JP2022067065A - Topical skin composition - Google Patents

Abstract

To provide a topical skin composition that does not cause secondary attachment to towel after applied to skin, gives no stickiness to the skin during application, giving the skin resilience with a finish having inconspicuous color irregularities, and demonstrates high effect of improving skin sagging.SOLUTION: A topical skin composition contains following components (A) and (B): (A) 0.001-30 mass% of a coat-forming polymer and (B) 0.01-15 mass% of a wrinkle improvement component.SELECTED DRAWING: None

Description

The present invention relates to an external skin preparation composition.

Aging causes more wrinkles and blemishes on human skin. 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.
For these, conventionally, cosmetics containing wrinkle improving ingredients and the like have been studied.
For example, Patent Document 1 describes that a cosmetic containing a fructosyl dipeptide and a guanidine derivative is excellent in wrinkle improving effect. Patent Document 2 describes that a cosmetic composition containing a vitamin B ₃ compound and ricinoleic acid brightens the skin.

Japanese Unexamined Patent Publication No. 2007-1905 Special Table 2016-533360 Gazette

However, conventional cosmetics are sticky at the time of application, and after being applied to the skin, they are inferior in usability, such as secondary adhesion to towels, and can sufficiently obtain wrinkle improving effect and color unevenness suppressing effect. I didn't.

By using a film-forming polymer in combination with a conventionally used wrinkle-improving component, the present inventors have no secondary adhesion after application to the skin, no stickiness at the time of application, and the skin feels elastic. The present invention has been completed by finding that a composition for external use on the skin having an excellent effect of improving sagging of the eyes, face line, cheeks, etc. can be obtained with a finish in which color unevenness is inconspicuous.

In the present invention, the following components (A) and (B):
(A) Film-forming polymer 0.001 to 30% by mass,
(B) Wrinkle improving component 0.01 to 15% by mass
The present invention relates to an external skin preparation composition containing.
Further, in the present invention, the following components (A) and (B):
(A) Film-forming polymer 0.001 to 30% by mass,
(B) Wrinkle improving component 0.01 to 15% by mass
The present invention relates to a method of applying a composition containing the above to the skin to control the shape of the skin.

After being applied to the skin, the composition for external use on the skin of the present invention has no secondary adhesion, is not sticky at the time of application, gives a feeling of elasticity to the skin, and gives a finish in which color unevenness is inconspicuous. It has an excellent effect of improving sagging of face lines and the like.

It is explanatory drawing of the evaluation method of the deformation ratio (L2 / L1) of a polymer by the method (1).

<Ingredient (A)>
The component (A) used in the present invention is a film-forming polymer, and may be any as long as it is used in a normal skin external preparation composition.
The basic skeleton of the film-forming polymer is, for example, obtained by addition polymerization of a condensation polymer such as polyurethane, polyester, polyether, polyurea; and a vinyl monomer such as a vinyl compound, a vinylidene compound, a vinylene compound, and a cyclic olefin. Vinyl-based polymer; Examples thereof include silicone-based polymer. Among these, silicone-based polymers and vinyl-based polymers are selected from the viewpoint of suppressing secondary adhesion after application to the skin and controlling the external shape of the skin in three dimensions without impairing the natural appearance. More than seeds are preferred, and silicone-based polymers are more preferred.

Among the components (A), the silicone-based polymer is preferably a polymer having a silicone structure, and the deformation ratio measured by the following method (1) is 0.3 or more and 1 or less, and the following method. In the bending resistance test by the cylindrical mandrel method performed according to (2), the minimum diameter of the cylindrical mandrel in which cracks do not occur in the polymer film is 2 mm or more and 25 mm or less.
Method (1): A 10% 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 in the portion to which the solution is applied is L1, the length of the polyethylene sheet in 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 was 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 that does not cause cracks in the polymer film on the test piece. Ask for.

When the silicone-based polymer of the component (A) satisfies the above-mentioned deformation ratio measured by the method (1), for example, a composition containing the polymer of the component (A) can be applied to the skin such as around the eyes and the face line. When the composition is then dried, the skin surface in close contact with the polymer shrinks along with the shrinkage of the film containing the polymer. Due to this action, the external shape of the skin can be controlled three-dimensionally without impairing the natural appearance.

A method for evaluating the deformation ratio (L2 / L1) of the silicone-based polymer of the component (A) according to the method (1) will be described with reference to FIG. First, a 10% by mass hexamethyldisiloxane solution of the component (A) 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 length direction from the above, 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 polyethylene sheet 1 coated with the solution is dried and then deformed (curled) by shrinkage of a polymer whose part is the component (A).
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 three-dimensionally controlling the external shape of the skin without impairing the natural appearance, the deformation ratio L2 / L1 evaluated by the method (1) of the silicone-based polymer of the component (A) is 0.3. The above, preferably 0.5 or more, more preferably 0.6 or more, still more preferably 0.7 or more, still more preferably 0.8 or more, still more preferably 0.85 or more, still more preferably 0. It is 9.9 or more, more preferably 0.95 or more, and the upper limit is 1.
Specifically, the deformation ratio can be evaluated by the method described in Examples.

Further, the silicone-based polymer of the component (A) has excellent bending resistance, and cracks do not occur in the film of the polymer of the component (A) in the bending resistance test by the cylindrical mandrel method performed by the method (2). The minimum diameter of the cylindrical mandrel is 2 mm or more and 25 mm or less. As a result, the film formed by the composition containing the silicone-based polymer of the component (A) 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 three-dimensionally control the external shape of the skin without impairing the natural appearance, the minimum diameter of the cylindrical mandrel that does not generate cracks is 2 mm. As mentioned above, it is preferably 3 mm or more. The specific range of the minimum diameter of the cylindrical mandrel is 2 to 25 mm, preferably 2 to 20 mm, more preferably 2 to 12 mm, still more preferably 2 to 8 mm, even more preferably 3 to 6 mm, still more preferably 3. It is ~ 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 silicone-based polymer of the component (A) to the minimum diameter (mm) of the mandrel obtained by the method (2), which is obtained by the method (1) [(deformation ratio) / (mandrel). Minimum diameter)] is preferably 0.01 or more, more preferably 0.02 or more, still more preferably 0.10 or more, from the viewpoint of three-dimensionally controlling the external shape of the skin without impairing the natural appearance. , More preferably 0.15 or more, and preferably 0. from the viewpoint of imparting sufficient strength and shape control effect for three-dimensionally controlling the external shape of the skin without impairing the natural appearance. It is 5 or less, more preferably 0.4 or less. The specific range of the ratio is preferably 0.01 to 0.5, more preferably 0.02 to 0.5, still more preferably 0.10 to 0.5, still more preferably 0.15 to 0. 5, and even more preferably 0.15 to 0.4.

In the present invention, the "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 carbon atoms and 12 or less carbon atoms, and p is an integer of 1 or more. From the viewpoint of sterically controlling the external shape of the skin when applied without impairing the natural appearance of the skin, R ¹ is preferably an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms. It is more preferably an alkyl group or a phenyl group having 1 or more and 12 or less carbon atoms, still more preferably an alkyl group having 1 or more and 3 or less carbon atoms, and still more preferably a methyl group.

The silicone-based polymer of the component (A) may have a silicone structure as long as it has a silicone structure, and may be a polymer having only a silicone structure. It is preferable to have.
When the polymer has a partially silicone structure, the silicone structure may be present in any of the main chain and 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 silicone-based polymer of the component (A) 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, phenyl-modified alkylsiloxysilicic acid and other silicone structure-containing silicic acid compounds; silicone dendrimers and the like.

(Silicone modified polymer containing norbornane structure)
In the present invention, 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 the 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 or more carbon atoms and 12 or less 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 equation, 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 from the viewpoint of sterically controlling the external shape of the skin without impairing the natural appearance. , Ethyl group, n-propyl group, 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 or more and 12 or less carbon atoms. From the viewpoint of sterically controlling the external shape of the skin without impairing the natural appearance, R ¹ is preferably an alkyl group having 1 or more and 12 or less carbon atoms or an aryl group having 6 or more and 12 or less carbon atoms. It is preferably an alkyl group or a phenyl group having 1 or more and 12 or less carbon atoms, more preferably an alkyl group having 1 or more and 3 or less carbon atoms, and even more preferably a methyl group. 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, preferably 0, 1 or a combination thereof, and 0 is more preferable from the same viewpoint.

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. From the same viewpoint, the cyclic silicone structure in the general formula (2) preferably has R ¹ and R ² as a methyl group and d as 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 three-dimensionally controlling the external shape of the skin without impairing the natural appearance, the ratio of the repeating unit represented by the general formula (1) or (2) in the norbornane structure-containing silicone-modified polymer is determined. Of the total number of repeating units in the polymer, it is preferably 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%.

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 unit represented by the above general formula (3) in the norbornane structure-containing silicone-modified polymer is determined in the polymer from the viewpoint of sterically controlling the external shape of the skin without impairing the natural appearance. Of the total number of repeating units, it is preferably 90% or less, 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 to 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 H-NMR measurement.

As the norbornene 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. / 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 5 from the viewpoint of achieving both shrinkage and bending resistance and controlling the external shape of the skin three-dimensionally without impairing the natural appearance. It is 10,000 or more, more preferably 100,000 or more, still more preferably 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 filtration chromatography (GPC) method using polystyrene as a standard substance, and specifically, can be measured by the method described in Examples.

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), addition polymerization of a cyclic olefin monomer represented by the following general formula (1a) or (2a) is carried out. You can get it. Further, 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 or more carbon atoms and 12 or less 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 used for the polymerization from the viewpoint of sterically controlling the external shape of the skin without impairing the natural appearance. The total monomer content is 100 mol%, preferably 90 mol% or less, more preferably 70 mol% or less, still more preferably 50 mol% or less, and preferably 5 mol% or more, more preferably 10 mol% or more. More preferably, it is 30 mol% or more.

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 sterically controlling the external shape of the skin without impairing the natural appearance, the copolymerization ratio of tris (trimethylsiloxy) silylnorbornene and norbornene is preferably 20/80 to 90/10 (mol). / Mol), more preferably 30/70 to 80/20 (mol / mol), still more preferably 50/50 to 70/30 (mol / mol).

The repeating units represented by the general formulas (1) to (3) and the above formula (6) all indicate 2,3-addition structural units of the cyclic olefin monomer which is the raw material monomer. It may contain 2,7-additional structural units obtained 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 Dictionary and Handbook, 16th Edition, Volume 2, 2016, p.2274): NORBORN. / TRIS (TRIMETHYLSILOXY) SILYLNORBORNENE COPOLYMER is a compound.
Examples of commercially available norbornane structure-containing silicone-modified polymers include isododecane solution of "NBN-30-ID" (norbornene / tris (trimethylsiloxy) silylnorbornene) copolymer manufactured by Shin-Etsu Chemical Co., Ltd.).

(Silicone modified pullulan)
Examples of the silicone-modified pullulan include pullulan having a silicone structure in the side chain. Specifically, the OH group in pullulan is defined from the viewpoint of sterically controlling the external shape of the skin without impairing the natural appearance. Silicone-modified pullulan in which at least a part of the hydrogen atom of the above is 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, and a are the same as described above, and from the same viewpoint, X is preferably a trimethylsiloxy group, and a is preferably 3.

In the general formula (7), from the same viewpoint, Z ¹ is preferably a divalent organic group, more preferably a divalent group represented by the following general formula (8) or (9), and 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 carbon atoms 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.

As commercially available silicone-modified pullulan, "TSPL-30-ID" (tri (trimethylsiloxy) silylpropylcarbamide pullulan isododecane solution) manufactured by Shin-Etsu Chemical Co., Ltd., "TSPL-30-D5" (tri (trimethylsiloxy) silyl) Cyclopentasiloxane solution of pullulan propylcarbamide) 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 terminal, 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, and more preferably 1 or more and 4 or less carbon atoms, from the viewpoint of sterically controlling the external shape of the skin without impairing the natural appearance. It is more preferably a methyl group. 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 atom of the alkyl group in the trialkylsiloxysilicic acid is replaced with a fluorine atom. 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, they are selected from the group consisting of trialkylsiloxysilicic acid and fluorine-modified alkylsiloxysilicic acid from the viewpoint of sterically controlling the external shape of the skin without impairing the natural appearance. One or more is preferable.

Examples of commercially available silicone structure-containing silicic acid compounds include "KF-7312J", "KF-7312K", "KF-7312T", "KF-7312L", "X-21-5249", and "X" manufactured by Shin-Etsu Chemical Industry Co., Ltd. -21-5250 ”,“ KF-9021 ”,“ X-21-5595 ”,“ X-21-5616 ”,“ KF-9021L ”,“ X-21-5249L ”,“ X-21-5250L ”, etc. Trimethylsiloxysilicic acid (solution), "XS66-B8226" (trifluoropropyldimethyl / cyclopentasiloxane solution of trimethylsiloxysilicic acid) manufactured by Momentive Performance Materials Japan LLC, "XS66-B8636" (trifluoro) A dimethicone solution of propyldimethyl / trimethylsiloxysilicic acid), "SilShine151" (phenylpropyldimethylsiloxysilicic acid) and the like can be used.

(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 three-dimensionally controlling the external shape of the skin without impairing the natural appearance.

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.

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 is exemplified. A propylene group is preferred. R ¹⁴ is an alkyl group having 1 or more and 10 or less carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group and a butyl group, and 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.

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, and the like, 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 sterically controlled from the viewpoint of sterically controlling the external shape of the skin without impairing the natural appearance. It is preferably 0.1% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more, based on all the repeating units in the vinyl-based polymer. 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-polytrimethylsiloxy) manufactured by Toray Dow Corning. Acrylic silicone dendrimers such as isododecane solution of methacrylate copolymer) can be mentioned.

Among the above-mentioned polymers, the silicone-based polymer of the component (A) includes silicone-modified polynorbornene, silicone-modified purulan, and trimethylsiloxy from the viewpoint of sterically controlling the external shape of the skin without impairing the natural appearance. One or more selected from the group consisting of silicic acid, trifluoropropyldimethyl / trimethylsiloxysilicic acid, and acrylic silicone dendrimers are preferred, with silicone-modified polynorbornene, silicone-modified purulan, trimethylsiloxysilicic acid, and trifluoropropyldimethyl / trimethyl. One or more selected from the group consisting of siloxysilicic acid is more preferable, and from the viewpoint of sterically controlling the external shape of the skin without impairing the natural appearance, the group consisting of silicone-modified polynorbornene and silicone-modified purulan. One or more selected from the above is more preferable, and silicone-modified polynorbornen is even more preferable.

Among the components (A), those having an anionic group or a cationic group are preferable as the vinyl-based monomer constituting the vinyl-based polymer.
As anionic groups, carboxy group (-COOM), sulfonic acid group (-SO ₃ M), phosphate group (-OPO ₃ M ₂ ) and other groups that dissociate and release hydrogen ions to exhibit acidity. , Or their dissociated ionic forms (-COO-, -SO _3- , -OPO ₃ ^2- , -OPO ₃ ^- M) and the like. In the chemical formula, M represents a hydrogen atom, an alkali metal, ammonium or an organic ammonium.
Examples of the vinyl-based monomer having an anionic group include acrylic acid, methacrylic acid, maleic acid, and styrene sulfonic acid.
Examples of the cationic group include a protonate of a primary, secondary or tertiary amino group, a quaternary ammonium group and the like.
Examples of the vinyl-based monomer having a cationic group include N, N-dimethylaminoethyl (meth) acrylate and N, N-dimethylaminopropyl (meth) acrylamide.

The vinyl-based polymer of the component (A) preferably contains a repeating unit derived from a vinyl-based monomer having an anionic group from the viewpoint of sterically controlling the external shape of the skin without impairing the natural appearance. It is a vinyl-based polymer, more preferably a vinyl-based polymer containing a repeating unit derived from one or more vinyl-based monomers selected from acrylic acid, methacrylic acid, maleic acid, styrene sulfonic acid and salts thereof. More preferably, it is one or more selected from polymethacrylic acid and sodium polystyrene sulfonate.
The vinyl-based polymer of the component (A) may be a copolymer containing a repeating unit derived from a vinyl-based monomer having an anionic group and a repeating unit derived from another monomer, but the skin may be used. From the viewpoint of sterically controlling the external shape of the vinyl-based monomer without impairing the natural appearance of the vinyl-based monomer, a homopolymer of a vinyl-based monomer having an anionic group is preferable.

The weight average molecular weight Mw of the vinyl polymer of the component (A) is preferably 10,000 or more, more preferably 30,000 or more, still more preferably 50,000 or more, and preferably 700,000 or less. It is preferably 500,000 or less, more preferably 300,000 or less. The weight average molecular weight Mw can be measured by a gel permeation chromatography (GPC) method using polystyrene as a standard material, and specifically, can be measured by the method described in Examples.
As the vinyl-based polymer of the component (A), a synthesized one may be used, or a commercially available product may be used.
When the vinyl-based polymer of the component (A) is obtained by synthesis, for example, in the presence of a polymerization initiator or the like, the above-mentioned vinyl-based monomer having an anionic group and, if necessary, other monomers are known. It can be obtained by the addition polymerization of the above method.
Examples of commercially available vinyl-based polymers of the component (A) include sodium polystyrene sulfonate manufactured by Alfa Aesar.

The component (A) can be used alone or in combination of two or more, and the content is in the entire composition from the viewpoint of three-dimensionally controlling the external shape of the skin without impairing the natural appearance. 0.001% by mass or more, preferably 0.01% by mass or more, more preferably 0.05% by mass or more, further preferably 0.1% by mass or more, 30% by mass or less, and 20% by mass or less. Is preferable, 15% by mass or less is more preferable, and 5% by mass or less is further preferable. The content of the component (A) is 0.001 to 30% by mass, preferably 0.01 to 20% by mass, more preferably 0.05 to 15% by mass, and 0.1 to 0.1 to 30% by mass in the total composition. 5% by mass is more preferable.

<Ingredient (B)>
The component (B) used in the present invention is a wrinkle-improving component, and may be any as long as it is used for a normal external skin preparation.
Specific examples thereof include vitamin A and its derivatives, vitamin B ₃ and its derivatives, and guanidine derivatives.
Examples of vitamin A and its derivatives include, but are not limited to, vitamin A (retinol), retinol, retinoic acid, vitamin A acetate, vitamin A palmitate, vitamin A propionic acid, and astaxanthin. Includes all A derivatives. It is also possible to use mixtures of these vitamins A and their derivatives, such as animal and vegetable oils containing them obtained from aquatic animals and plants. For example, vitamin A oil, carrot extract, carrot oil and the like can be mentioned.

Examples of vitamin B ₃ and its derivatives include nicotinamide, nicotinic acid, and nicotinyl alcohol, as well as tocopherol nicotinate, inositol hexanicotinate, myristyl nicotinate, nicotinyl amino acid, nicotinyl alcohol ester of carboxylic acid, and nicotin. Nicotinamide ester containing acid N-oxide and niacinamide N-oxide; nicotinamide derivative such as nicotinuric acid and nicotinylhydroxamic acid; nicotinyl alcohol ester such as carboxylic acid, salicylic acid, acetic acid, glycolic acid and palmitic acid; In addition, 2-chloronicotinamide, 6-aminonicotinamide, 6-methylnicotinamide, n-methylnicotinamide, n, n-diethylnicotinamide, n- (hydroxymethyl) -nicotinamide, quinophosphateimide, nicotin Anilide, n-benzylnicotinamide, n-ethylnicotinamide, niphenazone, nicotinaldehyde, isonicotic acid, methyl isonicotate, thionicotinamide, nearramid, 1- (3-pyridylmethyl) urea, 2-mercaptonicotinic acid, Examples include nicomol and niaplazine.
Vitamin B ₃ salts can also be used. Examples of the salt include organic salts or inorganic salts, for example, inorganic salts having anionic inorganic species (eg, chlorides, bromides, iodides, carbonates, preferably chlorides), organic carboxylates (mono, di-and). Examples thereof include tri-C1-C18 carboxylates such as acetates, salicylates, glycolates, lactates, malate and citrates, preferably monocarboxylates such as acetates).
In addition, vitamin B ₃ and its derivatives may be included as substantially pure substances or as extracts obtained from natural (eg, plant) raw materials.

Examples of the guanidine derivative include a guanidine derivative represented by the general formulas (16), (17) and (18) or an acid addition salt thereof.

[In the formula (16), X and Y are the same or different and represent an alkylene group having 2 to 8 carbon atoms, and D is a single bond, —CO— or a substituent may have 1 to 8 carbon atoms. 6 represents an alkylene group, E represents a hydrogen atom, a lower alkyl group, an aryl group which may have an aralkyl group or a substituent, x represents a number of 1 to 6, and y represents a number of 0 to 6. , And R ²¹ represents a hydrogen atom, a lower alkyl group or-(XO) _x- (YO) _y -DE. However, when R ¹ is a methyl group, − (XO) _x − (YO) _y −DE is not a hydroxyethyl group. In formula (17), R ²¹ has the same meaning as above, z represents a number from 1 to 10, and G represents a hydrogen atom, a hydroxyl group, a carboxyl group, a sulfonic acid group or a phosphoric acid group].

Represents a heterocyclic group selected from azetidine, pyrrolidine, piperidine, piperazine and morpholine, where R ²² and R ²³ are the same or different, with hydrogen atoms, alkyl groups, hydroxyalkyl groups, carboxyl groups, carboxyalkyl groups or amidino groups. show)
In general formula (18),

As the heterocyclic group represented by, pyrrolidine, piperidine, piperazine and morpholine are preferable.

Further, as the alkyl group represented by R ²² and R ²³ , a linear or branched alkyl group having 1 to 6 carbon atoms is preferable, and an alkyl group having 1 to 4 carbon atoms is more preferable. Specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group and the like, and a methyl group is preferable.

As the hydroxyalkyl group, a hydroxyalkyl group having 1 to 6 carbon atoms is preferable, and a hydroxyalkyl group having 1 to 4 carbon atoms is more preferable. Specific examples thereof include a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group and the like, and a hydroxymethyl group and a hydroxyethyl group are preferable.

Further, as the carboxyalkyl group, a carboxyalkyl group having 2 to 7 carbon atoms is preferable, and a carboxyalkyl group having 2 to 5 carbon atoms is more preferable. Specific examples thereof include a carboxymethyl group, a carboxyethyl group, a carboxypropyl group and a carboxybutyl group, and a carboxymethyl group and a carboxyethyl group are preferable.

Further, since the guanidine derivative (18) has an asymmetric carbon atom, it has steric isomers, but in the present invention, any of these steric isomers and a mixture thereof can be used.

Specific examples of the guanidine derivative (18) include N-amidino-proline, N-amidino-4-hydroxy-proline, 2-hydroxymethyl-1-pyrrolidincarboxamidine, 3-hydroxy-1-pyrrolidincarboxamidine, and the like. N-amidino-aziridine-2-carboxylic acid, N-amidino-2-piperidincarboxylic acid, N-amidino-3-piperidincarboxylic acid, N-amidino-4-piperidincarboxylic acid, N-amidino-4-piperidinpropionic acid , N-Amidinopyrrolidine, N-Amidinopiperidine, N-Amidino-2-methylpiperidine, N-Amidino-3-methylpiperidine, N-Amidino-4-methylpiperidine, N-Amidino-2-methylmorpholine, N-Amidino Examples thereof include -3-methylmorpholin, N-amidino-N'-methylpiperazine, N-amidino-N'-hydroxyethylpiperazine, N, N'-diamidino-piperazine and the like.

The acid for forming the salt of the guanidine derivative may be either an organic acid or an inorganic acid, for example, formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, hexane acid, heptanic acid, octanoic acid, nonanoic acid, etc. Decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, phenylacetic acid, silicic acid, benzoic acid, sorbic acid, nicotinic acid, urocanic acid, pyrrolidonecarboxylic acid, etc. Monocarboxylic acids; dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutamic acid, adipic acid, pimelic acid, cork acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, terephthalic acid; glycolic acid, Hydroxy acids such as lactic acid, malic acid, tartaric acid, citric acid, o, m or p-hydroxybenzoic acid; glycine, alanine, β-alanine, valine, leucine, phenylalanine, tyrosine, serine, threonine, methionine, cysteine, cystine, Amino acids such as proline, hydroxyproline, pipecolic acid, tryptophan, aspartic acid, asparagine, glutamic acid, glutamine, lysine, histidine, ornithine, arginine, aminobenzoic acid; lower alkylsulfonic acid such as methanesulfonic acid and trifluoromethanesulfonic acid; benzene Arylsulfonic acids such as sulfonic acid and p-toluenesulfonic acid; Hydrohalogenated acids such as hydrofluoric acid, hydrochloric acid, hydrobromic acid and hydroiodic acid; perchloric acid, sulfuric acid, nitric acid, phosphoric acid, carbonic acid and the like. Inorganic acid of.

As the guanidine derivative, 2- (2-hydroxyethoxy) ethylguanidine, N-amidino-proline, and 2- (2-hydroxyethoxy) ethylguanidine succinate are particularly preferable.

The guanidine derivative (16), (17) or a salt thereof is described in, for example, JP-A-8-92054, and the guanidine derivative (18) or a salt thereof is described in JP-A-8-109120, for example. It can be manufactured according to the method.

As the component (B), one or more selected from retinol, nicotinamide and N-amidinoproline are preferable from the viewpoint of enhancing the moisturizing of the skin and improving wrinkles.

The component (B) can be used alone or in combination of two or more, and the content is 0.01% by mass or more in the total composition from the viewpoint of enhancing the moisturizing of the skin and improving wrinkles. , 0.02% by mass or more, more preferably 0.04% by mass or more, further preferably 0.06% by mass or more, further preferably 15% by mass or less, preferably 12% by mass or less, and more preferably 10% by mass or less. It is preferably 9% by mass or less, and more preferably 9% by mass or less. The content of the component (B) is 0.01 to 15% by mass, preferably 0.02 to 12% by mass, more preferably 0.04 to 10% by mass, and 0.06 to 0.06 to 10% by mass in the total composition. 9% by mass is more preferable.

In the present invention, the mass ratio (B) / (A) of the component (B) to the component (A) suppresses secondary adhesion, suppresses stickiness at the time of application, improves elasticity to the skin, and makes color unevenness less noticeable. From the viewpoint of improving the slack improving effect of the eyes and face line in the finished product, 0.1 or more is preferable, 0.3 or more is more preferable, 0.5 or more is further preferable, and 0.7 or more is further more preferable. It is preferably 100 or less, more preferably 80 or less, further preferably 60 or less, and even more preferably 45 or less. The mass ratio (B) / (A) of the component (B) to the component (A) is preferably 0.1 to 100, more preferably 0.3 to 80, still more preferably 0.5 to 60, and 0. .7 to 45 are even more preferable.

<Ingredient (C)>
In the external skin preparation composition of the present invention, (C) volatile oil can be further used, which suppresses secondary adhesion and color unevenness, and is three-dimensional without impairing the natural appearance of the external shape of the skin. It can improve the sagging of the skin. Volatility means that the flash point is 35 ° C. or higher and lower than 90 ° C.
The volatile oil may be any one used in ordinary skin external preparation compositions, and one or more selected from volatile silicone oils and volatile hydrocarbon oils are preferable, and volatile silicone oils. Is more preferable.
Examples of the volatile silicone oil include hexamethyldisiloxane (dimethylpolysiloxane (0.65cs)), octamethyltrisiloxane (dimethylpolysiloxane (1cs)), dimethylpolysiloxane (1.5cs), and dimethylpolysiloxane (dimethylpolysiloxane (1.65cs)). Linear dimethylpolysiloxane such as 2cs); branched chain siloxane such as methyltrimethicone, tris (trimethylsilyl) methylsilane, tetrakis (trimethylsilyl) silane; octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane Cyclic dimethylsiloxane and the like.
Of these, linear dimethylpolysiloxane and branched chain-like siloxane are preferable from the viewpoint of excellent usability and suppressing unevenness in the finish, and hexamethyldisiloxane (dimethylpolysiloxane (0.65 cs)) and octamethyltrisiloxane. (Dimethylpolysiloxane (1cs)), dimethylpolysiloxane (1.5cs), dimethylpolysiloxane (2cs), and methyltrimethicone containing one or more types are more preferable, and at least hexamethyldisiloxane (dimethylpoly). Siloxane (0.65 cs)), octamethyltrisiloxane (dimethylpolysiloxane (1cs)), and methyltrimethicone containing one or more of them are more preferable, and at least hexamethyldisiloxane (dimethylpolysiloxane (0.65cs)). )), Those containing one or more of octamethyltrisiloxane (dimethylpolysiloxane (1cs)) are more preferable.

Examples of the volatile hydrocarbon oil include paraffinic hydrocarbon oils such as n-decane, n-undecane, and n-dodecane; isoparaffinic hydrocarbon oils such as isodecane, isododecane, and hydrogenated polyisobutene; cyclodecane, cyclododecane, and the like. Cyclic paraffin hydrocarbon oil can be mentioned. Of these, isoparaffin-based hydrocarbon oils are preferable, isoparaffin-based hydrocarbon oils having 8 to 16 carbon atoms are more preferable, and isoparaffin-based hydrocarbons having 10 to 16 carbon atoms are preferable from the viewpoint of excellent usability and suppressing unevenness in the finish. Oils are even more preferred, and those containing at least isododecane are even more preferred.

The volatile oil of the component (C) preferably contains one or more selected from isododecane and dimethylpolysiloxane having a kinematic viscosity at 25 ° C. of 2 cSt or less. The kinematic viscosity can be measured using, for example, an Ubbelohde viscometer.

The component (C) can be used alone or in combination of two or more, and the content suppresses secondary adhesion and color unevenness, and is three-dimensional without impairing the natural appearance of the external shape of the skin. From the viewpoint of improving the skin sagging, it is preferably 0.01% by mass or more, more preferably 1% by mass or more, still more preferably 10% by mass or more, and 25% by mass in the total composition. % Or more is more preferable, 70% by mass or less is preferable, 60% by mass or less is more preferable, 50% by mass or less is further preferable, and 43% by mass or less is further preferable. The content of the component (C) is preferably 0.01 to 70% by mass, more preferably 1 to 60% by mass, further preferably 10 to 50% by mass, and more preferably 25 to 43% by mass in the total composition. More preferred.

In the present invention, the mass ratio ((A) + (C)) / (B) of the total amount of the components (A) and (C) to the component (B) suppresses secondary adhesion and color unevenness, and the skin. From the viewpoint of improving the external shape three-dimensionally without impairing the natural appearance and improving the sagging of the skin, it is preferably 1 or more, more preferably 2 or more, further preferably 3 or more, and 700 or less. It is preferable, 600 or less is more preferable, and 530 or less is further preferable. Further, the mass ratio ((A) + (C)) / (B) of the total amount of the components (A) and (C) to the component (B) is preferably 1 to 700, more preferably 2 to 600, and 3 ~ 530 is more preferable.

<Component (D)>
The external skin preparation composition of the present invention can further contain (D) a surfactant. Of these, anionic surfactants, cationic surfactants, nonionic surfactants and amphoteric surfactants are preferable.
The surfactant is not limited as long as it is used for ordinary external skin preparations, but it suppresses secondary adhesion and color unevenness and improves the external shape of the skin three-dimensionally without impairing the natural appearance. From the viewpoint of the above, a nonionic surfactant is preferable.
Examples of the nonionic surfactant include sorbitan fatty acid ester, glycerin fatty acid ester, polyglycerin fatty acid ester, propylene glycol fatty acid ester, polyethylene glycol fatty acid ester, sucrose fatty acid ester, polyoxyethylene fatty acid ester, and polyoxyethylene sorbitan fatty acid ester. , Polyoxyethylene alkyl ether, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyoxyethylene propylene glycol fatty acid ester, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, polyoxyethylene hydrogenated castor oil fatty acid ester , Polyoxyethylene phytostanol ether, polyoxyethylene phytosterose ether, polyoxyethylene cholestanol ether, polyoxyethylene cholesteryl ether, alkyl glyceryl ether modified silicone, polyoxyalkylene modified silicone, polyoxyalkylene / alkyl co-modified silicone, Examples thereof include polyoxyalkylene / fluoroalkyl co-modified silicone.

Of these, in the case of water-in-oil emulsified cosmetics, one type of alkyl glyceryl ether-modified silicone and polyoxyalkylene-modified silicone is used from the viewpoint of enhancing the dispersion and solubility of water and water-soluble components in oil. Alternatively, it is preferable to contain two or more kinds, and it is more preferable to contain polyoxyalkylene-modified silicone.
Examples of the polyoxyalkylene-modified silicone include SH3771M, SH3772M, SH3773M, SH3775M, SH3749, DC5200 manufactured by Toray Dow Corning, and KF-6011, KF-6012, KF-6013, KF- of Shin-Etsu Chemical Co., Ltd. Commercially available products such as 6015, KF-6016, KF6017, and KF-6004 can be used.
Further, in the case of an oil-in-water emulsified cosmetic, polyoxyethylene sorbitan fatty acid ester and polyoxyethylene cured castor oil are preferable from the viewpoint of enhancing dispersibility in water and improving emulsification stability.

In the case of water-in-oil emulsified cosmetics, the nonionic surfactant preferably has an HLB value of 1 or more and 7 or less from the viewpoint of enhancing the dispersion and solubility of water and water-soluble components in oil. It is more preferable that the HLB value is 2 or more and 6 or less.
In the case of oil-in-water emulsified cosmetics, the nonionic surfactant preferably has an HLB value of 9 or more and 19 or less, and has an HLB value of 9 or more, from the viewpoint of enhancing dispersibility in water and improving emulsification stability. 12 or more and 18 or less are more preferable.

Here, HLB (hydrophilic-lipophilic balance <Hydrophilic-Lipophilic Balance>) indicates the molecular weight of the hydrophilic group portion in the total molecular weight of the surfactant, and for nonionic surfactants, Griffin ( It is obtained by the formula of Griffin).
The HLB of a mixed surfactant composed of two or more nonionic surfactants is obtained as follows. The HLB of the mixed surfactant is a phase addition average of the HLB values of each nonionic surfactant based on the blending ratio.

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

In any of the water-in-oil emulsified cosmetics and the oil-in-water emulsified cosmetics, the nonionic surfactant can be used alone or in combination of two or more, and the content is volatile oil. From the viewpoint of dissolving in and suppressing stickiness, it is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, further preferably 1% by mass or more, and preferably 10% by mass or less in the total composition. , 7% by mass or less is more preferable, 4% by mass or less is further preferable, and 3% by mass or less is further preferable.

In the present invention, the mass ratio ((A) + (B)) / (D) of the total amount of the components (A) and (B) to the component (D) suppresses secondary adhesion and color unevenness, and the skin. From the viewpoint of improving the external shape three-dimensionally without impairing the natural appearance and improving the sagging of the skin, it is preferably 0.02 or more, more preferably 0.04 or more, and 0.07 or more. More preferably, 0.1 or more is further preferable, 20 or less is preferable, 10 or less is more preferable, 6 or less is further preferable, and 4 or less is further preferable. The mass ratio ((A) + (B)) / (D) of the total amount of the components (A) and (B) to the component (D) is preferably 0.02 to 20, preferably 0.04 to 10. More preferably, 0.07 to 6 is even more preferable, and 0.1 to 4 is even more preferable.
<Other ingredients>

The external preparation composition for skin of the present invention may further contain powder, and may be any of organic powder, inorganic powder and the like.
Examples of the organic powder include polyamide resin, nylon resin, polyester resin, polyethylene resin, polytetrafluoroethylene resin, polypropylene resin, polystyrene resin, benzoguanamine resin, polymethylbenzoguanamine resin, polymethylmethacrylate, polyurethane resin, and vinyl. Resin, fluororesin, acrylic resin, melamine resin; silicone resin crosslinked with dimethyl silicone, silicone resin such as polymethylsilsesquioxane; butyl acrylate / vinyl acetate copolymer, styrene / acrylic acid copolymer, divinyl benzene Poly (meth) acrylic acid, poly (meth) sodium acrylate, poly (meth) acrylic acid ester, poly (meth) acrylic acid such as styrene copolymer, (lauryl methacrylate / ethylene glycol dimethacrylate) copolymer, etc. Examples thereof include crosslinked or non-crosslinked organic powders such as powders of one or more polymers or copolymers selected from alkylene glycols.

Examples of the inorganic powder include talc, kaolin, mica, sericite, gold mica, aluminum silicate / magnesium, calcium silicate, aluminum silicate, magnesium silicate, barium silicate, strontium silicate, and epoxy-treated aluminum. Aluminum powder, calcium phosphate, silicic acid anhydride, aluminum silicate anhydride, pyroferrite clay, bentonite, smectite, montmorillonite, vermiculite, hectrite, zeolite, hygilite, silica, alumina, zirconia, iron oxide (bengala, yellow iron oxide, Black iron oxide, γ-iron oxide), ocher, black titanium oxide, low-order titanium oxide, iron titanate, zinc oxide, aluminum hydroxide, aluminum oxide, cobalt oxide, chromium oxide, zirconium oxide, titanium oxide, titanium oxide sol , Iron oxide / titanium dioxide sintered product, cerium oxide, magnesium oxide, chromium hydroxide, titanium / titanium dioxide sintered product, cobalt titanate, manganese violet, cobalt violet, calcium carbonate, barium carbonate, magnesium carbonate, metal tungstate Salt, barium sulfate, calcined calcium sulfate (baked sekko), bismuth oxychloride, caramine, sodium loginate treated magnesium oxide, fluoroapatite, hydroxyapatite, ceramic powder, metal soap (zinc myristate, calcium palmitate, aluminum stearate, etc.) ), Etc., and two or more of these composite powders can be mentioned. Further, organic-inorganic composite powders such as acrylic resin-coated aluminum powder and titanium oxide-coated nylon powder can be mentioned.

Moreover, as a powder of a natural fiber, silk powder, wool powder, cellulose powder and the like can be mentioned.
Examples of the pearl luster pigment include mica titanium, iron oxide-coated mica titanium, titanium oxide-coated bismuth chloride, titanium oxide-coated talc, titanium oxide-coated glass flakes, fish scale foil and the like.

These powders can be used as they are, or can be hydrophobized.
The hydrophobizing treatment is not limited as long as it is a treatment applied to ordinary cosmetic powders, and is not limited to silicone treatment, alkoxysilane treatment, fatty acid treatment, lauroyl lysine treatment, lecithin treatment, N-acylamino acid treatment, and metal. Examples include soap treatment and fluorine compound treatment. Of these, silicone treatment is preferable. These processes can be performed by a usual method.

The powder can be used alone or in combination of two or more, and the content is preferably 0.01% by mass or more in the total composition from the viewpoint of giving a make-up effect to the skin, and is preferably 1% by mass. % Or more is more preferable, 5% by mass or more is further preferable, 10% by mass or more is further preferable, 40% by mass or less is preferable, 35% by mass or less is more preferable, 30% by mass or less is further preferable, and 25% by mass or less. Is even more preferable. The content of the powder is preferably 0.01 to 40% by mass, more preferably 1 to 35% by mass, further preferably 5 to 30% by mass, and more preferably 10 to 25% by mass in the total composition. More preferred.

In the present invention, the content of water is preferably 1% by mass or more, more preferably 10% by mass or more, and 20% by mass in the total composition from the viewpoint of suppressing color unevenness and obtaining a non-sticky feeling. % Or more is more preferable, 50% by mass or less is preferable, 45% by mass or less is more preferable, and 40% by mass or less is further preferable.

In the external preparation composition for skin of the present invention, in addition to the above-mentioned components, various commonly used components can be arbitrarily used as long as the effects of the present invention are not impaired. Examples of these components include oily components other than the above, water-soluble polymers, antioxidants, ultraviolet absorbers, vitamins, preservatives, pH adjusters, fragrances, plant extracts, moisturizers, colorants, and cold substances. Examples include sensitizers, antiperspirants, bactericides, skin activators and the like.

The external preparation composition for skin of the present invention can be applied to any form such as an oily composition and an emulsified composition which can be produced by a usual method. It is preferably an emulsified composition, more preferably a water-in-oil emulsified cosmetic, more preferably an oil-in-water emulsified cosmetic, and even more preferably a water-in-oil emulsified cosmetic. As the preparation, it can be applied as a liquid, a milky liquid, a paste, a cream, a gel, a solid, a sheet or the like.
The skin external preparation composition of the present invention can be used for cosmetics, non-pharmaceutical products, and pharmaceutical applications, and can be used for lotions, emulsions, creams, beauty liquids, dispersions, gels, ointments, packs, mousses, aerosols, and poultices. Skin care cosmetics such as cleaning agents; UV protection cosmetics such as sunscreen emulsions and sunscreen creams; makeup bases, foundations, concealers, blushers, eye shadows, mascara, eyeliners, eyebrows, overcoats, lipsticks, etc. It can be applied as an up cosmetic.

In the present invention, the shape of the skin can be controlled by applying the composition containing the components (A) and (B) to the skin.
The method of application to the skin is not limited, and either application or spraying may be used.
In addition, controlling the shape of the skin means that the surface of the skin is covered from the outside to form a three-dimensional improvement without impairing the natural appearance of the external shape of the skin. For example, it is possible to improve slack in the eyes and face line.

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 performed by the following methods.

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

(Deformation rate)
A 10% by mass hexamethyldisiloxane solution of the polymer of the component (A) used in each composition was prepared. 0.005 g of this solution is applied to one side of a polyethylene sheet 1 (“LL film” manufactured by Enshu Kasei Kogyo Co., Ltd.) having a width (W) of 20 mm × a length (L0) of 100 mm × a thickness of 0.03 mm, as shown in FIG. 1 (a). In a constant temperature bath set at 40 ° C., the polyethylene sheet 1 was applied to a range of width 20 mm × length 50 mm (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 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 in the portion 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 taken as the average value of the values measured on the two long sides of the polyethylene sheet 1.

(Bending resistance)
A 30% by mass hexamethyldisiloxane solution of the polymer of the component (A) used in each composition was prepared. This solution was applied to a polyethylene terephthalate film (Toray Industries, Inc. "Lumirror 100T60") having a width of 50 mm, a length of 100 mm, and a thickness of 0.1 mm using a 200 μm applicator, and placed in a constant temperature bath set at 40 ° C. for 120 minutes. The film was dried 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 (Bending tester manufactured by Ericssen, Model 266), diameters 32 mm, 25 mm, 20 mm, 16 mm, 12 mm, 10 mm, with the surface of the test piece on the polymer film side facing outward. Flexibility tests were performed sequentially from the larger diameter cylindrical mandrel using 8 mm, 6 mm, 4 mm, 3 mm, and 2 mm cylindrical mandrels. The test was terminated when cracks were generated in the polymer membrane, and the minimum diameter (mm) of the cylindrical mandrel in which cracks did not occur was taken as the bending resistance value. The smaller this value is, the better the bending resistance is.

(No secondary adhesion to towels)
Five expert panelists applied each composition to the skin, and after 4 hours had passed, the lack of secondary adhesion to the towel when the skin was pressed with a cotton towel was sensory-evaluated according to the following criteria. The results are shown by the total score of 5 people.
5: Does not adhere to the towel.
4: It hardly adheres to the towel.
3: Slightly adheres to the towel.
2: Adhere to the towel.
1: It adheres to the towel considerably.

(Non-sticky)
Immediately after applying each composition to the skin, the non-stickiness was sensory-evaluated by five specialized panelists according to the following criteria. The results are shown by the total score of 5 people.
5: I don't feel sticky.
4: I don't feel too sticky.
3: I feel a little sticky.
2: I feel sticky.
1: I feel quite sticky.

(Skin elasticity)
Immediately after applying each composition to the skin, the elasticity of the skin was sensory-evaluated by five specialized panelists according to the following criteria. The results are shown by the total score of 5 people.
5: I feel the elasticity of the skin.
4: Feel the elasticity of the skin.
3: I feel the elasticity of the skin a little.
2: I don't feel the elasticity of the skin so much.
1: I don't feel the elasticity of my skin.

(Finish with inconspicuous color unevenness)
Immediately after applying each composition to the skin, five specialized panelists sensory-evaluated the inconspicuous color unevenness of the finished product according to the following criteria. The results are shown by the total score of 5 people.
5: Color unevenness is not noticeable.
4: Color unevenness is not so noticeable.
3: Color unevenness is a little noticeable.
2: Color unevenness is noticeable.
1: Color unevenness is quite noticeable.

(Effect of improving sagging around the eyes)
Immediately after applying each composition to the skin, the effect of improving the sagging of the eyes was sensory-evaluated by five specialized panelists according to the following criteria. The results are shown by the total score of 5 people.
5: The slack around the eyes has improved considerably.
4: The slack around the eyes has improved.
3: The slack around the eyes improved a little.
2: The slack around the eyes does not improve much.
1: The slack around the eyes does not improve.

Examples 1 to 19, Comparative Examples 1 to 2
The skin external preparation composition (water-in-oil emulsification foundation) having the compositions shown in Tables 1 and 2 is manufactured, and the non-adhesiveness to the towel, the non-stickiness, the elasticity of the skin, and the uneven color are inconspicuous. The finish and the effect of improving the sagging around the eyes were evaluated. The results are also shown in Tables 1 and 2.

(Production method)
A solution in which the components (A), (B) and other components were mixed was dispersed with a disper and then stirred with a homomixer to obtain a skin external preparation composition.

In the table, * 1 is 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 norbornene) A solution of the 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.

Example 20
In the same manner as in Examples 1 to 19, skin external preparation compositions (water-in-oil emulsified foundation) having the compositions shown in Table 3 were produced.
The obtained external skin composition has no secondary adhesion to the towel, is not sticky when applied, gives a feeling of elasticity of the skin, and gives a finish in which color unevenness is inconspicuous, and has an effect of improving the sagging of the eyes. Is also excellent.

Examples 21-22
In the same manner as in Examples 1 to 19, skin external preparation compositions (oil-in-water emulsified cosmetics (liquid type foundation)) having the compositions shown in Table 4 were produced.
All of the obtained external skin preparation compositions have no secondary adhesion to the towel, are not sticky when applied, feel the elasticity of the skin, obtain a finish in which color unevenness is inconspicuous, and improve the sagging of the eyes. It is also excellent in effect.

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

Claims (7)

The following components (A) and (B):
(A) Film-forming polymer 0.001 to 30% by mass,
(B) Wrinkle improving component 0.01 to 15% by mass
A skin external preparation composition containing. The film-forming polymer of the component (A) is a polymer having a silicone structure, the deformation ratio measured by the following method (1) is 0.3 or more and 1 or less, and the film-forming polymer is carried out by the following method (2). The skin external preparation composition according to claim 1, wherein the minimum diameter of the cylindrical mandrel that does not cause cracks in the film of the polymer in the bending resistance test by the cylindrical mandrel method is a polymer of 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 in the portion to which the solution is applied is L1, the length of the polyethylene sheet in 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 was 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 that does not cause cracks in the polymer film on the test piece. Ask for. The skin external preparation composition according to claim 1 or 2, wherein the component (B) is one or more selected from vitamin A and its derivatives, vitamin B ₃ and its derivatives, and guanidine derivatives. The skin external preparation composition according to any one of claims 1 to 3, wherein the component (B) is one or more selected from retinol, nicotinamide and N-amidinoproline. The skin external preparation composition according to any one of claims 1 to 4, wherein the mass ratio (B) / (A) of the component (B) to the component (A) is 0.1 to 100. The skin external preparation composition according to any one of claims 1 to 5, further comprising (C) a volatile oil. The following components (A) and (B):
(A) Film-forming polymer 0.001 to 30% by mass,
(B) Wrinkle improving component 0.01 to 15% by mass
A method of applying a composition containing the above to the skin to control the shape of the skin.

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