JP2005325060A - Skin care preparation for external use - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a skin care preparation for external use having excellent moisture retaining effects and an excellent feeling of use without an unpleasant touch such as stickiness. <P>SOLUTION: This skin care preparation for external use comprises the following components (A) and (B). (A) an aqueous polymer containing one or more kinds of constituent units derived from monomers represented by formula (I), one or more kinds of constituent units derived from monomers represented by formula (II) and one or more kinds of constituent units derived from monomers represented by formula (III) and having 3-40 mass% content of the constituent units derived from the monomers represented by formula (I) on the average in one molecule and 300,000-10,000,000 number-average molecular weight measured by GPC (gel permeation chromatography) and expressed in terms of a polyethylene glycol and (B) a polyhydric alcohol. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an external preparation for skin, and more particularly to an external preparation for skin suitable for cosmetics.

  In skin preparations such as cosmetics, increasing the moisture content in the skin, that is, imparting moisture retention, increases the barrier function of stratum corneum cells and prevents the invasion of stimulating factors from the outside. Has become one of the major themes. Usually, for such moisturizing, measures such as increasing the content of polyhydric alcohol and blending moisturizing polymers such as sodium hyaluronate and sodium chonditine sulfate are taken. In this case, since there is an uncomfortable feeling in use such as stickiness derived from polyhydric alcohol or moisturizing polymer, it cannot be said to be a very preferable measure. (See, for example, Patent Document 1 and Patent Document 2) Searching for cosmetics that satisfy both the feeling of use and moisture retention has been made, but in reality, such cosmetics have not yet been obtained. On the other hand, various attempts have been made to develop a polymer having hydrophilicity by combining a monomer having a fluorohydrocarbon group and a hydrophilic monomer by applying polymer technology. A functional material is obtained in which the coating becomes hydrophobic when formed (see, for example, Patent Document 3, Patent Document 4, Patent Document 5, Patent Document 6, and Patent Document 7). Even in the case of a functional polymer, a polymer having characteristics that satisfy both the feeling of use and the moisture retention has not been obtained.

JP 2004-107242 A JP 2004-99564 A Japanese Patent Laid-Open No. 11-158037 Japanese Patent Laid-Open No. 11-158039 JP 2004-115502 A JP 2001-316422 A Japanese Patent Laid-Open No. 2001-200009

  This invention is made | formed in such a condition, and makes it a subject to provide the skin external preparation which was excellent in the usability | use_condition which has the outstanding moisturizing effect and there is no unpleasant feelings, such as stickiness.

As a result of diligent research to solve the above-mentioned problems, the present inventors have combined a polyhydric alcohol and a fluorine-containing acrylic copolymer having a specific composition to provide an excellent feeling of use without an unpleasant feel such as stickiness. It was found that an external preparation for skin having a high moisturizing effect was obtained, and the present invention was completed based on this finding.
That is, the present invention is as follows.
(1) An external preparation for skin comprising components A and B.
A) One or more structural units derived from the monomer represented by the general formula (I), one or more structural units derived from the monomer represented by the general formula (II), and the general formula (III) And the content of the structural unit derived from the monomer represented by the general formula (I) is 3 to 40% by mass on average in one molecule. An aqueous copolymer having a number average molecular weight in terms of polyethylene glycol measured by GPC (gel permeation chromatography) of 300,000 to 10,000,000.
B) Polyhydric alcohol

一般式（Ｉ）
（式（Ｉ）中、Ｒ^１は水素原子又は炭素数１〜３のアルキル基を表し、Ｒ^２は３〜２１個の置換フッ素原子を有する炭素数２〜１２のアルキル基を表す。）

Formula (I)
(In formula (I), R ¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ² represents an alkyl group having 2 to 12 carbon atoms having 3 to 21 substituted fluorine atoms.)

一般式（ＩＩ）
（式（ＩＩ）中、Ｒ^３は水素原子又は炭素数１〜３のアルキル基を表し、Ｒ^４は水酸基を有していてもよい炭素数２〜４のアルキレン基を表し、Ｒ^５は水素原子、炭素数６〜１０の芳香族基、炭素数１〜２０の脂肪族炭化水素基、又は炭素数１〜１２のアシル基を表す。ｎは２〜９０の数値を表す。）

Formula (II)
(In Formula (II), R ³ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ⁴ represents an alkylene group having 2 to 4 carbon atoms which may have a hydroxyl group, and R ⁵ represents hydrogen. An atom, an aromatic group having 6 to 10 carbon atoms, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an acyl group having 1 to 12 carbon atoms, n represents a numerical value of 2 to 90.)

一般式（ＩＩＩ）
（式（ＩＩＩ）中、Ｒ^６は水素原子又は炭素数１〜３のアルキル基を表し、Ｒ^７はひとつの水素原子が水酸基で置換されている炭素数２〜６のアルキル基を表す。）
（２） 前記一般式（ＩＩ）で表されるモノマーが、下記一般式（ＩＶ）で表されるものであることを特徴とする（１）に記載の皮膚外用剤。

Formula (III)
(In formula (III), R ⁶ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ⁷ represents an alkyl group having 2 to 6 carbon atoms in which one hydrogen atom is substituted with a hydroxyl group.)
(2) The external preparation for skin according to (1), wherein the monomer represented by the general formula (II) is represented by the following general formula (IV).

一般式（ＩＶ）
（式（ＩＶ）中、Ｒ^８は水素原子又は炭素数１〜３のアルキル基を表し、Ｒ^９は水素原子、炭素数６〜１０の芳香族基、炭素数１〜２０の脂肪族炭化水素基、又は炭素数１〜１２のアシル基を表す。ｑは４〜９０の数値を表す。）

Formula (IV)
(In formula (IV), R ⁸ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ⁹ represents a hydrogen atom, an aromatic group having 6 to 10 carbon atoms, or an aliphatic hydrocarbon having 1 to 20 carbon atoms. Group or a C1-C12 acyl group, q represents a numerical value of 4 to 90.)

(3) The skin external preparation according to (1) or (2), wherein the polyhydric alcohol is a polyhydric alcohol having 2 to 6 carbon atoms.
(4) The skin external preparation according to any one of (1) to (3), wherein the content of the polyhydric alcohol is 8 to 45% by mass.

    ADVANTAGE OF THE INVENTION According to this invention, the skin external preparation excellent in the moisturizing effect and excellent in the usability without stickiness etc. is obtained.

Hereinafter, the present invention will be described in detail.
(1) One or more structural units derived from the monomer represented by the general formula (I) contained in the aqueous copolymer used in the skin external preparation of the present invention. The aqueous copolymer used in the skin external preparation of the present invention comprises: One or more structural units derived from a monomer represented by the following general formula (I) (hereinafter also referred to as “structural unit (I)”) are included as essential structural units.

一般式（Ｉ）
（式（Ｉ）中、Ｒ１は水素原子又は炭素数１〜３のアルキル基を表し、Ｒ２は３〜２１個の置換フッ素原子を有する炭素数２〜１２のアルキル基を表す。）

Formula (I)
(In formula (I), R1 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R2 represents an alkyl group having 2 to 12 carbon atoms having 3 to 21 substituted fluorine atoms.)

  Here, examples of the alkyl group represented by R1 include a methyl group, an ethyl group, a propyl group, a 1-methylethyl group, and a cyclopropyl group. In the present invention, R1 is preferably a hydrogen atom or a methyl group. Moreover, as a C2-C12 alkyl group which has 3-21 substituted fluorine atoms represented by R2, 2,2,2-trifluoroethyl group, 2,2,3,3-tetrafluoropropyl Group, 1,1,1,3,3,3-hexafluoroisopropyl group, 2,2,3,3,4,4,5,5-octafluoropentyl group, 1H, 1H, 2H, 2H-nonafluoro Hexyl group, 1H, 1H, 7H-dodecafluoroheptyl group, 1H, 1H-tridecafluoroheptyl group, 1H, 1H-pentadecafluorooctyl group, 1H, 1H, 2H, 2H-heptadecafluorodecyl group, 1H, Preferred examples include 1H, 11H-eicosafluoroundecyl group and the like. Such a compound represented by the general formula (I) can be obtained by condensing an acid chloride derived from acrylic acid or α-alkylacrylic acid and an alcohol containing a fluorine atom in the presence of an alkali. Further, some of the compounds represented by the general formula (I) are already commercially available, and can be used. As an example, there are biscoat 3F, 3FM, 4F, 4FM, 6FM, 8F, 8FM, 17F, and 17FM (all manufactured by Osaka Organic Chemical Industry Co., Ltd.).

  In the aqueous copolymer for use in the external preparation for skin of the present invention, the structural unit (I) may be only one type, but if it satisfies the general formula (I), two or more types should be combined to form a structural unit. You can also.

  In the aqueous copolymer used in the skin external preparation of the present invention, the proportion of the structural unit (I) is 3 to 40% by mass, preferably 3 to 35% by mass, based on the total structural units constituting the aqueous copolymer. %, More preferably 5 to 30% by weight. The structural unit (I) derived from the monomer represented by the above general formula (I) maintains the hydrophilic-hydrophobic balance on the skin of the aqueous copolymer used in the skin external preparation of the present invention, and the skin external preparation. If the proportion of the structural unit (I) is too smaller than the above range, the water-soluble copolymer can ensure water solubility, but the hydrophilicity is too high to prevent stickiness of the external preparation for skin. Sometimes. On the other hand, when the amount is more than the above range, the water-soluble copolymer cannot be ensured in water, and it may be difficult to prepare a skin external preparation.

(2) One or more structural units derived from the monomer represented by the general formula (II) contained in the aqueous copolymer used in the skin external preparation of the present invention. The aqueous copolymer used in the skin external preparation of the present invention comprises: One or more structural units derived from a monomer represented by the following general formula (II) (hereinafter also referred to as “structural unit (II)”) are included as essential structural units.

一般式（ＩＩ）
（式（ＩＩ）中、Ｒ３は水素原子又は炭素数１〜３のアルキル基を表し、Ｒ４は水酸基を有していてもよい炭素数２〜４のアルキレン基を表し、Ｒ５は水素原子、炭素数６〜１０の芳香族基、炭素数１〜２０の脂肪族炭化水素基、又は炭素数１〜１２のアシル基を表す。ｎは２〜９０の数値を表す。）

Formula (II)
(In formula (II), R3 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R4 represents an alkylene group having 2 to 4 carbon atoms which may have a hydroxyl group, and R5 represents a hydrogen atom or carbon. An aromatic group having 6 to 10 carbon atoms, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an acyl group having 1 to 12 carbon atoms, and n represents a numerical value of 2 to 90.)

  Here, examples of the alkyl group represented by R3 include a methyl group, an ethyl group, a propyl group, a 1-methylethyl group, and a cyclopropyl group. In the present invention, R3 is preferably a hydrogen atom or a methyl group. Examples of the alkylene group represented by R4 include an ethylene group, a propylene group, an isopropylene group, a 2-hydroxypropylene group, a 1-hydroxy-2-methylethylene group, and a 2-hydroxy-1-methylethylene group. Of these, ethylene group or propylene group is preferable, and ethylene group is more preferable. In addition, among the groups represented by R5, examples of the aromatic group having 6 to 10 carbon atoms include a phenyl group, a benzyl group, a methylphenyl group, and an ethylphenyl group; Examples of hydrogen groups include methyl, ethyl, butyl, tertiary butyl, hexyl, cyclohexyl, octyl, 2-ethylhexyl, lauryl, myristyl, palmityl, stearyl, and oleyl. Examples of the acyl group having 1 to 12 carbon atoms include a formyl group, an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a valeryl group, and a lauroyl group. Of these, the group represented by R5 is preferably an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and more preferably an alkyl group having 1 to 12 carbon atoms. n is a numerical value of 2 to 90, more preferably 4 to 90.

  Among the monomers represented by the above general formula (II), specific examples of the monomer in which R4 is a propylene group include polypropylene glycol (6) monoacrylate, polypropylene glycol (9) monoacrylate, and polypropylene glycol (13) monoacrylate. , Polypropylene glycol (9) monomethacrylate, polypropylene glycol (13) monomethacrylate and the like. Many of these polymers are commercially available. As an example, there are trade names “Blemmer” AP-400, AP-550, AP-800, PP-500, PP-800 (all manufactured by NOF Corporation) and the like. A specific example of the monomer in which R4 is an ethylene group will be described later.

Among the structural units derived from the monomer represented by the general formula (II), a structural unit derived from the monomer represented by the general formula (IV) is particularly preferable.

一般式（ＩＶ）
（式（ＩＶ）中、Ｒ８は水素原子又は炭素数１〜３のアルキル基を表し、Ｒ９は水素原子、炭素数６〜１０の芳香族基、炭素数１〜２０の脂肪族炭化水素基、又は炭素数１〜１２のアシル基を表す。ｑは４〜９０の数値を表す。）

Formula (IV)
(In the formula (IV), R8 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R9 represents a hydrogen atom, an aromatic group having 6 to 10 carbon atoms, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, Or represents an acyl group having 1 to 12 carbon atoms, q represents a numerical value of 4 to 90.)

  Specific examples of the monomer represented by the general formula (IV) include polyethylene glycol (4.5) monoacrylate, polyethylene glycol (4.5) monomethacrylate, polyethylene glycol (10) monoacrylate, polyethylene. Glycol (8) monomethacrylate, polyethylene glycol (23) monoacrylate, polyethylene glycol (23) monomethacrylate, methoxypolyethylene glycol (9) acrylate, methoxypolyethylene glycol (4) methacrylate, methoxypolyethylene glycol (9) methacrylate, methoxypolyethylene glycol (23) Methacrylate, methoxypolyethylene glycol (90) Methacrylate, Lauroxypolyethylene glycol (4) Acrylic , Lauroxy polyethylene glycol (18) acrylate, Lauroxy polyethylene glycol (4) Methacrylate, Stearoxy polyethylene glycol (4) Methacrylate, Stearoxy polyethylene glycol (9) Methacrylate, Stearoxy polyethylene glycol (30) Methacrylate, Oleoxy Polyethylene glycol (18) acrylate, oleyloxy polyethylene glycol (18) methacrylate, nonyl phenoxy polyethylene glycol (5) acrylate, nonyl phenoxy polyethylene glycol (30) acrylate, lauroyloxy polyethylene glycol (10) methacrylate, stearoyloxy polyethylene glycol ( 40) Acrylate, stearoyloxypolyethylene Recall (40) methacrylate, and the like. The numbers in parentheses indicate the value of q.

  These hydrophilic monomers can be obtained in high yield by an esterification reaction of the corresponding polyethylene glycol, polyethylene glycol monoether, polyethylene glycol monoester and acrylic acid or methacrylic acid chloride or anhydride. Moreover, since there are already many commercial products, it is also possible to use such commercial products. For example, the trade names Blemmer Blemmer AE-200, AE-400, PE-200, PE-350, AME-400, PME-200, PME-400, PME-1000, PME-4000, ALE-200. ALE-800, PLE-200, PSE-200, PSE-400, PSE-1300, ANE-300, ANE-1300, etc. (all manufactured by NOF Corporation).

  The structural unit (II) contained in the aqueous copolymer used in the external preparation for skin of the present invention may be only one kind, but if it satisfies the above general formula (II), two or more kinds of structural units (II) are combined. You may have. The aqueous copolymer used in the external preparation for skin of the present invention contains one or more structural units (II) in a total amount of 20 to 70% by mass, preferably 20 to 65%, based on all the structural units constituting the aqueous copolymer. More preferably, it has 25-60 mass%.

  The structural unit derived from the monomer represented by the general formula (II) is responsible for the water solubility of the aqueous copolymer used in the skin external preparation of the present invention and a suitable feel of the skin external preparation, If the content of II) is less than the above range, the solubility of the aqueous copolymer in water will be reduced, making it difficult to prepare a topical skin preparation. It is not preferable because it may not be possible to suppress the touch.

(3) One or more structural units derived from the monomer represented by the general formula (III) contained in the aqueous copolymer used in the skin external preparation of the present invention. The aqueous copolymer used in the skin external preparation of the present invention comprises: One or more structural units derived from a monomer represented by the following general formula (III) (hereinafter also referred to as “structural unit (III)”) are included as essential structural units.

一般式（ＩＩＩ）
（式（ＩＩＩ）中、Ｒ６は水素原子又は炭素数１〜３のアルキル基を表し、Ｒ７はひとつの水素原子が水酸基で置換されている炭素数２〜６のアルキル基を表す。）

Formula (III)
(In formula (III), R6 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R7 represents an alkyl group having 2 to 6 carbon atoms in which one hydrogen atom is substituted with a hydroxyl group.)

  Here, examples of the alkyl group represented by R6 include a methyl group, an ethyl group, a propyl group, a 1-methylethyl group, and a cyclopropyl group. In the present invention, R6 is preferably a hydrogen atom or a methyl group. Examples of the alkyl group having 2 to 6 carbon atoms in which one hydrogen atom of R7 is substituted with a hydroxyl group include 2-hydroxyethyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-methyl-2hydroxy Examples thereof include an ethyl group, a 4-hydroxybutyl group, and a 3-hydroxybutyl group. Of these, a 2-hydroxyethyl group, a 2-hydroxypropyl group, and a 3-hydroxypropyl group are preferable.

  Specific examples of the monomer represented by the general formula (III) include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, and 3-hydroxypropyl acrylate. 3-hydroxypropyl methacrylate, 1-methyl-2hydroxyethyl acrylate, 1-methyl-2hydroxyethyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, etc. Can be mentioned. These monomers can be obtained in high yield by an esterification reaction between the corresponding dihydric alcohol and acrylic acid or methacrylic acid chloride or anhydride. Since many commercial products already exist, it is also possible to use such commercial products.

  In the aqueous copolymer used in the skin external preparation of the present invention, the structural unit (III) may be only one kind, but if it satisfies the general formula (III), two or more kinds may be combined to form a structural unit. it can.

  The aqueous copolymer used in the external preparation for skin of the present invention comprises 10 to 55% by mass, preferably 15 to 50% by mass, more preferably 15 to 50% by mass of the structural unit (III) with respect to all the structural units constituting the aqueous copolymer. Has 20-45 mass%. The structural unit (III) derived from the monomer represented by the general formula (III) maintains the hydrophilic-hydrophobic balance on the skin of the aqueous copolymer used in the skin external preparation of the present invention. If the proportion of the structural unit (III) is more than the above range, the water-soluble copolymer can ensure water solubility, but the hydrophilicity is too high to prevent stickiness of the skin external preparation. Sometimes. On the other hand, if the amount is less than the above range, the hydrophobicity is too strong and the external preparation for skin may not be applied to the skin, which is not preferable.

(4) Other optional structural units that can be included in the aqueous copolymer used in the external skin preparation of the present invention The aqueous copolymer used in the external skin preparation of the present invention is other than the above essential structural units (I) to (III) Furthermore, it is possible to have an arbitrary structural unit derived from a monomer that can usually constitute a copolymer as long as the function and effect of the external preparation for skin of the present invention are not impaired. Examples of the monomer for deriving such an arbitrary structural unit include polymerizable carboxylic acids such as acrylic acid, methacrylic acid, and maleic acid; (methacrylic acid amide, methacrylic acid amide, acrylic acid monoalkylamide, methacrylic acid monoalkylamide, etc. ) Acrylate amide; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, hexyl (meth) acrylate, (meth ) (Meth) acrylic acid alkyl esters such as 2-ethylhexyl acrylate; (meth) acrylic acid aryl esters such as benzyl (meth) acrylate; methoxymethyl (meth) acrylate, methoxyethyl (meth) acrylate, etc. (Meth) acrylic acid alkoxyalkyl ester; vinyl acetate Vinylpyrrolidone, styrene, α-methylstyrene, acrylonitrile and the like. Most of these monomers are commercially available.

(5) Aqueous copolymer used in the external preparation for skin of the present invention The aqueous copolymer used for the external preparation for skin of the present invention is composed of the above structural units (I), (II) and (III), and other optional components as necessary. Is a copolymer containing the structural unit in its skeleton. The copolymer is usually a random copolymer in which structural units are bonded at random, but may be a block copolymer or a graft copolymer.

  The number average molecular weight in terms of polyethylene glycol measured by GPC (gel permeation chromatography) is 300,000 to 10,000,000, preferably 400,000 to 8,000,000, more preferably 400. , 000 to 6,000,000.

  The method for producing the aqueous copolymer used in the external preparation for skin of the present invention is not particularly limited. For example, a monomer for deriving each structural unit is mixed in a solvent, and a polymerization reaction is carried out according to a method usually used for polymerization of acrylic monomers. It can be obtained by a method. Furthermore, as conditions for increasing the molecular weight of the copolymer, for example, radical solution polymerization is used as an example, polymerization at a high monomer concentration, reduction of the amount of initiator, dripping of a monomer, use of a chain transfer agent such as 2-mercaptoethanol Etc.

  In the skin external preparation of the present invention, such an aqueous polymer can contain only one species, or can contain two or more species in combination. Such an aqueous polymer has a function of remarkably suppressing the appearance of an unpleasant feeling of use such as the appearance of a sticky feeling due to a polyhydric alcohol or the like in the external preparation for skin of the present invention. The preferable content of the aqueous copolymer in the external preparation for skin of the present invention is 0.1 to 15% by mass, more preferably 0.5 to 10% by mass, based on the total amount of external preparation for skin. If the content of the aqueous copolymer is too small, an unpleasant feeling of use such as stickiness due to the polyhydric alcohol may not be suppressed, and if it is too large, formulation may be difficult.

(6) Polyhydric alcohol which is an essential component of the external preparation for skin of the present invention The external preparation for skin of the present invention is characterized by containing polyhydric alcohol as an essential component. The polyhydric alcohol used in the external preparation for skin of the present invention can be used without particular limitation as long as it is usually used in external preparations for skin such as cosmetics. The polyhydric alcohol is preferably exemplified. Examples of such polyhydric alcohols include ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, glycerin, polyglycerin, 1,3 butylene glycol, pentaerythritol, 1,2 pentanediol, isoprene glycol, and 1,2. Preferred examples include sugar alcohols such as xylene glycol and sorbitol. These can be contained alone or in combination of two or more. In the external preparation for skin of the present invention, the polyhydric alcohol functions as a main element that realizes excellent moisture retention. From such a viewpoint, the content of the polyhydric alcohol in the external preparation for skin of the present invention is preferably 8 to 45 mass%, more preferably 10 to 40 mass%, based on the total amount of the external preparation for skin. . If the amount of the polyhydric alcohol is too small, a sufficient moisturizing effect cannot be imparted to the external preparation for skin, and if the amount of the polyhydric alcohol is too large, the aqueous copolymer may become insoluble and formulation may be difficult. is there.

(7) External preparation for skin of the present invention The external preparation for skin of the present invention is characterized by containing one or more of the aqueous copolymers and one or more polyhydric alcohols. The polyhydric alcohol exhibits an excellent moisturizing effect, and the interaction between the polyhydric alcohol and the aqueous copolymer suppresses unpleasant feeling of use such as stickiness during use due to the polyhydric alcohol. In addition, the water-based polymer itself also has an excellent water dispersion loss suppressing action, whereby the external preparation for skin of the present invention has excellent moisturizing properties and excellent usability. In the present invention, the topical skin preparation is a general term for compositions that are externally administered to the skin, and examples thereof include cosmetics, skin external medicines, and external goods, and any of these may be the skin of the present invention. Although an external preparation can be applied, it is particularly preferably applied to cosmetics. The cosmetic can be applied without particular limitation as long as it is a commonly known formulation such as lotion, cosmetic liquid, milky lotion, cream, peel-off pack, foam pack, under-makeup, foundation and the like.

  Furthermore, it is possible to mix | blend the arbitrary components which can be normally mix | blended with cosmetics other than an aqueous copolymer and a polyhydric alcohol in the skin external preparation of this invention. Examples of these optional components include hydrocarbons such as squalane, liquid paraffin, light liquid isoparaffin, heavy liquid isoparaffin, microcrystalline wax, and solid paraffin; dimethicone, femethicone, cyclomethicone, amodimethicone, polyether-modified silicone Silicones such as jojoba oil, carnauba wax, owl, beeswax, gallow, octyldodecyl oleate, isopropyl myristate, neopentyl glycol diisostearate, diisostearate malate; stearic acid, laurin Fatty acids such as acid, myristic acid, palmitic acid, isostearic acid, isopalmitic acid, behenic acid, oleic acid; behenyl alcohol, cetanol, oleyl alcohol, octadec Higher alcohols such as alcohol; castor oil, coconut oil, hydrogenated coconut oil, coconut oil, wheat germ oil, isostearic acid triglyceride, isooctanoic acid triglyceride, olive oil, and other triglycerides; sorbitan sesquioleate, sorbitan monooleate, sorbitan trioleate Sorbitan sesquistearate, sorbitan monostearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan monostearate, polyoxyethylene stearate, polyoxyethylene oleate, polyoxyethylene glyceryl fatty acid ester, polyoxyethylene alkyl ether, Nonionic surfactants such as polyoxyethylene hydrogenated castor oil; sodium lauryl stearate, polyoxyethylene alkyl sulfate, Anionic surfactants such as rufosuccinic acid ester salts; Cationic surfactants such as quaternary alkyl ammonium salts; Amphoteric surfactants such as alkyl betaines; Crystalline cellulose, cross-linked methylpolysiloxane, polyethylene powder, acrylic resin powder Organic powders such as talc, mica, sericite, magnesium carbonate, calcium carbonate, titanium dioxide, iron oxide, bitumen, ultramarine, titanium mica, titanium sericite, silica, etc. Acrylic / alkyl methacrylate copolymers and / or salts thereof, carboxyvinyl polymers and / or salts thereof, thickeners such as xanthan gum and hydroxypropyl cellulose; retinol, retinoic acid, tocopherol, riboflavin, pyridoxine, ascorbic acid, ascorbine Acid Active ingredients such as vitamins such as acid ester salts, terpenes such as glycyrrhetinate, glycyrrhetin, ursolic acid, oleanolic acid, steroids such as estradiol, ethinylestradiol, estriol; phenoxyethanol, parabens, hibiten gluconate, Preferred examples include antiseptics such as benzalkonium chloride; ultraviolet absorbers such as dimethylaminobenzoic acid esters, cinnamic acid esters, and benzophenones. These are appropriately selected according to the application.

  Hereinafter, the present invention will be described in more detail with reference to examples, but it goes without saying that the present invention is not limited to such examples.

<Production Example of Monomer Represented by General Formula (I) Deriving Structural Unit (I)>
<Production example 1>
12.8,1H, 2H, 2H-nonafluoro-1-hexanol 52.8 g as fluoroalcohol and 50 g of triethylamine were dissolved in 500 ml of tetrahydrofuran. While the resulting solution was ice-cooled and stirred, a solution prepared by dissolving 18.1 g of acrylic acid chloride as an acid chloride in 100 ml of tetrahydrofuran was added dropwise to this solution over 2 hours. After completion of the dropwise addition, the white precipitate formed was filtered, and tetrahydrofuran and triethylamine were removed from the filtrate using a rotary evaporator. It was confirmed that the compound obtained by NMR measurement was 1H, 1H, 2H, 2H-nonafluorohexyl acrylate, which is a monomer represented by the above general formula (I).

<Production Examples 2-5>
A monomer represented by the above general formula (I) was produced in the same manner as in Production Example 1 except that the kind and amount of fluoroalcohol and acid chloride were changed as shown in Table 1 in Production Example 1.

<Production Example of Monomer Represented by General Formula (II) Deriving Structural Unit (II)>
<Production Example 6>
103 g of polyethylene glycol # 1000 as a polyethylene glycol compound and 50 g of triethylamine were dissolved in 500 ml of tetrahydrofuran. While the resulting solution was ice-cooled and stirred, a solution prepared by dissolving 5.2 g of methacrylic acid chloride as an acid chloride in 100 ml of tetrahydrofuran was added dropwise to this solution over 2 hours. After completion of dropping, the produced white precipitate was filtered, and tetrahydrofuran and triethylamine were removed from the filtrate using a rotary evaporator to obtain a product. By NMR measurement, it was confirmed that the obtained compound was polyethylene glycol (23) monomethacrylate, which is a monomer represented by the above general formula (II).

<Production Examples 7-8>
A monomer represented by the above general formula (II) was produced in the same manner as in Production Example 6 except that in Production Example 6, the types and amounts of the polyethylene compound and acid chloride were changed as shown in Table 2.

<Production Example of Aqueous Copolymer for Use in External Preparation for Skin of the Present Invention>
<Production Example 9>
2,2,3,3,4,4,5,5-octafluoropentyl acrylate (manufactured by Osaka Organic Chemical Co., Ltd., trade name “Biscoat 8F”) was added to a flask equipped with a nitrogen inlet tube, a condenser and a stirrer. ) 13.2 g, 41.8 g of methoxypolyethylene glycol (4) methacrylate (Nippon Yushi Co., Ltd., trade name “Blenmer PME-200”), methoxypolyethylene glycol (23) methacrylate (Nippon Yushi Co., Ltd., trade name) “Blenmer PME-1000”) 16.9 g, 2-hydroxyethyl methacrylate (Tokyo Chemical Industry Co., Ltd.) 48.1 g, 2-mercaptoethanol 0.12 g, and 300 ml of isopropyl alcohol and 300 ml of water The mixture was stirred and mixed. While stirring was continued, nitrogen gas substitution was performed for 1 hour. A solution prepared by dissolving 0.5 g of ammonium persulfate in 20 ml of water was added, and the reaction was continued at 65 ° C. for 16 hours while further stirring. After completion of the reaction, the pH was adjusted to 7.0, and isopropyl alcohol was removed with a rotary evaporator to obtain an aqueous solution of aqueous copolymer 1, which is an aqueous copolymer used in the present invention. The number average molecular weight in terms of polyethylene of this aqueous copolymer was measured by the following method and found to be 6.0 × 10 ⁶ .

<Method for measuring molecular weight of aqueous copolymer>
The number average molecular weight in terms of polyethylene glycol of the aqueous copolymer 1 obtained as an aqueous solution was measured by high performance liquid chromatography equipped with a GPC column. The measurement conditions are shown below.
-Measurement conditions-
Detector: RI
Column: shodex OHpak SB-806M HQ 8.0 × 300mm
Column temperature: Room temperature Mobile phase: Water flow rate: 1.0 mL / min

<Production Example 10>
To a flask equipped with a nitrogen introduction tube, a cooler, a dropping device and a stirring device, a mixed solvent consisting of 200 ml of ethyl alcohol and 300 ml of water and a solution of 0.3 g of ammonium persulfate dissolved in 10 ml of water were added and stirred. While continuing stirring, nitrogen gas replacement was performed for 1 hour and then heated to 70 ° C. While continuing stirring, 4,0.0 g of 2,2,3,3-tetrafluoropropyl methacrylate (manufactured by Osaka Organic Chemical Co., Ltd., trade name “Biscoat 4FM”), polypropylene glycol (6) monoacrylate (Nippon Yushi Co., Ltd.) Manufactured under the trade name “Blemmer AP-400”) and 100.0 g of propylene glycol monoacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 100 ml of ethyl alcohol over 2 hours using a dropping device. It was dripped. Furthermore, reaction was performed at 70 degreeC for 10 hours. After completion of the reaction, the pH was adjusted to 7.0, and ethyl alcohol was removed by a rotary evaporator to obtain an aqueous solution of aqueous copolymer 2, which is an aqueous copolymer used in the present invention. The number average molecular weight in terms of polyethylene of this aqueous copolymer was measured by the same method as in Production Example 9 and found to be 8.0 × 10 ⁵ .

<Production Example 11>
In a flask equipped with a nitrogen introduction tube, a condenser and a stirrer, 9.0 g of 1H, 1H, 2H, 2H-heptadecafluorodecyl acrylate (manufactured by Osaka Organic Chemical Co., Ltd., trade name “Biscoat 17F”), methoxypolyethylene 45.0 g of glycol (90) methacrylate (manufactured by NOF Corporation, trade name “Blemmer PME-4000”), 22.5 g of 2-hydroxyethyl methacrylate (manufactured by Tokyo Chemical Industry), methyl methacrylate (Tokyo Chemical Industry Co., Ltd.) )) A mixed solvent consisting of 73.5 g, 2-mercaptoethanol 0.06 g and 150 ml of isopropyl alcohol and 150 ml of water was taken and mixed with stirring. While stirring was continued, nitrogen gas substitution was performed for 1 hour. A solution prepared by dissolving 0.2 g of ammonium persulfate in 10 ml of water was added, and the reaction was continued at 70 ° C. for 18 hours while further stirring. After completion of the reaction, the pH was adjusted to 7.0, and isopropyl alcohol was removed with a rotary evaporator to obtain an aqueous solution of aqueous copolymer 3, which is an aqueous copolymer used in the present invention. The polyethylene-converted number average molecular weight of this aqueous copolymer was measured in the same manner as in Production Example 9, and found to be 6.0 × 10 ⁵ .

<Production Example 12>
In a flask equipped with a nitrogen inlet tube, a condenser and a stirrer, 25.0 g of 2,2,2-trifluoroethyl methacrylate (manufactured by Osaka Organic Chemical Co., Ltd., trade name “Biscoat 3FM”), 1,1,1 , 3,3,3-hexafluoroisopropyl methacrylate (produced by Osaka Organic Chemical Co., Ltd., trade name “Biscoat 6FM”) 10.0 g, oleyloxypolyethylene glycol (18) methacrylate (compound of Production Example 7) 45.0 g, 20.0 g of 2-hydroxyethyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.03 g of 2-mercaptoethanol and 200 ml of ethyl acetate were taken and mixed with stirring. While stirring was continued, nitrogen gas substitution was performed for 1 hour. A solution prepared by dissolving 0.2 g of benzoyl peroxide in 10 ml of ethyl acetate was added, and the reaction was carried out by refluxing for 8 hours while continuing stirring. After completion of the reaction, water was added to this solution, and flushing was performed to obtain an aqueous solution of aqueous copolymer 4, which is the aqueous copolymer used in the present invention. The number average molecular weight in terms of polyethylene of this aqueous copolymer was measured by the same method as in Production Example 9 and found to be 4.0 × 10 ⁵ .

<Production Example 13>
0.02 g of 2-mercaptoethanol, 0.2 g of azobisisobutyronitrile and 100 ml of isopropyl alcohol were taken and stirred and mixed in a flask equipped with a nitrogen introduction tube, a cooler, a dropping device and a stirring device. While continuing stirring, nitrogen gas replacement was performed for 1 hour, and then the mixture was heated to 80 ° C. While continuing stirring, 12.0 g of 1H, 1H, 7H-dodecafluoroheptyl methacrylate (Compound of Production Example 2), 40.8 g of Lauroyloxypolyethylene glycol (10) acrylate (Compound of Production Example 8), 4-acrylic acid 4- A solution obtained by dissolving 7.2 g of hydroxybutyl (manufactured by Tokyo Chemical Industry Co., Ltd.) in 100 ml of ethyl alcohol was dropped over 2 hours using a dropping device. Furthermore, after reacting at 80 ° C. for 10 hours, this solution was added to a large amount of n-hexane, and the resulting precipitate was dried and then dissolved in water to form an aqueous copolymer 5 which is an aqueous copolymer used in the present invention. An aqueous solution of was obtained. The number average molecular weight in terms of polyethylene of this aqueous copolymer was measured by the same method as in Production Example 9 and found to be 5.0 × 10 ⁵ .

<Production Example 14>
Into a flask equipped with a nitrogen introduction tube, a condenser and a stirrer, 18.0 g of 1H, 1H, 2H, 2H-nonafluorohexyl acrylate (Compound of Production Example 1), nonylphenoxypolyethylene glycol (30) acrylate (Nippon Yushi ( Co., Ltd., trade name “Blemmer ANE-1300” 18.0 g, methoxypolyethylene glycol (4) methacrylate (manufactured by NOF Corporation, trade name “Blemmer PME-200”) 30.0 g, 4-hydroxy acrylate 12.0 g of butyl (manufactured by Tokyo Chemical Industry Co., Ltd.), 22.0 g of 2-hydroxyethyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.05 g of 2-mercaptoethanol and 400 ml of ethyl acetate were taken and mixed with stirring. While stirring was continued, nitrogen gas substitution was performed for 1 hour. A solution prepared by dissolving 0.3 g of benzoyl peroxide in 10 ml of ethyl acetate was added, and the reaction was carried out by refluxing for 8 hours while continuing stirring. After completion of the reaction, water was added to this solution, and flushing was performed to obtain an aqueous solution of aqueous copolymer 6, which is the aqueous copolymer used in the present invention. It was 3.0 * 10 < ⁶ > when the polyethylene conversion number average molecular weight of this aqueous copolymer was measured by the method similar to manufacture example 9.

<Production Example 15>
In a flask equipped with a nitrogen introduction tube, a condenser and a stirring device, 2,2,3,3-tetrafluoropropyl acrylate (manufactured by Osaka Organic Chemical Co., Ltd., trade name “Biscoat 4F”) 10.8 g, 1H, 1H -1.2 g of tridecafluoroheptyl acrylate (Compound of Production Example 3), stearoxy polyethylene glycol (30) methacrylate (manufactured by NOF Corporation, trade name “Blenmer PSE-1300”), 27.0 g of methacrylate 2- 15.0 g of hydroxyethyl (manufactured by Tokyo Chemical Industry Co., Ltd.), 6.0 g of ethyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.08 g of 2-mercaptoethanol and 180 ml of isopropyl alcohol and 120 ml of water Was mixed with stirring. While stirring was continued, nitrogen gas substitution was performed for 1 hour. A solution prepared by dissolving 0.5 g of ammonium persulfate in 10 ml of water was added, and the reaction was continued at 70 ° C. for 12 hours while further stirring. After completion of the reaction, the pH was adjusted to 7.0, and isopropyl alcohol was removed with a rotary evaporator to obtain an aqueous solution of aqueous copolymer 7, which is an aqueous copolymer used in the present invention. It was 1.0 * 10 < ⁶ > when the polyethylene conversion number average molecular weight of this aqueous copolymer was measured by the method similar to manufacture example 9.

<Production Example 16>
In a flask equipped with a nitrogen introduction tube, a condenser and a stirrer, 2.8 g of 1H, 1H, 11H-eicosafluoroundecyl methacrylate (the compound of Production Example 5), nonylphenoxypolyethylene glycol (5) acrylate (Nippon Yushi ( Co., Ltd., trade name “Blemmer AE-300”) 11.2 g, polyethylene glycol (10) monoacrylate (manufactured by NOF Corporation, trade name “Blemmer AE-400”) 12.0 g, 2-hydroxy acrylate 12.0 g of ethyl (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.0 g of styrene (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.02 g of 2-mercaptoethanol and 160 ml of toluene were taken and mixed with stirring. While stirring was continued, nitrogen gas substitution was performed for 1 hour. A solution in which 0.2 g of azobisisobutyronitrile was dissolved in 10 ml of toluene was added, and the reaction was continued at 70 ° C. for 8 hours while continuing stirring. After completion of the reaction, water was added to this solution, and flushing was performed to obtain an aqueous solution of aqueous copolymer 8, which is the aqueous copolymer used in the present invention. It was 2.0 * 10 < ⁶ > when the polyethylene conversion number average molecular weight of this aqueous copolymer was measured by the method similar to manufacture example 9.

<Production Example 17>
In a flask equipped with a nitrogen inlet tube, a condenser and a stirrer, 6.0 g of 2,2,2-trifluoroethyl acrylate (manufactured by Osaka Organic Chemical Co., Ltd., trade name “Biscoat 3F”), stearoxy polyethylene glycol ( 9) 42.0 g of methacrylate (manufactured by NOF Corporation, trade name “Blemmer PSE-400”), 12.0 g of 2-hydroxyethyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.03 g of 2-mercaptoethanol A mixed solvent consisting of 150 ml of ethyl alcohol and 150 ml of water was taken and mixed with stirring. While stirring was continued, nitrogen gas substitution was performed for 1 hour. A solution in which 0.3 g of potassium persulfate was dissolved in 10 ml of water was added, and the reaction was carried out at 80 ° C. for 12 hours while further stirring. After completion of the reaction, the pH was adjusted to 7.0, and ethyl alcohol was removed with a rotary evaporator to obtain an aqueous solution of aqueous copolymer 9, which is an aqueous copolymer used in the present invention. The number average molecular weight in terms of polyethylene of this aqueous copolymer was measured by the same method as in Production Example 9 and found to be 4.0 × 10 ⁵ .

<Production Example 18>
2,2,3,3,4,4,5,5-octafluoropentyl methacrylate (trade name “Biscoat 8FM” manufactured by Osaka Organic Chemical Co., Ltd.) was added to a flask equipped with a nitrogen inlet tube, a condenser and a stirrer. ) 15.0 g, polyethylene glycol (4.5) monoacrylate (manufactured by NOF Corporation, trade name “Blenmer AE-200”) 30.0 g, 2-hydroxyethyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) A mixed solvent composed of 9.0 g, propylene glycol monoacrylate (Tokyo Chemical Industry Co., Ltd.) 6.0 g, 2-mercaptoethanol 0.03 g, isopropyl alcohol 180 ml and water 120 ml was taken and mixed with stirring. While stirring was continued, nitrogen gas substitution was performed for 1 hour. A solution prepared by dissolving 0.5 g of ammonium persulfate in 10 ml of water was added, and the reaction was continued at 70 ° C. for 9 hours while further stirring. After completion of the reaction, the pH was adjusted to 7.0, and isopropyl alcohol was removed with a rotary evaporator to obtain an aqueous solution of aqueous copolymer 10, which is an aqueous copolymer used in the present invention. The polyethylene-converted number average molecular weight of this aqueous copolymer was measured by the same method as in Production Example 9. The result was 7.0 × 10 ⁶ .

<Production Example 19>
In a flask equipped with a nitrogen inlet tube, a condenser and a stirrer, 6.0 g of 1H, 1H-pentadecafluorooctyl methacrylate (the compound of Production Example 4), 2,2,2-trifluoroethyl acrylate (Osaka Organic Chemistry ( 12.0 g, trade name “Biscoat 3F”), polyethylene glycol (23) monomethacrylate (compound of Production Example 6) 24.0 g, 4-hydroxybutyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) 12. A mixed solvent consisting of 0 g, methoxyethyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) 6.0 g, 2-mercaptoethanol 0.04 g, isopropyl alcohol 180 ml, and water 120 ml was taken and mixed. While stirring was continued, nitrogen gas substitution was performed for 1 hour. A solution prepared by dissolving 0.5 g of ammonium persulfate in 10 ml of water was added, and the reaction was continued at 70 ° C. for 12 hours while further stirring. After completion of the reaction, the pH was adjusted to 7.0, and isopropyl alcohol was removed with a rotary evaporator to obtain an aqueous solution of aqueous copolymer 11 which is an aqueous copolymer used in the present invention. The polyethylene-converted number average molecular weight of this aqueous copolymer was measured in the same manner as in Production Example 9, and found to be 6.0 × 10 ⁵ .

<Production Example 20>
15.0 g of 1,1,1,3,3,3-hexafluoroisopropyl methacrylate (manufactured by Osaka Organic Chemical Co., Ltd., trade name “Biscoat 6FM”) in a flask equipped with a nitrogen introduction tube, a condenser and a stirrer , Lauroxypolyethylene glycol (18) acrylate (Nippon Yushi Co., Ltd., trade name “Blenmer ALE-800”) 27.0 g, 2-hydroxyethyl methacrylate (Tokyo Chemical Industry Co., Ltd.) 15.0 g, acetic acid A mixed solvent composed of 3.0 g of vinyl (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.1 g of 2-mercaptoethanol, 180 ml of isopropyl alcohol, and 120 ml of water was taken and mixed with stirring. While stirring was continued, nitrogen gas substitution was performed for 1 hour. A solution prepared by dissolving 0.3 g of ammonium persulfate in 10 ml of water was added, and the reaction was further performed at 80 ° C. for 10 hours while further stirring. After completion of the reaction, the pH was adjusted to 7.0, and isopropyl alcohol was removed with a rotary evaporator to obtain an aqueous solution of aqueous copolymer 12, which is an aqueous copolymer used in the present invention. The polyethylene-converted number average molecular weight of this aqueous copolymer was measured by the same method as in Production Example 9 and found to be 1.5 × 10 ⁶ .

<Production Example of Aqueous Copolymer Not belonging to Aqueous Copolymer Used for Skin External Preparation of the Present Invention>
<Production Example 21>
2,2,3,3,4,4,5,5-octafluoropentyl methacrylate (trade name “Biscoat 8FM” manufactured by Osaka Organic Chemical Co., Ltd.) was added to a flask equipped with a nitrogen inlet tube, a condenser and a stirrer. 0.4 g, Methoxypolyethylene glycol (23) methacrylate (Nippon Yushi Co., Ltd., trade name “Blenmer PME-1000”) 24.0 g, 2-hydroxyethyl methacrylate (Tokyo Chemical Industry Co., Ltd.) A mixed solvent consisting of 0 g, 9.6 g of methyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.1 g of 2-mercaptoethanol and 200 ml of isopropyl alcohol and 100 ml of water was taken and mixed with stirring. While stirring was continued, nitrogen gas substitution was performed for 1 hour. A solution prepared by dissolving 0.3 g of ammonium persulfate in 10 ml of water was added, and the reaction was performed at 80 ° C. for 12 hours while further stirring. After completion of the reaction, the pH was adjusted to 7.0, and isopropyl alcohol was removed with a rotary evaporator to obtain an aqueous solution of copolymer 13. It was 2.0 * 10 < ⁶ > when the polyethylene conversion number average molecular weight of this aqueous copolymer was measured by the method similar to manufacture example 9.

<Production Example 22>
2,2,3,3,4,4,5,5-octafluoropentyl methacrylate (trade name “Biscoat 8FM” manufactured by Osaka Organic Chemical Co., Ltd.) was added to a flask equipped with a nitrogen inlet tube, a condenser and a stirrer. 4.0 g, methoxypolyethylene glycol (23) methacrylate (manufactured by NOF Corporation, trade name “Blenmer PME-1000”) 16.0 g, 2-hydroxyethyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) 20.0 g and isopropyl A mixed solvent composed of 200 ml of alcohol and 100 ml of water was taken and mixed with stirring. While stirring was continued, nitrogen gas substitution was performed for 1 hour. A solution in which 1.0 g of ammonium persulfate was dissolved in 10 ml of water was added, and the reaction was continued at 80 ° C. for 12 hours while further stirring. After completion of the reaction, the pH was adjusted to 7.0, and isopropyl alcohol was removed with a rotary evaporator to obtain an aqueous solution of aqueous copolymer 14. It was 3.0 * 10 < ⁴ > when the polyethylene conversion number average molecular weight of this polymer was measured by the method similar to manufacture example 9. FIG.

<Production Example 23>
2,2,3,3,4,4,5,5-octafluoropentyl methacrylate (trade name “Biscoat 8FM” manufactured by Osaka Organic Chemical Co., Ltd.) was added to a flask equipped with a nitrogen inlet tube, a condenser and a stirrer. ) 20.0 g, methoxypolyethylene glycol (23) methacrylate (manufactured by NOF Corporation, trade name “Blenmer PME-1000”) 8.0 g, 2-hydroxyethyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) 12.0 g and isopropyl A mixed solvent composed of 200 ml of alcohol and 100 ml of water was taken and mixed with stirring. While stirring was continued, nitrogen gas substitution was performed for 1 hour. A solution in which 1.0 g of ammonium persulfate was dissolved in 10 ml of water was added, and the reaction was continued at 80 ° C. for 12 hours while further stirring. After completion of the reaction, the pH was adjusted to 7.0, and isopropyl alcohol was removed with a rotary evaporator. As a result, the polymer became insoluble in water and precipitated.

  In accordance with the formulation shown below, a cosmetic liquid that is an external preparation for skin of the present invention was prepared. That is, the component No. 1 to 12 (I) and component no. The mixture (b) of 13 to 14 was stirred and mixed to make a uniform solution. Further, while (i) was stirred, (b) was slowly added, and the two solutions were mixed to obtain a cosmetic liquid 1. In addition, although the formulation of cosmetics is shown in the following Table 3, all the numerical values in the table are mass%.

  A cosmetic liquid 2 was prepared according to Table 3 in the same manner as in Example 1.

  A cosmetic liquid 3 was prepared according to Table 3 in the same manner as in Example 1.

  A cosmetic liquid 4 was prepared according to Table 3 in the same manner as in Example 1.

<Comparative Example 1>
A comparative serum was prepared according to Table 3 in the same manner as in Example 1. The aqueous copolymer 5 was insolubilized, and (a) in Table 3 did not become a uniform solution, so that no usable cosmetic liquid was obtained.

  A cosmetic liquid 5 was prepared according to Table 4 in the same manner as in Example 1.

  A serum 6 was prepared according to Table 4 in the same manner as in Example 1.

  A cosmetic liquid 7 was prepared in accordance with Table 4 in the same manner as in Example 1.

  A serum 8 was prepared according to Table 4 in the same manner as in Example 1.

<Comparative example 2>
A comparative serum 2 was prepared according to Table 4 in the same manner as in Example 1.

  In accordance with the formulation shown in Table 5 below, lotion 9 which is an external preparation for skin of the present invention was prepared. That is, the component Nos. 1-4 mixture (I) and component no. The mixture (b) of 5 to 18 was stirred and mixed to make a uniform solution. Further, while (i) was stirred, (b) was slowly added, and the two solutions were mixed to obtain a skin lotion 9.

  A lotion 10 was prepared according to Table 5 in the same manner as in Example 9.

  As in Example 9, lotion 11 was prepared according to Table 5.

  A lotion 12 was prepared according to Table 5 in the same manner as in Example 9.

<Comparative Example 3>
Comparative lotion 3 was prepared according to Table 5 in the same manner as in Example 9.

  According to the formulation shown in Table 6, a cream that is an external preparation for skin of the present invention was prepared. That is, the component no. 1 to 6 (I) and No. 1 The mixture (b) of 7 to 14 was heated to 80 ° C. and stirred and mixed to obtain uniform solutions. While maintaining the temperature at 80 ° C., while stirring, (b) was gradually added to (i) to emulsify, and stirred and cooled to obtain cream 13.

  A cream 14 was prepared according to Table 6 in the same manner as in Example 1.

  A cream 15 was prepared according to Table 6 in the same manner as in Example 1.

  A cream 16 was prepared according to Table 6 in the same manner as in Example 1.

<Comparative Example 3>
Comparative cream 3 was prepared according to Table 6 in the same manner as in Example 1.

  In accordance with the formulation shown in Table 7, an emulsion that is an external preparation for skin of the present invention was prepared. That is, the component No. No. 1-9 mixture (I) and No. 1 The mixture (b) of 10 to 19 was heated to 80 ° C. and stirred and mixed to obtain uniform solutions. While maintaining the temperature at 80 ° C., while stirring, (b) was gradually added to emulsify and stirred and cooled to obtain an emulsion 17.

  An emulsion 18 was prepared according to Table 7 in the same manner as in Example 1.

  An emulsion 19 was prepared according to Table 7 in the same manner as in Example 1.

  An emulsion 20 was prepared according to Table 7 as in Example 1.

<Comparative Example 5>
A comparative emulsion 5 was prepared according to Table 7 in the same manner as in Example 1.

<Test Example 1: Evaluation of stickiness of external preparation for skin>
Sensation of stickiness when using serum 1-8, comparative serum 2, lotion 9-12, comparative lotion 3, cream 13-16, comparative cream 4, milk 17-20, and comparative milk 5 using the evaluation panel evaluated. The stickiness was evaluated by five skilled evaluators according to the following five-level evaluation criteria. The evaluation score was an average value of 5 people. That is, the higher this score value, the less sticky it is during use. The results are shown in Table 8.
Evaluation criteria 1 Very sticky.
2 Clearly sticky.
3 Slightly sticky.
4 Almost non-sticky.
5 Not sticky at all.

<Test Example 2: Evaluation of adhesiveness of a skin external preparation coating film>
The cosmetic liquids 1-8, the comparative cosmetic liquid 2, the skin lotion 9-12, the comparative skin lotion 3, the cream 13-16, the comparative cream 4, the milky lotion 17-20, and the comparative milky lotion 5 are each applied on a slide glass, and 40 degreeC. A test film was prepared by drying for 1 hour at a relative humidity of 30%. The adhesion of the test film was evaluated using a handy compression tester KES-G5 (manufactured by Kato Tech Co., Ltd.). The adhesiveness was expressed as an adhesive force (g) when the head of the apparatus was peeled off from the coating film. That is, the higher this value, the higher the adhesiveness of the coating film. The results are shown in Table 8.

<Test Example 3; Evaluation of moisturizing ability of external preparation for skin>
The inner part of the forearm is washed with soap and dried, and after drying, serum 1-8, comparative serum 2, lotion 9-12, comparative lotion 3, cream 13-16, comparative cream 4, milk 17-20 And comparative emulsion 5 was applied. After 30 minutes, the stratum corneum moisture content was measured using SKICON-200EX (manufactured by IBS). The measurement was performed at 25 ° C. and a relative humidity of 50%. It measured about the case where a cosmetic liquid was not apply | coated by the same method, and was set as the blank. The stratum corneum moisture content was represented by the specific resistance value (μS) of the skin at the site where the cosmetic liquid was applied. The higher this value, the higher the stratum corneum moisture content, that is, the beauty liquid has a moisturizing ability. The results are shown in Table 8. As shown in Table 8, it was clear that the external preparation for skin of the present invention had almost no stickiness, not only a good feeling during use, but also a high moisturizing ability.

  The present invention can be applied to cosmetics having excellent moisture retention and usability.

Claims (4)

The skin external preparation characterized by containing the component A and B shown next.
A) One or more structural units derived from the monomer represented by the general formula (I), one or more structural units derived from the monomer represented by the general formula (II), and the general formula (III) And the content of the structural unit derived from the monomer represented by the general formula (I) is 3 to 40 mass on average in one molecule. %, And an aqueous copolymer having a number average molecular weight in terms of polyethylene glycol measured by GPC (gel permeation chromatography) of 300,000 to 10,000,000.
B) Polyhydric alcohol

Formula (I)
(In formula (I), R1 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R2 represents an alkyl group having 2 to 12 carbon atoms having 3 to 21 substituted fluorine atoms.)

Formula (II)
(In formula (II), R3 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R4 represents an alkylene group having 2 to 4 carbon atoms which may have a hydroxyl group, and R5 represents a hydrogen atom or carbon. An aromatic group having 6 to 10 carbon atoms, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an acyl group having 1 to 12 carbon atoms, and n represents a numerical value of 2 to 90.)

Formula (III)
(In formula (III), R6 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R7 represents an alkyl group having 2 to 6 carbon atoms in which one hydrogen atom is substituted with a hydroxyl group.) The external preparation for skin according to claim 1, wherein the monomer represented by the general formula (II) is represented by the following general formula (IV).

Formula (IV)
(In the formula (IV), R8 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R9 represents a hydrogen atom, an aromatic group having 6 to 10 carbon atoms, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, Or represents an acyl group having 1 to 12 carbon atoms, q represents a numerical value of 4 to 90.) The skin external preparation according to claim 1 or 2, wherein the polyhydric alcohol is a polyhydric alcohol having 2 to 6 carbon atoms. The skin external preparation according to any one of claims 1 to 3, wherein the content of the polyhydric alcohol is 8 to 45 mass%.