JP2004123727A - Skin care preparation for external use of oil-in-water emulsion type - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a skin care preparation for external use of an oil-in-water emulsion type, having both an excellent touch in use and an excellent moisture retaining function. <P>SOLUTION: This skin care preparation for external use of the oil-in-water emulsion type is obtained by mixing a copolymer with other optional components, wherein the copolymer contains constitutional units derived from a monomer expressed by formula (I) (R<SP>1</SP>is H or a 1-3C alkyl; and R<SP>2</SP>is a 5-12C alkyl having 8-21 fluorine atoms) and a monomer expressed by formula (II) (R<SP>3</SP>is H or a 1-3C alkyl; R<SP>4</SP>is a 2-4C alkylene which may have hydroxy; R<SP>5</SP>is H, a 6-20C aromatic or a 1-20C aliphatic hydrocarbon residue or a 1-20C acyl; and (n) is 4 to 50), and the constitutional unit derived from the monomer expressed by formula (I) is contained in an amount of 5-25 wt% based on the total constitutional units. It is preferable that the skin care preparation contains the copolymer containing the constitutional unit expressed by formula (I) in an amount of 5-9.8 wt% and the constitutional unit expressed by formula (II) in an amount of 30.2-45 wt.%, and further containing a constitutional unit expressed by formula (IV) such as methyl and ethyl (meth)acrylates and isopropyl methacrylate in an amount of 50-60 wt%. <P>COPYRIGHT: (C)2004,JPO

Description

The present invention relates to an oil-in-water emulsified skin external preparation, and more particularly, to an oil-in-water emulsified skin external preparation having a better moisturizing function than conventional oil-in-water emulsified skin external preparations.

Conventionally, an oil-in-water emulsified skin external preparation has an excellent feeling of use such as a refreshing feeling, has been frequently used, and has been used as a makeup cosmetic. However, as compared with an oil-in-water emulsified skin external preparation, the emollient function such as prevention of evaporation of water from the skin was inferior, and there was a problem that the skin care function was unsatisfactory in terms of skin care function. . In order to solve these problems, measures have been taken to add humectants such as polyhydric alcohols and sodium hyaluronate, but the former requires a large amount to be added in order to improve the effect. In addition, since the aqueous solution itself has an extremely sticky feeling, the latter often impairs a good feeling of use of an external preparation for skin in the form of an oil-in-water emulsion, and has not yet reached a drastic solution. (See, for example, Patent Document 1, Patent Document 2, and Patent Document 3) On the other hand, compounds represented by the following general formulas (I) to (IV) are known as raw materials for polymers or copolymers. is there. However, by changing the constitutional ratio of these constituent units to make them water-soluble, and blending them into oil-in-water emulsified skin external preparations, and improving the moisturizing function while maintaining a good feeling of use of oil-in-water emulsified skin external preparations It was not known at all to use.

In order to improve the moisturizing function, one or more of the copolymers derived from the monomer represented by the general formula (I) may be used in an amount of 5 to 9.8% by weight, ) 30.2 to 45% by weight of one or more of the monomers derived from the monomer represented by the general formula (II), and It was also not known that copolymers containing 60% by weight were particularly preferred.

JP-A-2003-12489 JP-A-10-279424 JP 2001-19631 A

The present invention has been made under such circumstances, and it is an object of the present invention to provide an oil-in-water emulsified skin external preparation having an excellent moisturizing function while maintaining the original excellent feeling of use.

In view of such circumstances, the present inventors have intensively studied for means for providing an oil-in-water emulsified skin external preparation having an excellent moisturizing function while maintaining the original excellent feeling of use. The present inventors have found that the above-mentioned problems can be solved by incorporating a copolymer containing a specific amount of a specific structural unit into a skin external preparation in the form of an oil-in-water emulsion, and have completed the present invention. That is, the present invention relates to the oil-in-water skin external preparations shown in the following (1) to (7).

(1) It contains at least one structural unit derived from the monomer represented by the general formula (I) and at least one structural unit derived from the monomer represented by the general formula (II), and An oil-in-water emulsified external skin preparation comprising a copolymer, wherein the content of the structural unit derived from the monomer represented by the formula (I) is 5 to 25% by weight of the total structural unit.

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８〜２１個の置換フッ素原子を有する炭素数５〜１２のアルキル基を表す。）

General formula (I)
(In the 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 5 to 12 carbon atoms having 8 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６〜２０の芳香族基、炭素数１〜２０の脂肪族炭化水素基、又は炭素数１〜２０のアシル基を表す。ｎは４〜５０の数値を表す。）

General formula (II)
(In the 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 is a hydrogen atom. Represents an atom, an aromatic group having 6 to 20 carbon atoms, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an acyl group having 1 to 20 carbon atoms, and n represents a numerical value of 4 to 50.)

(2) The oil-in-water emulsified dosage form according to (1), wherein the content of the structural unit derived from the monomer represented by the general formula (II) is 20 to 80% by weight of the total structural unit. External preparation for skin.
(3) The oil-in-water emulsified skin according to (1) or (2), wherein the monomer represented by the general formula (II) is a monomer represented by the following general formula (III). External preparation.

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は水素原子、炭素数６〜２０の芳香族基、炭素数１〜２０の脂肪族炭化水素基、又は炭素数１〜２０のアシル基を表す。ｑは８〜４０の数値を表す。）

General formula (III)
(In the formula (III), R ⁶ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ⁷ represents a hydrogen atom, an aromatic group having 6 to 20 carbon atoms, and an aliphatic hydrocarbon having 1 to 20 carbon atoms. Represents a group or an acyl group having 1 to 20 carbon atoms. Q represents a numerical value of 8 to 40.)

(4) 1) 5 to 9.8% by weight of one or more structural units derived from the monomer represented by the general formula (I) 2) Configuration derived from the monomer represented by the general formula (II) 3) to 45% by weight of at least one unit, and 3) 50 to 60% by weight of at least one of structural units derived from the monomer represented by the general formula (IV). An external preparation for skin in the form of an oil-in-water emulsion.

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８〜２１個の置換フッ素原子を有する炭素数５〜１２のアルキル基を表す。）

General formula (I)
(In the 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 5 to 12 carbon atoms having 8 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６〜２０の芳香族基、炭素数１〜２０の脂肪族炭化水素基、又は炭素数１〜２０のアシル基を表す。ｎは４〜５０の数値を表す。）

General formula (II)
(In the 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 is a hydrogen atom. Represents an atom, an aromatic group having 6 to 20 carbon atoms, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an acyl group having 1 to 20 carbon atoms, and n represents a numerical value of 4 to 50.)

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は炭素数１〜３のアルキル基を表す。）

General formula (IV)
(In the formula (IV), R ⁸ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ⁹ represents an alkyl group having 1 to 3 carbon atoms.)

(5) The skin external preparation in the form of an oil-in-water emulsion according to (4), wherein the monomer represented by the general formula (II) is a monomer represented by the following general formula (III).

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は水素原子、炭素数６〜２０の芳香族基、炭素数１〜２０の脂肪族炭化水素基、又は炭素数１〜２０のアシル基を表す。ｑは８〜４０の数値を表す。）

General formula (III)
(In the formula (III), R ⁶ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ⁷ represents a hydrogen atom, an aromatic group having 6 to 20 carbon atoms, and an aliphatic hydrocarbon having 1 to 20 carbon atoms. Represents a group or an acyl group having 1 to 20 carbon atoms. Q represents a numerical value of 8 to 40.)

(6) The skin external preparation in the form of an oil-in-water emulsion according to any one of (1) to (5), which comprises the copolymer as an emollient.
(7) The skin external preparation in the form of an oil-in-water emulsion according to (6), wherein the function as an emollient agent is a transcutaneous water loss suppressing effect.

According to the present invention, it is possible to provide an oil-in-water emulsified skin external preparation having an excellent feeling in use and an excellent moisturizing function.

Hereinafter, embodiments of the present invention will be described.
(1) Skin external preparation in oil-in-water emulsified form of the present invention The skin external preparation in oil-in-water emulsified form of the present invention is a structural unit derived from a monomer represented by the general formula (I) (hereinafter referred to as a “structural unit ( I) ") and a copolymer comprising at least one structural unit derived from a monomer represented by the general formula (II) (hereinafter, referred to as" structural unit (II) ") as a structural unit. It is contained as a component.

1) Structural unit (I)
One of the essential structural units of the copolymer which is an essential component of the oil-in-water emulsified skin external preparation of the present invention is a structural unit (I) derived from a monomer represented by the following general formula (I).

一般式（Ｉ）

General formula (I)

Here, in the 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 5 to 12 carbon atoms having 8 to 21 substituted fluorine atoms. Examples of the alkyl group for R ¹ include a methyl group, an ethyl group, a propyl group, a 1-methylethyl group, and a cyclopropyl group. Preferred as R ¹ is a hydrogen atom or a methyl group.

Examples of the alkyl group having 5 to 12 carbon atoms having 8 to 21 substituted fluorine atoms represented by R ² include 1H, 1H, 5H-octafluoropentyl, 1H, 1H, 2H, 2H-nonafluorohexyl. A 1H, 1H, 7H-dodecafluoroheptyl group, 1H, 1H-tridecafluoroheptyl group, 1H, 1H, 2H, 2H-heptadecafluorodecyl group, 1H, 1H, 11H-eicosafluoroundecyl group and the like. It can be preferably exemplified.

化合物 The compound represented by the general formula (I) can be obtained by condensing an acid chloride derived from acrylic acid or α-alkylacrylic acid with an alcohol containing a fluorine atom in the presence of an alkali. Some of the compounds represented by the general formula (I) are already commercially available and can be used (specific examples: Biscoat 8F, 8FM, manufactured by Osaka Organic Chemical Co., Ltd.). .17F, 17FM).

In the copolymer which is an essential component of the oil-in-water emulsified skin external preparation of the present invention, the structural unit (I) may be only one kind, or a combination of two or more kinds as long as it satisfies the general formula (I). It can also be a structural unit.

In the copolymer which is an essential component of the oil-in-water emulsified skin external preparation of the present invention, one or more of the structural units (I) may be used in a total amount of 5 to 25% by weight based on all structural units constituting the copolymer. %, Preferably 5 to 20% by weight, more preferably 5 to 9.8% by weight, and still more preferably 7 to 9.8% by weight.

This is because, in order to improve the moisturizing function of the oil-in-water emulsified skin preparation for external use and to suitably carry out formulation, the copolymer, which is an essential component, needs a moderately hydrophobic element, This is because the content of the structural unit (I) derived from the monomer represented by the general formula (I) having properties is preferably determined within the above range.

2) Structural unit (II)
Another essential structural unit of the copolymer which is an essential component of the oil-in-water emulsified skin external preparation of the present invention is a structural unit (II) derived from a monomer represented by the following general formula (II). .

一般式（ＩＩ）

General formula (II)

In the 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 is a hydrogen atom. Represents an aromatic group having 6 to 20 carbon atoms, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an acyl group having 1 to 20 carbon atoms. n represents a numerical value of 4 to 50.

Examples of the alkyl group for R ³ include a methyl group, an ethyl group, a propyl group, a 1-methylethyl group, and a cyclopropyl group. R ³ is preferably a hydrogen atom or a methyl group. Examples of the alkylene group for R ⁴ include an ethylene group, a propylene group, a 1-methylethylene group, a 2-methylethylene group, a 2-hydroxypropylene group, a 1-hydroxy-2-methylethylene group, and a 2-hydroxy-1- A preferred example is a methylethylene group. Among them, preferred are an ethylene group and a 2-hydroxypropylene group.

Of the groups of R ^5, examples of the aromatic group having 6 to 20 carbon atoms, a phenyl group, a benzyl group, methylphenyl group, ethylphenyl group and the like. Examples of the aliphatic hydrocarbon group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a butyl group, a tert-butyl group, a hexyl group, a cyclohexyl group, an octyl group, a 2-ethylhexyl group, and a lauryl group. , Myristyl, palmityl, stearyl, oleyl and the like. Preferred examples of the acyl group having 1 to 20 carbon atoms include an acetyl group, a butenoyl group, a capryloyl group, a caprynoyl group, a benzoyl group, a lauroyl group, a myristoyl group, a palmitoyl group, a stearoyl group, and an oleoyl group. Among these, a particularly preferable group as R ⁵ is an alkyl group having 1 to 12 carbon atoms (aliphatic hydrocarbon group). n is a numerical value of 4 to 50, preferably 8 to 40.

の う ち Among the monomers represented by the general formula (II), particularly preferred are those represented by the general formula (III).

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は水素原子、炭素数６〜２０の芳香族基、炭素数１〜２０の脂肪族炭化水素基、又は炭素数１〜２０のアシル基を表す。ｑは８〜４０の数値を表す。）

General formula (III)
(In the formula (III), R ⁶ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ⁷ represents a hydrogen atom, an aromatic group having 6 to 20 carbon atoms, and an aliphatic hydrocarbon having 1 to 20 carbon atoms. Represents a group or an acyl group having 1 to 20 carbon atoms. Q represents a numerical value of 8 to 40.)

Specific examples of such a monomer represented by the general formula (III) include polyethylene glycol (9) monoacrylate, polyethylene glycol (9) monomethacrylate, methyl polyoxyethylene (9) acrylate, and methyl polyoxyethylene. (9) Methacrylate, octylphenyl polyoxyethylene (10) acrylate, octylphenyl polyoxyethylene (10) methacrylate, nonylphenyl polyoxyethylene (15) acrylate, nonylphenyl polyoxyethylene (15) methacrylate, oleyl polyoxyethylene ( 18) Acrylate, oleyl polyoxyethylene (18) methacrylate, polyethylene glycol (23) monoacrylate, polyethylene glycol (23) monomethacrylate G, methyl polyoxyethylene (23) acrylate, methyl polyoxyethylene (23) methacrylate, cetyl polyoxyethylene (23) acrylate, cetyl polyoxyethylene (23) methacrylate, dodecyl polyoxyethylene (23) acrylate, dodecyl polyoxy Examples thereof include ethylene (23) methacrylate, lauroyl polyoxyethylene (10) acrylate, lauroyl polyoxyethylene (10) methacrylate, stearoyl polyoxyethylene (40) acrylate, and stearoyl polyoxyethylene (40) methacrylate. The number in parentheses indicates the value of n.

These monomers can be obtained in high yield by the esterification reaction of the corresponding polyethylene glycol, polyethylene glycol monoether, polyethylene glycol monoester with acrylic acid or methacrylic acid chloride or anhydride. Since many commercial products already exist, such commercial products can also be used.

In the copolymer which is an essential component of the oil-in-water emulsified skin external preparation of the present invention, the structural unit (II) may be only one type, or two or more types may be used as long as they satisfy the general formula (II). You can also.

In the copolymer, the proportion of the structural unit (II) is preferably 20 to 80% by weight (average weight percentage), more preferably 25% by weight, based on all the structural units constituting the copolymer. To 75%, more preferably 30.2 to 45% by weight.

As described above, in order to improve the moisturizing function of an oil-in-water emulsified skin external preparation, an appropriate hydrophobic element is required in the physical properties of the copolymer, and the general formula (II) having a hydrophilic property is required. This is because the content of the structural unit (II) derived from the monomer represented by the formula (1) is preferably determined within the above range.

3) Other Structural Units The copolymer which is an essential component of the oil-in-water emulsified skin external preparation of the present invention can contain various structural units in addition to the above-mentioned structural units (I) and (II).
Among them, it is preferable to contain a structural unit derived from the monomer represented by the general formula (IV) (hereinafter, referred to as “structural unit (IV)”).

一般式（ＩＶ）

General formula (IV)

Here, in the formula (IV), R ⁸ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ⁹ represents an alkyl group having 1 to 3 carbon atoms. Among the groups represented by R ^8, methyl as the alkyl group group, an ethyl group, a propyl group, a 1-methylethyl group, cyclopropyl group can be exemplified. Preferred examples of R ⁸ include a hydrogen atom and a methyl group. Examples of the alkyl group represented by R ⁹ include a methyl group, an ethyl group, a propyl group, a 1-methylethyl group, and a cyclopropyl group. Of these, a methyl group is preferable.

Specific examples of the monomer represented by the general formula (IV) include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, and isopropyl methacrylate, and most of them are commercially available. is there.

When the structural unit (IV) is included as a structural unit in the copolymer which is an essential component of the oil-in-water emulsified skin external preparation of the present invention, the structural unit (IV) may be only one type, but the general formula (IV) ) Can be used in combination of two or more.

When the copolymer contains one or more structural units (IV), a preferable content of the structural units is 50 to 60% by weight based on all the structural units constituting the copolymer. By containing the structural unit (IV) at the above ratio, the cosmetic film formed by the oil-in-water emulsified external preparation for skin can be imparted with a suitable occlusive property, and the moisturizing function can be improved.

In the copolymer which is an essential component of the oil-in-water emulsified skin external preparation of the present invention, in addition to these structural units, those derived from monomers commonly used in copolymers may optionally be used as structural units to achieve the effects of the present invention. Can be contained within a range not to impair. Examples of the monomer for deriving such an optional structural unit include polymerizable carboxylic acids such as acrylic acid, methacrylic acid, and maleic acid, (acrylic acid amide, methacrylic acid amide, acrylic acid monoalkylamide, methacrylic acid monoalkylamide, and the like). ) Acrylamides, n-butyl (meth) acrylate, isobutyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, (meth) acrylic acid 2 Alkyl (meth) acrylate having alkyl group (aliphatic hydrocarbon group) having 4 or more carbon atoms such as ethylhexyl, aryl (meth) acrylate such as benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate 2, hydroxypropyl (meth) acrylate, 4 hydroxy (Meth) acrylic acid hydroxyalkyl alkyl esters such as butyl (meth) acrylate, (meth) acrylic acid alkoxyalkyl esters such as methoxymethyl (meth) acrylate and methoxyethyl (meth) acrylate, 1H, 1H-trifluoro Fluoroalkyl (meth) acrylates having 7 or less substituted fluorine atoms, such as ethyl (meth) acrylate, 1H, 1H, 3H-tetrafluoropropyl (meth) acrylate, and 1H-hexafluoroisopropyl (meth) acrylate; acetic acid Examples thereof include vinyl, vinylpyrrolidone, styrene, α-methylstyrene, and acrylonitrile.

4) Copolymer which is an essential component of an oil-in-water emulsified skin external preparation of the present invention The copolymer which is an essential component of an oil-in-water emulsified skin external preparation of the present invention contains the above structural units (I) and (II), and In some cases, it is a copolymer containing the structural unit (IV) and other structural units in its skeleton, and is usually a random copolymer in which the structural units are randomly bonded, but may be a block copolymer or a graft copolymer. It may be a copolymer. The average molecular weight is not particularly limited, but preferably has a weight average molecular weight in terms of polyethylene glycol of 5,000 to 300,000, more preferably 7,7, as measured by GPC (gel permeation chromatography). It is about 000 to 200,000.

The method for producing the copolymer is not particularly limited, but the copolymer can be obtained by mixing monomers for deriving each structural unit in a solvent, and performing a polymerization reaction according to a method generally used for polymerization of an acrylic monomer.

The copolymer thus obtained is applied to the skin to suppress the amount of transcutaneously dissipated water by a non-sticky film formed on the skin, as shown in the Examples described below, and thereby, the skin has an effect on the skin. It functions as an emollient in skin external preparations to enhance the moisturizing function in the skin. For this reason, the moisturizing function can be exhibited without impairing the "fresh feeling of use" of the oil-in-water emulsified form.

5) Skin external preparation in oil-in-water emulsified form The skin external preparation in oil-in-water emulsified form of the present invention comprises the above-mentioned copolymer, which is an essential component, and other optional cosmetic preparations usually used in skin external preparations such as skin external preparations. And the components of The external preparation for skin referred to in the present invention means a general term of a composition to be externally applied to the skin, and examples thereof include cosmetics including quasi-drugs, and external medicines for skin. Examples of these applications include the use of oil-in-water emulsified emulsions or creams in cosmetics for skin conditioning, and protection of damaged areas as a base for anti-inflammatory agents administered to damaged areas of the skin. Make-up cosmetics that do not show bulk due to powders when used in external medicine for skin or contained in make-up cosmetics such as foundation for the purpose of preventing water dispersion from occurring from the damaged site It can be preferably exemplified.

Here, the copolymer may contain only one kind, or may contain two or more kinds in combination.
The preferred content of the copolymer in the oil-in-water emulsified skin external preparation of the present invention is 0.1 to 50% by weight in total, and more preferably 1 to 40% by weight. If the content of the copolymer is too small, the moisturizing function of the skin external preparation in the form of an oil-in-water emulsion may not be sufficiently improved, and if it is too large, formulation may be difficult.

油 In the oil-in-water emulsified skin external preparation of the present invention, any component other than the above-mentioned copolymer, which can be generally added to the skin external preparation, can be added. As these optional components, for example, squalane, liquid paraffin, light liquid isoparaffin, heavy liquid isoparaffin, microcrystalline wax, hydrocarbons such as solid paraffin, dimethicone, femethicone, cyclomethicone, amodimethicone, polyether-modified silicone Silicones, such as jojoba oil, carnauba wax, mokuro, beeswax, gay wax, octyldodecyl oleate, isopropyl myristate, neopentyl glycol diisostearate, diisostearate malate, stearic acid, laurin Acids, myristic acid, palmitic acid, isostearic acid, fatty acids such as isopalmitic acid, behenic acid, oleic acid, behenyl alcohol, cetanol, oleyl alcohol, octadecyl Higher alcohols such as alcohol, castor oil, coconut oil, hydrogenated coconut oil, camellia oil, wheat germ oil, triglycerides such as isostearic acid triglyceride, isooctanoic acid triglyceride and olive oil, 1,3-butanediol, glycerin, diglycerin , Dipropylene glycol, polyethylene glycol, 1,2-pentanediol, 1,2-hexylene glycol, polyhydric alcohols such as isoprene glycol, sorbitan sesquiolate, sorbitan monooleate, sorbitan triolate, sorbitan sesquistearate, sorbitan mono Stearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan monostearate, polyoxyethylene stearate, polyoxyethylene oleate, polyoxyethylene sorbitan Nonionic surfactants such as oxyethylene glyceryl fatty acid ester, polyoxyethylene alkyl ether, and polyoxyethylene hydrogenated castor oil; anionic surfactants such as sodium lauryl stearate, polyoxyethylene alkyl sulfate, and sulfosuccinate; Cationic surfactants such as quaternary alkylammonium salts, amphoteric surfactants such as alkyl betaine, organic powders such as crystalline cellulose and cross-linked methylpolysiloxane, polyethylene powder, acrylic resin powder, talc, mica, Powders which may be surface-treated such as sericite, magnesium carbonate, calcium carbonate, titanium dioxide, iron oxide, navy blue, ultramarine, titanium mica, titanium sericite, silica, etc., acrylic acid / alkyl methacrylate copolymer and / or Its salt, carboki Sivinyl polymers and / or salts thereof, thickeners such as xanthan gum and hydroxypropyl cellulose, retinol, retinoic acid, tocopherol, riboflavin, pyridoxine, ascorbic acid, vitamins such as ascorbic acid phosphate, glycyrrhizinate, glycyrrhetin, Active ingredients such as terpenes such as ursolic acid and oleanolic acid, steroids such as estradiol, ethinyl estradiol, and estriol; preservatives such as phenoxyethanol, parabens, hibitene gluconate, and benzalkonium chloride; and dimethylaminobenzoate esters And ultraviolet absorbers such as cinnamic acid esters and benzophenones. These are appropriately selected according to the use and the like. Of these, particularly preferred are polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan monostearate, polyoxyethylene stearate, polyoxyethylene oleate, polyoxyethylene glyceryl fatty acid ester, polyoxyethylene alkyl ether, and polyoxyethylene cured. Polyoxyethylene-added nonionic surfactants such as castor oil, which are hydrophilic and have an HLB of 10 or more, higher alcohols such as cetyl alcohol or batyl alcohol, and glyceryl ether of higher alcohols. The preferred content is 1 to 4% by weight of the nonionic surfactant and 1 to 3% by weight of the higher alcohol or glyceryl ether of the higher alcohol. In addition, since powdery materials do not give a bulky feeling, powder is also a preferable optional component. The preferred content of the powder is 1 to 25% by weight.

油 The oil-in-water emulsified skin external preparation of the present invention can be produced by treating these essential components and optional components according to a conventional method. As a method of incorporating a copolymer into an oil-in-water emulsified skin external preparation, an aqueous solution in which the copolymer is dissolved is prepared in advance, and this is mixed with other components constituting the oil-in-water emulsified skin external preparation. preferable.

The thus obtained external preparation for skin in the form of an oil-in-water emulsion of the present invention has the excellent feeling of use inherent to the external preparation for skin in the form of an oil-in-water emulsion and also has an excellent moisturizing function.

1) Production Example of Monomer Represented by General Formula (I) Deriving Structural Unit (I) Production Example 1
52.8 g of 1H, 1H, 2H, 2H-nonafluoro-1-hexanol as a fluoroalcohol and 50 g of triethylamine were dissolved in 500 ml of tetrahydrofuran. While cooling with ice and stirring, a solution of 18.1 g of acrylic acid chloride as an acid chloride in 100 ml of tetrahydrofuran was dropped into this solution over 2 hours. After completion of the dropwise addition, the formed white precipitate was filtered, and tetrahydrofuran and triethylamine were removed from the filtrate using a rotary evaporator. NMR measurement confirmed that the obtained compound was 1H, 1H, 2H, 2H-nonafluorohexyl acrylate.

Production Examples 2 to 5
The raw material was changed according to Production Example 1 to produce a monomer represented by the general formula (I).
Table 1 shows the results.

2) Production example of monomer represented by general formula (II) for deriving structural unit (II)
Production Example 6
80 g of polyethylene glycol # 400 as a polyethylene glycol compound and 50 g of triethylamine were dissolved in 500 ml of tetrahydrofuran. To this solution, a solution of 10.5 g of methacrylic acid chloride as an acid chloride dissolved in 100 ml of tetrahydrofuran was added dropwise over 2 hours while cooling with ice and stirring. After completion of the dropwise addition, the formed white precipitate was filtered, and tetrahydrofuran and triethylamine were removed from the filtrate using a rotary evaporator. It was confirmed by NMR measurement that the obtained compound was polyethylene glycol (9) monomethacrylate.

Production Examples 7 to 11
According to Production Example 6, the raw material was changed to prepare a monomer represented by the general formula (II). Table 2 shows the results.

3) Production example of copolymer which is an essential component of oil-in-water emulsified skin external preparation of the present invention
Production Example 12
12.7 g of 1H, 1H, 2H, 2H-heptadecafluorodecyl acrylate (manufactured by Osaka Organic Chemicals, trade name "Biscoat 17F") in a flask equipped with a nitrogen inlet tube, a condenser and a stirring device, and methylpolyoxyethylene ( 23) A mixed solvent composed of 52.7 g of methacrylate (manufactured by Shin-Nakamura Chemical Co., trade name “NK Ester M-230G”), 69.7 g of methyl methacrylate (manufactured by Tokyo Kasei), 300 ml of isopropyl alcohol and 200 ml of water was stirred and mixed. . The nitrogen gas was replaced for one hour while the stirring was continued. A solution in which 2.3 g of ammonium persulfate was dissolved in 20 ml of water was added, and the reaction was carried out at 65 ° C. for 16 hours while stirring was continued. After completion of the reaction, isopropyl alcohol was removed with a rotary evaporator to obtain an aqueous solution of Copolymer 1.

Production Example 13
In a flask equipped with a nitrogen inlet tube, a condenser and a stirrer, 1.2 g of 1H, 1H, 7H-dodecafluoroheptyl methacrylate (the compound of Production Example 2), 1H, 1H, 11H-eicosafluoroundecyl acrylate (Production) A mixed solvent consisting of 3.0 g of the compound of Example 5), 22.8 g of stearoyl polyoxyethylene (40) acrylate (Preparation Example 11), 33.0 g of ethyl acrylate, 200 ml of ethyl alcohol, and 100 ml of water was stirred and mixed. The nitrogen gas was replaced for one hour while the stirring was continued. A solution prepared by dissolving 1.0 g of ammonium persulfate in 10 ml of water was added, and the reaction was carried out at 70 ° C. for 12 hours while stirring was continued. After completion of the reaction, isopropyl alcohol was removed with a rotary evaporator to obtain an aqueous solution of copolymer 2.

Production Example 14
In a flask equipped with a nitrogen inlet tube, a condenser and a stirrer, 3.1 g of 1H, 1H-tridecafluoroheptyl acrylate (the compound of Production Example 3) and methyl polyoxyethylene (9) acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) 9.5 g of NK ester AM-90G), 12.0 g of oleyl polyoxyethylene (18) methacrylate (compound of Production Example 8), 35.4 g of isopropyl methacrylate (manufactured by Tokyo Chemical Industry), and 300 ml of ethyl acetate. Stir and mix. The nitrogen gas was replaced for one hour while the stirring was continued. A solution prepared by dissolving 0.5 g of benzoyl peroxide in 10 ml of ethyl acetate was added, and the reaction was carried out by refluxing for 8 hours while stirring was continued. After completion of the reaction, water was added to this solution, and flushing was performed to obtain an aqueous solution of Copolymer 3.

Production Example 15
In a flask equipped with a nitrogen inlet tube, a condenser and a stirrer, 4.8 g of 1H, 1H, 11H-eicosafluoroundecyl acrylate (the compound of Production Example 5) and stearoyl polyoxyethylene (40) acrylate (Production Example 11) 22.2 g), 24.0 g of methyl methacrylate (manufactured by Tokyo Kasei), 9.0 g of ethyl methacrylate (manufactured by Tokyo Kasei), 200 ml of isopropyl alcohol, and 100 ml of water were stirred and mixed. The nitrogen gas was replaced for one hour while the stirring was continued. A solution in which 1.0 g of ammonium persulfate was dissolved in 10 ml of water was added, and the mixture was reacted at 70 ° C. for 18 hours while stirring was continued. After completion of the reaction, isopropyl alcohol was removed with a rotary evaporator to obtain an aqueous solution of Copolymer 4.

Production Example 16
In a flask equipped with a nitrogen inlet tube, a condenser and a stirrer, 8.0 g of 1H, 1H-pentadecafluorooctyl methacrylate (compound of Production Example 4) and lauroyl polyoxyethylene (10) acrylate (compound of Production Example 10) 32.0 g and 200 ml of isopropyl alcohol were taken and mixed by stirring. The nitrogen gas was replaced for one hour while the stirring was continued. A solution prepared by dissolving 0.5 g of benzoyl peroxide in 10 ml of isopropyl alcohol was added, and the mixture was reacted at 80 ° C. for 8 hours while stirring was continued. After the reaction was completed, a large amount of n-hexane was added to this solution, and the resulting precipitate was dried and then dissolved in water to obtain an aqueous solution of copolymer 5.

Production Example 17
In a flask equipped with a nitrogen inlet tube, a condenser and a stirrer, 9.0 g of 1H, 1H-tridecafluoroheptyl acrylate (compound of Production Example 3), polyethylene glycol (9) monomethacrylate (compound of Production Example 6) 36 0.0 g, 15.0 g of n-butyl methacrylate (manufactured by Tokyo Chemical Industry) and 300 ml of ethyl acetate were mixed with stirring. The nitrogen gas was replaced for one hour while the stirring was continued. A solution prepared by dissolving 0.5 g of benzoyl peroxide in 10 ml of ethyl acetate was added, and the reaction was carried out by refluxing for 8 hours while stirring was continued. After completion of the reaction, water was added to this solution, and flushing was performed to obtain an aqueous solution of copolymer 6.

Production Example 18
6.0 g of 1H, 1H, 1H-trichlorofluorodecyl acrylate (manufactured by Osaka Organic Chemicals, trade name "Biscoat 17F") was placed in a flask equipped with a nitrogen inlet tube, a condenser and a stirrer. 18.0 g of fluoroethyl methacrylate (manufactured by Osaka Organic Chemicals, trade name "Biscoat 3FM"), 24.0 g of methyl polyoxyethylene (23) methacrylate (manufactured by Shin-Nakamura Chemical, trade name "NK Ester M-230G"), 2- A mixed solvent consisting of 12.0 g of hydroxyethyl methacrylate (manufactured by Tokyo Kasei), 180 ml of isopropyl alcohol and 120 ml of water was taken and mixed with stirring. The nitrogen gas was replaced for one hour while the stirring was continued. A solution prepared by dissolving 1.0 g of ammonium persulfate in 10 ml of water was added, and the reaction was carried out at 70 ° C. for 12 hours while stirring was continued. After completion of the reaction, the isopropyl alcohol was removed with a rotary evaporator to obtain an aqueous solution of Copolymer 7.

Production Example 19
In a flask equipped with a nitrogen inlet tube, a condenser and a stirrer, 1.2 g of 1H, 1H, 11H-eicosafluoroundecyl acrylate (compound of Production Example 5), 1H, 1H, 5H-octafluoropentyl methacrylate (Osaka) 1.6 g of organic chemical, trade name "Biscoat 8FM"), 26.0 g of oleyl polyoxyethylene (18) methacrylate (compound of Production Example 8), 11.2 g of styrene (manufactured by Tokyo Chemical Industry) and 250 ml of toluene were stirred and mixed. did. The nitrogen gas was replaced for one hour while the stirring was continued. A solution prepared by dissolving 0.5 g of azobisisobutyronitrile in 10 ml of toluene was added, and the mixture was reacted at 70 ° C. for 8 hours while stirring was continued. After the completion of the reaction, after the completion of the reaction, water was added to this solution, and flushing was performed to obtain an aqueous solution of Copolymer 8.

Production Example 20
In a flask equipped with a nitrogen inlet tube, a condenser and a stirrer, 3.6 g of 1H, 1H, 2H, 2H-nonafluorohexyl acrylate (compound of Production Example 1) and nonylphenyl polyoxyethylene (15) acrylate (Production Example) 7), 18.0 g of polyoxyethylene (23) monomethacrylate (the compound of Production Example 9), 10.4 g of ethyl acrylate (manufactured by Tokyo Chemical Industry), 20.4 g of ethyl acrylate, 150 ml of ethyl alcohol, and 150 ml of water. Stir and mix. The nitrogen gas was replaced for one hour while the stirring was continued. A solution in which 1.0 g of potassium persulfate was dissolved in 10 ml of water was added, and the mixture was reacted at 80 ° C. for 12 hours while stirring was continued. After the reaction was completed, ethyl alcohol was removed with a rotary evaporator to obtain an aqueous solution of copolymer 9.

Production Example 21
In a flask equipped with a nitrogen inlet tube, a condenser and a stirrer, 5.6 g of 1H, 1H-heptadecafluorodecyl acrylate (“Biscoat 17F” manufactured by Osaka Organic Chemicals) and methyl polyoxyethylene (23) methacrylate (Shin Nakamura Chemical) A mixed solvent consisting of 24.0 g of “NK Ester M-230G”, 18.0 g of methyl methacrylate (manufactured by Tokyo Kasei), 12.0 g of 2-hydroxyethyl methacrylate (manufactured by Tokyo Kasei), 180 ml of isopropyl alcohol, and 120 ml of water Stir and mix. The nitrogen gas was replaced for one hour while the stirring was continued. A solution prepared by dissolving 1.0 g of ammonium persulfate in 10 ml of water was added, and the reaction was carried out at 70 ° C. for 12 hours while stirring was continued. After completion of the reaction, isopropyl alcohol was removed with a rotary evaporator to obtain an aqueous solution of Copolymer 10.

本 Hereinafter, the present invention will be described specifically with reference to Examples, but it goes without saying that the present invention is not limited to these Examples.

<Examples 1 to 5, Comparative Example 1>
According to the following formulation, a cream as an external preparation for skin in the form of an oil-in-water emulsion of the present invention was prepared. That is, the mixture (a) of components 1 to 9 and the mixture (b) of components 10 to 19 in Table 3 were heated to 80 ° C., and (b) was gradually added to (a), emulsified, and cooled by stirring. To get the cream.
Hereinafter, the numerical values in the tables describing the examples and comparative examples of the skin external preparation in the form of an oil-in-water emulsified formulation represent% by weight.

<Examples 6 to 9, Comparative Example 2>
According to the following formulation, an emulsion as an external preparation for skin in the form of an oil-in-water emulsion of the present invention was prepared. That is, a mixture (a) of components 1 to 8 and a mixture (b) of components 9 to 18 in Table 4 were heated to 80 ° C., (b) was gradually added to (a), emulsified, stirred and cooled. To obtain an emulsion.

<Examples 10 to 13 and Comparative Example 3>
According to the following formulation, a foundation which is an oil-in-water emulsified skin external preparation of the present invention was prepared. That is, the mixture (a) of the components 1 to 8 in Table 5 was heated to 80 ° C, the components 9 to 12 (b) were added, and the mixture was vigorously stirred and mixed with a disper (high-speed disperser). While maintaining the temperature at 80 ° C., a mixture of components (13) to (21) heated to 80 ° C. is gradually added to the mixture of (a) and (b), and the mixture is emulsified, stirred and cooled to form a creamy foundation. Got.

<Test Example 1: Evaluation of moisturizing function of oil-in-water emulsified skin external preparation>
The skin external preparations in the form of oil-in-water emulsified formulations of Examples 1 to 13 and Comparative Examples 1 to 3 were applied to the cheeks of panelists with remarkably rough skin. After standing for 5 minutes, transepidermal water loss (TWL) at the application site was measured using TEWAMETER ™ 210 (courage + khazaka). Table 6 shows the results. In addition, the smaller the value of TWL, the lower the water evaporation from the skin surface, that is, the more excellent the moisturizing function of the applied oil-in-water emulsified skin external preparation is.
The TWL value of the panel without any treatment was 28 to 30 (g / m2hr).

<Test Example 2: Evaluation of feeling of use of skin external preparation in oil-in-water emulsified form>
The skin external preparations in the form of oil-in-water emulsions of Examples 1 to 13 and Comparative Examples 1 to 3 were applied to the cheeks, and the sticky feeling (unsuitable feeling of use) felt at this time was evaluated by 20 panelists. The feeling of stickiness was evaluated on a 5-point scale according to the following criteria. In other words, the smaller the score number, the better the feeling of use. Table 6 shows the results. The numerical values in the table represent the average scores of 20 panelists.
1: No stickiness is felt.
2: The sticky feeling is slightly felt.
3: The sticky feeling is slightly felt.
4: The sticky feeling is clearly felt.
5: The sticky feeling is considerably felt.

From Test Examples 1 and 2, it can be seen that all of the oil-in-water emulsified skin external preparations of the present invention have significantly improved moisturizing functions while maintaining the original excellent feeling in use.

Claims (7)

It contains at least one structural unit derived from the monomer represented by the general formula (I) and at least one structural unit derived from the monomer represented by the general formula (II), and further includes the above-mentioned general formula (I 3.) An external preparation for skin in the form of an oil-in-water emulsion, comprising a copolymer, wherein the content of the structural unit derived from the monomer represented by the formula (1) is from 5 to 25% by weight of the total structural unit.

General formula (I)
(In the 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 5 to 12 carbon atoms having 8 to 21 substituted fluorine atoms.)

General formula (II)
(In the 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 is a hydrogen atom. Represents an atom, an aromatic group having 6 to 20 carbon atoms, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an acyl group having 1 to 20 carbon atoms, and n represents a numerical value of 4 to 50.) The oil-in-water emulsified dosage form for external use on the skin according to claim 1, wherein the content of the structural unit derived from the monomer represented by the general formula (II) is 20 to 80% by weight of the total structural unit. Agent. The skin external preparation in the form of an oil-in-water emulsion according to claim 1 or 2, wherein the monomer represented by the general formula (II) is a monomer represented by the following general formula (III).

General formula (III)
(In the formula (III), R ⁶ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ⁷ represents a hydrogen atom, an aromatic group having 6 to 20 carbon atoms, and an aliphatic hydrocarbon having 1 to 20 carbon atoms. Represents a group or an acyl group having 1 to 20 carbon atoms. Q represents a numerical value of 8 to 40.) 1) 5 to 9.8% by weight of one or more structural units derived from the monomer represented by the general formula (I) 2) One type of structural unit derived from the monomer represented by the general formula (II) 30.2 to 45% by weight of the above, and 3) an oil-in-water emulsified form containing a copolymer containing 50 to 60% by weight of one or more structural units derived from a monomer represented by the general formula (IV). External preparation for skin.

General formula (I)
(In the 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 5 to 12 carbon atoms having 8 to 21 substituted fluorine atoms.)

General 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 is a hydrogen atom Represents an aromatic group having 6 to 20 carbon atoms, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an acyl group having 1 to 20 carbon atoms, and n represents a numerical value of 4 to 50.)

General formula (IV)
(In the formula (IV), R ⁸ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ⁹ represents an alkyl group having 1 to 3 carbon atoms.) The skin external preparation according to claim 4, wherein the monomer represented by the general formula (II) is a monomer represented by the following general formula (III).

General formula (III)
(In the formula (III), R ⁶ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ⁷ represents a hydrogen atom, an aromatic group having 6 to 20 carbon atoms, and an aliphatic hydrocarbon having 1 to 20 carbon atoms. Represents a group or an acyl group having 1 to 20 carbon atoms. Q represents a numerical value of 8 to 40.) The skin external preparation in the form of an oil-in-water emulsion, according to any one of claims 1 to 5, wherein the copolymer is contained as an emollient. 7. The external preparation for skin in the form of an oil-in-water emulsion according to claim 6, wherein the function as an emollient agent is a transcutaneous water loss suppressing effect.