, and more preferably the area above the wrinkle is relatively small. Under wrinkles A wider range of the side area.

Figures 2 to 4 show an example of the application of the above composition in the application method of the present invention.

Fig. 2 is a form in which the composition is applied to the skin around wrinkles (rule wrinkles) in a flat or band shape, Fig. 2(a) is a form where the composition is applied to the area above the wrinkles, Fig. 2(b), (c) The composition is applied to the upper and lower areas of the wrinkles. From the viewpoint of making wrinkles more inconspicuous, it is better to apply the composition as shown in Figure 2(c) where the area where the composition is applied is the area on the upper and lower sides of the wrinkle, and the area on the upper side of the wrinkle is larger than the lower side of the wrinkle The area is wider.

Figure 3 (a), (b), and (c) show the composition applied to the skin around wrinkles (law lines) in a linear form. Figure 4 (a) and (b) show the wrinkles (law lines). ) The skin of the peripheral part is coated with the composition in the form of dots. As shown in Figures 3 and 4, in the case of applying the above composition in a line or dot form, from the viewpoint of stretching the skin equally from both sides of the wrinkle, it is preferable to apply the composition to Enclose the areas above and below the wrinkles.

In the application method of the present invention, the amount of the above-mentioned composition used is not particularly limited as long as the effect of making wrinkles appear inconspicuous is not particularly limited, for example, the amount is 0.01 g or more and 10 g or less.

In the application method of the present invention, it is preferable to include a step of applying the composition to the periphery of wrinkles of the skin, etc.; and then a step of drying the composition to shrink the polymer. Due to this drying, the above-mentioned polymer in the composition coated on the skin shrinks, and the shrinkage action stretches and stretches the skin around the wrinkles, flattening the uneven shape of the skin surface, and then exerts The effect of making wrinkles inconspicuous.

After drying, the above composition can be removed as needed. Alternatively, the above composition can also be After applying the product to the skin and then drying, apply makeup without removing the above-mentioned composition.

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

<1> A method for improving skin wrinkles is to apply a composition containing a polymer with a silicone structure 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 in the bending resistance test of the cylindrical mandrel method by the following method (2), the polymer The minimum diameter of the cylindrical mandrel without film cracking is 2mm or more and 25mm or less.

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

Method (2): Prepare a 30% by mass hexamethyldisiloxane solution of the above polymer. 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 coater, and dried in a thermostat set at 40° C. for 120 minutes to prepare a test piece. Using this test piece, the bending resistance test was carried out according to the cylindrical mandrel method specified in JIS K5600-5-1:1999, and the minimum diameter of the cylindrical mandrel without cracks in the polymer film on the test piece was obtained. .

<2> A method for improving skin wrinkles, comprising the steps of: applying a composition containing a polymer having a silicone structure to the wrinkle periphery of the skin; and then drying the composition to make the composition Steps of polymer shrinkage;

The polymer has a deformation ratio of 0.3 or more and 1 or less measured by the above method (1), and in the bending resistance test of the cylindrical mandrel method by the above method (2), the polymer film The minimum diameter of the cylindrical mandrel without cracks is 2 mm or more and 25 mm or less.

烷構造之聚矽氧改質聚合物、聚矽氧改質聚三葡萄糖、含有聚矽氧構造之矽酸化合物、及聚矽氧樹枝狀聚合物所構成群的1種以上，上述組成物中之該聚合物的含量為0.1質量%以上且30質量%以下，藉上述方法(1)所測定之變形比例為0.5以上且1以下。 <3> The method of <1> or <2>, wherein the polymer is selected from

One or more of the group consisting of polysiloxane-modified polymer with alkane structure, polysiloxane-modified triglucose, silicic acid compound containing polysiloxane structure, and polysiloxane dendrimer, among the above compositions The content of the polymer is 0.1% by mass or more and 30% by mass or less, and the deformation ratio measured by the above method (1) is 0.5 or more and 1 or less.

<4> The method of any one of <1> to <3>, wherein the deformation ratio obtained by the above method (1) is relative to the minimum diameter of the mandrel obtained by the above method (2) (mm The ratio of) [(deformation ratio)/(minimum diameter of mandrel)] is 0.01 or more and 0.5 or less.

<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.

烷構造之聚矽氧改質聚合物及聚矽氧改質聚三葡萄糖所構成群的1種以上。 <6> The method according to any one of <1> to <5>, wherein the polymer is selected from

One or more of the group consisting of polysiloxane-modified polymer with alkane structure and polysiloxane-modified triglucose.

<7> The method according to any one of <1> to <6>, wherein in the bending resistance test of the cylindrical mandrel method carried out by the above method (2), the film of the polymer does not cause turbulence. The minimum diameter of the cracked cylindrical mandrel is 2mm or more and 12mm or less.

<8> The method according to any one of <1> to <7>, wherein the deformation ratio measured by the above method (1) is 0.85 or more and 1 or less.

<9> The method of any one of <1> to <8>, wherein the deformation ratio obtained by the above method (1) is relative to the minimum diameter of the mandrel obtained by the above method (2) (mm ) Ratio The rate [(deformation ratio)/(minimum diameter of mandrel)] is 0.10 or more and 0.5 or less.

烷構造之聚矽氧改質聚合物。 <10> The method of any one of <1> to <9>, wherein the above-mentioned polymer contains

Polysiloxane modified polymer with alkane structure.

烷構造之聚矽氧改質聚合物為下式(6)所示之聚矽氧改質聚降

烯。 <11> The method as in <10>, which contains

The polysiloxane modified polymer with alkane structure is the polysiloxane modified polymer shown in the following formula (6)

Ene.

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

<12> The method as in <11>, wherein the ratio of e to f in the above formula (6) is e/f=20/80~90/10 (mol/mol).

<13> The method according to any one of <1> to <12>, wherein, in the bending resistance test of the cylindrical mandrel method carried out by the above method (2), the film of the polymer does not cause turbulence. The minimum diameter of the cracked cylindrical mandrel is 3mm or more and 5mm or less.

<14> The method according to any one of <1> to <13>, wherein the deformation ratio measured by the above method (1) is 0.95 or more and 1 or less.

<15> The method of any one of <1> to <14>, wherein the deformation ratio obtained by the above method (1) is relative to the minimum diameter of the mandrel obtained by the above method (2) (mm The ratio of) [(deformation ratio)/(minimum diameter of mandrel)] is 0.15 or more and 0.4 or less.

烷構造之聚矽氧改質聚合物及聚矽氧改質聚三葡萄糖 所構成群的1種以上，上述組成物中之該聚合物的含量為1質量%以上且20質量%以下；藉上述方法(1)所測定之變形比例為0.85以上且1以下；藉上述方法(2)所進行之圓筒形心軸法的耐彎曲性試驗中，該聚合物之膜不發生龜裂的圓筒形心軸之最小直徑為2mm以上且12mm以下。 <16> The method according to any one of <1> to <3>, wherein the polymer is selected from

One or more of the group consisting of polysiloxane-modified polymer with alkane structure and polysiloxane-modified triglucose, the content of the polymer in the above composition is 1% by mass or more and 20% by mass or less; The deformation ratio measured by the method (1) is 0.85 or more and 1 or less; in the bending resistance test of the cylindrical mandrel method by the method (2) above, the polymer film does not crack The minimum diameter of the mandrel is 2mm or more and 12mm or less.

烷構造之聚矽氧改質聚合物及聚矽氧改質聚三葡萄糖所構成群的1種以上，上述組成物中之該聚合物的含量為1質量%以上且20質量%以下；藉上述方法(1)所測定之變形比例為0.85以上且1以下；藉上述方法(2)所進行之圓筒形心軸法的耐彎曲性試驗中，該聚合物之膜不發生龜裂的圓筒形心軸之最小直徑為2mm以上且12mm以下；藉上述方法(1)所求得之變形比例相對於藉上述方法(2)所求得之心軸最小直徑(mm)的比率[(變形比例)/(心軸最小直徑)]為0.10以上且0.5以下。 <17> The method according to any one of <1> to <3>, wherein the polymer is selected from

One or more of the group consisting of polysiloxane-modified polymer with alkane structure and polysiloxane-modified triglucose, the content of the polymer in the above composition is 1% by mass or more and 20% by mass or less; The deformation ratio measured by the method (1) is 0.85 or more and 1 or less; in the bending resistance test of the cylindrical mandrel method by the method (2) above, the polymer film does not crack The minimum diameter of the mandrel is 2mm or more and 12mm or less; the ratio of the deformation ratio obtained by the above method (1) to the minimum diameter of the mandrel (mm) obtained by the above method (2) [(deformation ratio )/(Minimum diameter of mandrel)] is 0.10 or more and 0.5 or less.

烷構造之聚矽氧改質聚合物，上述組成物中之該聚合物的含量為1質量%以上且20質量%以下；藉上述方法(1)所測定之變形比例為0.95以上且1以下；藉上述方法(2)所進行之圓筒形心軸法的耐彎曲性試驗中，該聚合物之膜不發生龜裂的圓筒形心軸之最小直徑為3mm以上且5mm以下。 <18> The method of any one of <1> to <3>, wherein the above-mentioned polymer contains

Polysiloxane modified polymer with alkane structure, the content of the polymer in the above composition is 1% by mass or more and 20% by mass or less; the deformation ratio measured by the above method (1) is 0.95 or more and 1 or less; In the bending resistance test of the cylindrical mandrel method by the above method (2), the minimum diameter of the cylindrical mandrel without cracking of the polymer film is 3 mm or more and 5 mm or less.

烷構造之聚矽氧改質聚合物，上述組成物中之該聚合物的含量為1質量%以上且20質量%以下；藉上述方法(1)所測定之變形比例為0.95以上且1以下；藉上述方法(2)所進行之圓筒形心軸法的耐 彎曲性試驗中，該聚合物之膜不發生龜裂的圓筒形心軸之最小直徑為3mm以上且5mm以下；藉上述方法(1)所求得之變形比例相對於藉上述方法(2)所求得之心軸最小直徑(mm)的比率[(變形比例)/(心軸最小直徑)]為0.15以上且0.4以下。 <19> The method according to any one of <1> to <3>, wherein the polymer contains

Polysiloxane modified polymer with alkane structure, the content of the polymer in the above composition is 1% by mass or more and 20% by mass or less; the deformation ratio measured by the above method (1) is 0.95 or more and 1 or less; In the bending resistance test of the cylindrical mandrel method by the above method (2), the minimum diameter of the cylindrical mandrel without cracking of the polymer film is 3mm or more and 5mm or less; by the above method (1) The ratio [(deformation ratio)/(minimum spindle diameter)] of the obtained deformation ratio to the minimum diameter of the mandrel (mm) obtained by the above method (2) is 0.15 or more and 0.4 or less.

烯，上述組成物中之該聚合物的含量為1質量%以上且20質量%以下；藉上述方法(1)所測定之變形比例為0.95以上且1以下；藉上述方法(2)所進行之圓筒形心軸法的耐彎曲性試驗中，該聚合物之膜不發生龜裂的圓筒形心軸之最小直徑為3mm以上且5mm以下。 <20> The method according to any one of <1> to <3>, wherein the above-mentioned polymer is a polysiloxy modified polymer represented by the following formula (6)

The content of the polymer in the above composition is 1% by mass or more and 20% by mass or less; the deformation ratio measured by the above method (1) is 0.95 or more and 1 or less; by the above method (2) In the bending resistance test by the cylindrical mandrel method, the minimum diameter of the cylindrical mandrel on which the polymer film does not crack is 3 mm or more and 5 mm or less.

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

<21> The method of <20>, wherein the ratio of e to f in the above formula (6) is e/f=20/80~90/10 (mol/mol).

烯，上述組成物中之該聚合物的含量為1質量%以上且20質量%以下；藉上述方法(1)所測定之變形比例為0.95以上且1以下；藉上述方法(2)所進行之圓筒形心軸法的耐彎曲性試驗中，該聚合物之膜不發生龜裂的圓筒形心軸之最小直徑為 3mm以上且5mm以下；藉上述方法(1)所求得之變形比例相對於藉上述方法(2)所求得之心軸最小直徑(mm)的比率[(變形比例)/(心軸最小直徑)]為0.15以上且0.4以下。 <22> The method according to any one of <1> to <3>, wherein the above-mentioned polymer is a polysiloxane modified polysiloxane represented by the following formula (6)

The content of the polymer in the above composition is 1% by mass or more and 20% by mass or less; the deformation ratio measured by the above method (1) is 0.95 or more and 1 or less; by the above method (2) In the bending resistance test of the cylindrical mandrel method, the minimum diameter of the cylindrical mandrel without cracking of the polymer film is 3mm or more and 5mm or less; the deformation ratio obtained by the above method (1) The ratio [(deformation ratio)/(minimum mandrel diameter)] to the minimum diameter of the mandrel (mm) obtained by the above method (2) is 0.15 or more and 0.4 or less.

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

<23> The method of <22>, wherein the ratio of e to f in the above formula (6) is e/f=20/80~90/10 (mol/mol).

<24> The method according to any one of <1> to <23>, wherein the above-mentioned composition system further contains a volatilization with a volatilization rate of 14% or more after drying at 1 atmosphere, 40°C, and 60%RH for 30 minutes Sex oil.

<25> The method of <24>, wherein the content of the volatile oil in the above 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 water content in the composition is 5% by mass or less.

<28> The method of any one of <1> to <27>, which is a method of applying the composition to the periphery of wrinkles of the skin, and the area where the composition is applied in the periphery of the wrinkles contains and wrinkles At least part of the area where the directions cross.

<29> The method of <28>, wherein the above-mentioned area is an area along the wrinkle direction.

<30> The method such as <28> or <29>, wherein the above-mentioned areas are the two sides of the wrinkle.

<31> The method according to any one of <27> to <30>, wherein the above-mentioned composition is applied to the above-mentioned area in a plane, band, line or dot shape.

<32> The method according to any one of <1> to <31>, wherein the above-mentioned wrinkle improvement method stretches and stretches the skin around the wrinkle by the contraction effect of the above-mentioned polymer, in a non-invasive control The method of skin shape.

[Example]

The following examples illustrate the present invention, but the present invention is not limited to the scope of the examples. In addition, in this example, various measurements and evaluations were performed by the following methods.

(Number average molecular weight Mn)

The number average molecular weight of the polymer is measured by the gel filtration 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 in series

Detector: RI

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

Flow rate: 1.0mL/min

Column temperature: 40℃

(Deformation ratio)

A 10% by mass hexamethyldisiloxane solution of the polymer used in the composition of each example was prepared. Put the solution on one side of polyethylene sheet 1 ("LL film" manufactured by Enshu Chemical Co., Ltd.) shown in Figure 1(a) with a width (W) of 20 mm × a length (L0) of 100 mm × a thickness of 0.03 mm) 0.005g is applied from one end 1a of the short side of the polyethylene sheet 1 to the lengthwise direction in the range of width 20mm×length 50mm (the part 2 shown in Figure 1(a)), in a constant temperature bath set at 40°C Let dry for 10 minutes. In the dried polyethylene sheet (Figure 1(b)), the length of the polyethylene sheet coated with the above solution is set to L1 (50mm), and the part that is deformed (curled) due to shrinkage after drying Set the length of the polyethylene sheet as L2, calculate L2/L1, and use this value as the deformation ratio of the polymer. L2 is set as the average value of the measured values on the two long sides of the polyethylene sheet 1.

(Bending resistance)

Prepare a 30% by mass hexamethyldisiloxane solution of the polymer used in the composition of each example. Use a 200μm applicator to apply the solution to a polyethylene terephthalate film (“Lumirror 100T60” manufactured by Toray Co., Ltd.) with a width of 50 mm × a length of 100 mm × a thickness of 0.1 mm, and set it at 40°C. Dry for 120 minutes in a constant temperature bath to produce a film (test piece) with a polymer film.

Using the obtained test piece, a bending resistance test was performed according to the cylindrical mandrel method specified in JIS K5600-5-1:1999. Use a type 1 bending test device (Erichsen's bending test machine, Model 266), with the polymer film side of the test piece as the outside, and use diameters 32mm, 25mm, 20mm, 16mm, 12mm, 10mm, 8mm, 6mm , 4mm, 3mm and 2mm cylindrical mandrels, starting from the larger diameter cylindrical mandrel for bending resistance test. The test was terminated when cracks occurred in the polymer film, and the minimum diameter (mm) of the cylindrical mandrel without cracks was used as the value of the bending resistance. The smaller this value is It shows that the bending resistance is better.

(Wrinkle improvement effect)

According to the form shown in Figure 2(c), 0.2g of the composition of each example was applied with the fingers in a way of enclosing the lips of the half face of the subject. After drying at room temperature (25°C) for 10 minutes, a specialist judge evaluated the effect of wrinkle improvement according to the following five-stage criteria.

5: Wrinkles become quite slight

4: Wrinkles become slight

3: Wrinkles become slightly slight

2: Wrinkles are retained without changes

1: No change

Examples 1 to 7, Comparative Example 1 (manufacturing and evaluation of composition)

All the ingredients shown in Table 1 were blended and evenly mixed with a disperser to prepare the composition shown in Table 1. Using the obtained composition, the skin wrinkle improvement evaluation was performed according to the above-mentioned method. The results are shown in Table 1. In addition, the compounding amount described in Table 1 is the effective ingredient amount (mass %) of each component.

[Table 1]

The blending ingredients in Table 1 are as follows.

烯/參(三甲基矽氧基)矽基降

烯)共聚物的異十二烷溶液，有效份濃度：30質量%)依50℃減壓乾燥12小時，使用所得固形份。 *1: "NBN-30-ID" manufactured by Shin-Etsu Chemical Co., Ltd. (e/f=60/40 (mol/mol) in the following formula (6), Mn=360,000)

Ene / ginseng (trimethylsiloxy) silyl drop

The isododecane solution of ene) copolymer, effective concentration: 30% by mass), dried under reduced pressure at 50°C for 12 hours, and used the obtained solid content.

*2: The isododecane solution of "TSPL-30-ID" (tris(trimethylsiloxy)silylpropyl urethane triglucose) manufactured by Shin-Etsu Chemical Co., Ltd., effective concentration: 30 mass %) Dry under reduced pressure at 50°C for 12 hours, and use the obtained solid content.

＊3: "XS66-B8226" (trifluoropropyldimethyl/trimethylsiloxy silicic acid cyclopentasiloxane solution, effective concentration: 50% by mass) manufactured by Momentive Performance Materials Japan contract company Dry under reduced pressure at 50°C for 12 hours, and use the obtained solid content.

＊4: "X21-5595" (isododecane solution of trimethylsiloxysilicate, effective concentration: 60% by mass) manufactured by Shin-Etsu Chemical Co., Ltd., dried under reduced pressure at 50°C for 12 hours, and used The solid content obtained.

＊5: The isododecane solution of "FA 4002 ID Silicone Acrylate" (acrylate-polytrimethylsiloxy methacrylate copolymer) manufactured by Toray Dow Corning Co., Ltd. is effectively concentrated. Degree: 40% by mass) was dried under reduced pressure at 50°C for 12 hours, and the obtained solid content was used.

*6: The isododecane solution of "KP-550" (graft copolymer composed of acrylic polymer and dimethylpolysiloxane) manufactured by Shin-Etsu Chemical Co., Ltd., effective concentration: 40% by mass ) Dry under reduced pressure at 50°C for 12 hours, and use the obtained solid content.

*7: "KF-96L-0.65cs" manufactured by Shin-Etsu Chemical Co., Ltd., hexamethyldisiloxane

Regarding the wrinkle improvement effect, the result of Example 1 is shown in FIG. 5, and the result of Comparative Example 1 is shown in FIG. Figures 5(a) and 6(a) are photos of the surrounding area of the decree before applying the composition, and Figs. 5(b) and 6(b) are photographs of the surrounding area of the decree after applying the composition. As shown in FIG. 5, compared with the small wrinkles in the nasolabial folds and their surroundings that became less noticeable by the method of Example 1, the comparative example 1 shown in FIG. 6 did not see an improvement effect.

(Industrial availability)

According to the method of the present invention, the skin shape can be controlled non-invasively, so that skin wrinkles are not obvious.

1‧‧‧Polyethylene sheet

1a‧‧‧One end of the short side of polyethylene sheet 1

2‧‧‧The part coated with polymer solution

Claims (9)

A method for improving skin wrinkles is to apply a composition containing a polymer with a silicone structure to the skin, wherein: The deformation ratio of the polymer measured by the following method (1) is 0.3 or more and 1 or less, and in the bending resistance test of the cylindrical mandrel method by the following method (2), the polymer is The minimum diameter of the cylindrical mandrel without film cracking is 2mm or more and 25mm or less; Method (1): Prepare a 10% by mass hexamethyldisiloxane solution of the above polymer; on one side of a polyethylene sheet with a width of 20 mm × a length of 100 mm × a thickness of 0.03 mm, the solution is 0.005 g from the short side Coat one end from one end to the length in the range of width 20mm×length 50mm, and dry in a constant temperature bath set at 40°C for 10 minutes; set the length of the polyethylene sheet coated with the above solution to L1, and dry it The length of the polyethylene sheet that is deformed due to shrinkage is set to L2, and the value of L2/L1 is used as the deformation ratio; Method (2): Prepare a 30% by mass hexamethyldisiloxane solution of the above polymer; use a 200 μm coater to apply the solution to a polyterephthalene of 50 mm in width × 100 mm in length × 0.1 mm in thickness The ethylene formate film was dried in a constant temperature bath set at 40°C for 120 minutes to prepare a test piece; using the test piece, the bending resistance test was carried out according to the cylindrical mandrel method specified in JIS K5600-5-1:1999 , Calculate the minimum diameter of the cylindrical mandrel without cracks in the polymer film on the test piece. A method for improving skin wrinkles, comprising the steps of: applying a composition containing a polymer having a silicone structure to the wrinkle periphery of the skin; and then drying the composition to shrink the polymer Steps; where, The polymer has a deformation ratio of 0.3 or more and 1 or less measured by the following method (1), and in the bending resistance test of the cylindrical mandrel method by the following method (2), the The minimum diameter of the cylindrical mandrel without cracking of the polymer film is 2mm or more and 25mm or less; Method (1): Prepare a 10% by mass hexamethyldisiloxane solution of the above polymer; on one side of a polyethylene sheet with a width of 20 mm × a length of 100 mm × a thickness of 0.03 mm, the solution is 0.005 g from the short side Coat one end from one end to the length in the range of width 20mm×length 50mm, and dry in a constant temperature bath set at 40°C for 10 minutes; set the length of the polyethylene sheet coated with the above solution to L1, and dry it The length of the polyethylene sheet that is deformed due to shrinkage is set to L2, and the value of L2/L1 is used as the deformation ratio; Method (2): Prepare a 30% by mass hexamethyldisiloxane solution of the above polymer; use a 200 μm coater to apply the solution to a polyterephthalene of 50 mm in width × 100 mm in length × 0.1 mm in thickness The ethylene formate film was dried in a constant temperature bath set at 40°C for 120 minutes to prepare a test piece; using the test piece, the bending resistance test was carried out according to the cylindrical mandrel method specified in JIS K5600-5-1:1999 , Calculate the minimum diameter of the cylindrical mandrel without cracks in the polymer film on the test piece. A method for applying a composition containing a polymer with a silicone structure to the periphery of wrinkles of the skin, wherein: The polymer has a deformation ratio of 0.3 or more and 1 or less measured by the following method (1), and in the bending resistance test of the cylindrical mandrel method by the following method (2), the polymer The minimum diameter of the cylindrical mandrel without film cracking is 2mm or more and 25mm or less; Method (1): Prepare a 10% by mass hexamethyldisiloxane solution of the above polymer; on one side of a polyethylene sheet with a width of 20 mm × a length of 100 mm × a thickness of 0.03 mm, the solution is 0.005 g from the short side Coat one end in the lengthwise direction in the range of 20mm×50mm in width, and dry in a constant temperature bath set at 40℃ for 10 minutes; The length of the part of the polyethylene sheet is set to L1, the length of the part of the polyethylene sheet that is deformed by shrinkage after drying is set to L2, and the value of L2/L1 is used as the deformation ratio; Method (2): Prepare a 30% by mass hexamethyldisiloxane solution of the above polymer; use a 200 μm coater to apply the solution to a polyterephthalene of 50 mm in width × 100 mm in length × 0.1 mm in thickness The ethylene formate film was dried in a constant temperature bath set at 40°C for 120 minutes to prepare a test piece; using the test piece, the bending resistance test was carried out according to the cylindrical mandrel method specified in JIS K5600-5-1:1999 , Calculate the minimum diameter of the cylindrical mandrel without cracks in the polymer film on the test piece. The method of claim 2 or 3, wherein the area where the composition is applied to the wrinkle periphery includes at least a part of the area that intersects the wrinkle direction. The method of claim 4, wherein the above-mentioned area is an area along the wrinkle direction. Such as the method of claim 4 or 5, wherein the above-mentioned areas are both sides of the wrinkles. 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. The method according to any one of claims 1 to 7, wherein the above-mentioned polymer is selected from the group consisting of polysiloxane modified polymer

A group consisting of olefin, polysiloxane modified polytriglucose, trimethylsiloxysilicic acid, trifluoropropyl dimethyl/trimethylsiloxysilicic acid, and acrylic-based polysiloxy dendrimer More than one kind of. Such as the method of any one of claims 1 to 8, wherein the ratio of the deformation ratio obtained by the above method (1) to the minimum diameter of the mandrel (mm) obtained by the above method (2) [( The deformation ratio)/(minimum diameter of the mandrel)] is 0.01 or more and 0.5 or less.

Images