JP2004115502A - Aqueous gel type cosmetic - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aqueous gel type cosmetic, maintaining an excellent fresh feeling on using and widely improved with the maintenance of cosmetic effect. <P>SOLUTION: This aqueous gel type cosmetic is obtained by mixing a copolymer containing constitutional units induced from monomers expressed by formulae (I) and (II), and as necessary by formula (IV), and having 5-25 wt. % constitutional unit from a monomer of (I) based on the total constituting units, especially preferably a copolymer containing 5-9.8 wt. % (I), 30.2-45 wt. % (II) and 50-60 wt. % (IV), with other optional components. In the above formulae, R<SP>1</SP>is H or a 1-3C alkyl; R<SP>2</SP>is a 5-12C alkyl having 8-21F; 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 1-20C aromatic, a 1-20C aliphatic hydrocarbon or a 1-20C acyl; and (n) is 4-50. <P>COPYRIGHT: (C)2004,JPO

Description

The present invention relates to an aqueous gel type cosmetic, and more particularly, to an aqueous gel type cosmetic suitable for improving the persistence of a cosmetic effect.

ゲ ル Gel-type cosmetics having water as a continuous phase, so-called aqueous gel-type cosmetics, are increasingly being favored for use in summer, especially from a refreshing feeling. However, since the continuous phase is water, the cosmetic film to be formed is easily broken by sweat and the like, and the persistence of the cosmetic effect when applied to the skin is often not sufficient, so that the feeling of use is particularly suitable in summer when it is particularly suitable. In many cases, it is necessary to sacrifice the persistence of the cosmetic effect, and the range of use is limited. In order to improve the persistence of the cosmetic effect when applied to the skin, a method of blending a fluorine compound is effective, but conventional fluorine compounds have low solubility in water and low affinity with water. Therefore, it was difficult to mix it with the aqueous gel type cosmetic. (See, for example, Patent Document 1, Patent Document 2, and Patent Document 3) A method of improving the durability of a cosmetic effect by blending a polymer emulsion to improve the strength of the decorative film is also considered. Was strong and the refreshing feeling of the aqueous gel was sometimes impaired. (For example, see Patent Document 4)

In other words, there is a demand for the development of an aqueous gel type cosmetic in which the persistence of a cosmetic effect when applied to the skin is remarkably improved while maintaining a suitable feeling of use centered on a refreshing feeling. At present, fees have not yet been obtained.

On the other hand, the compounds represented by the following general formulas (I) to (IV) are known as raw materials for polymers or copolymers, and among them, the structural units represented by the general formulas (I) and (II) ) (Or a copolymer containing a constitutional unit derived from a monomer represented by the general formula (III)) is already known as a hydrophobic film-forming agent for cosmetics such as nail color. However, by changing the constitutional ratio of these constitutional units, forming a water-soluble copolymer, blending it in an aqueous gel type cosmetic, and applying it to the skin while maintaining a suitable feeling of use centered on a refreshing feeling It was not known at all to improve the cosmetic effect. In order to improve the persistence of such a cosmetic effect, one or more of the above-mentioned copolymers derived from the monomer represented by the general formula (I) may be used in an amount of 5 to 9.8. %, 2) at least one of the monomers derived from the monomer represented by the general formula (II) is 30.2 to 45% by weight, and 3) one of the monomers derived from the monomer represented by the general formula (IV) It was not known that a copolymer containing the above in an amount of 50 to 60% by weight was particularly preferable. That is, it contains at least one structural unit derived from a monomer represented by the following general formula (I) and at least one structural unit derived from a monomer represented by the following general formula (II), and Aqueous gel cosmetics containing a copolymer characterized in that the content of the structural unit derived from the monomer represented by the general formula (I) is 5 to 25% by weight of the total structural unit, is not known at all. .

JP 2003-81756 A JP 2000-256127 A JP-A-11-236317 JP-A-2000-26239

The present invention has been made under such circumstances, and a water-based gel-type cosmetic in which the persistence of a cosmetic effect when applied to the skin is remarkably improved while maintaining a suitable feeling of use centered on a refreshing feeling. The task is to provide

According to the present invention, it is possible to provide an aqueous gel cosmetic in which an excellent refreshing sensation during use is maintained and the persistence of the cosmetic effect is remarkably improved.

In view of such circumstances, the present inventors have provided an aqueous gel type cosmetic composition in which the persistence of a cosmetic effect when applied to the skin is remarkably improved while maintaining a suitable feeling of use centered on a refreshing feeling. As a result of diligent studies in search of means to perform the above, it was found that the above-mentioned problems can be solved by a water-soluble fluorine copolymer, that is, an aqueous gel-type cosmetic containing a copolymer containing a specific amount of a specific structural unit, and to complete the present invention. Reached. That is, the present invention relates to the following techniques (1) to (8).
(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 aqueous gel cosmetic 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、Ｒ１は水素原子又は炭素数１〜３のアルキル基を表し、Ｒ２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), R1 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R2 represents an alkyl group having 5 to 12 carbon atoms having 8 to 21 substituted fluorine atoms.)

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６〜２０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), 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 a carbon 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.)

(2) The aqueous gel cosmetic 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. Fees.
(3) The aqueous gel cosmetic according to (1) or (2), 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、Ｒ６は水素原子又は炭素数１〜３のアルキル基を表し、Ｒ７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), R6 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R7 represents a hydrogen atom, an aromatic group having 6 to 20 carbon atoms, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, Or represents 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). Aqueous gel type cosmetic.

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), R1 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R2 represents an alkyl group having 5 to 12 carbon atoms having 8 to 21 substituted fluorine atoms.)

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６〜２０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), 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 a carbon 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.)

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は炭素数１〜３のアルキル基を表す。）

General formula (IV)
(In the formula (IV), R8 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R9 represents an alkyl group having 1 to 3 carbon atoms.)

(5) The aqueous gel cosmetic 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、Ｒ６は水素原子又は炭素数１〜３のアルキル基を表し、Ｒ７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。）
（６）更に、カルボキシビニルポリマー、アクリル酸・メタクリル酸（Ｃ１０〜３０）アルキル及び生理的に許容されるこれらの塩から選択される１種乃至は２種以上を含有することを特徴とする、（１）〜（５）何れか１項に記載の化粧料。
（７）メークアップ化粧料であることを特徴とする、（１）〜（６）何れか１項に記載の化粧料。
（８）夏用であることを特徴とする、（１）〜（７）何れか１項に記載の化粧料。

General formula (III)
(In the formula (III), R6 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R7 represents a hydrogen atom, an aromatic group having 6 to 20 carbon atoms, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, Or represents an acyl group having 1 to 20 carbon atoms. Q represents a numerical value of 8 to 40.)
(6) It further comprises one or more selected from carboxyvinyl polymer, alkyl (C10-30) acrylate / methacrylate and physiologically acceptable salts thereof, The cosmetic according to any one of (1) to (5).
(7) The cosmetic according to any one of (1) to (6), which is a makeup cosmetic.
(8) The cosmetic according to any one of (1) to (7), which is used for summer.

Hereinafter, embodiments of the present invention will be described.
The aqueous gel cosmetic of the present invention comprises one or more structural units derived from the monomer represented by the general formula (I) (hereinafter, referred to as “structural unit (I)”) and a compound represented by the general formula (II) And a copolymer containing, as an essential component, at least one structural unit derived from a monomer to be produced (hereinafter, referred to as “structural unit (II)”).
1) Structural unit (I)
One of the essential structural units of the copolymer, which is an essential component of the aqueous gel cosmetic 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), R1 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R2 represents an alkyl group having 5 to 12 carbon atoms having 8 to 21 substituted fluorine atoms. Examples of the alkyl group for R1 include a methyl group, an ethyl group, a propyl group, a 1-methylethyl group, and a cyclopropyl group. Preferred as R1 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 R2 include a 1H, 1H, 5H-octafluoropentyl group, 1H, 1H, 2H, 2H-nonafluorohexyl group, Preferred are 1H, 1H, 7H-dodecafluoroheptyl, 1H, 1H-tridecafluoroheptyl, 1H, 1H, 2H, 2H-heptadecafluorodecyl, 1H, 1H, 11H-eicosafluoroundecyl and the like. Can be illustrated.

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. Examples of such commercially available products include trade names “Viscoat 8F”, “Viscoat 8FM”, “Viscoat 17F”, and “Viscoat 17FM” (all manufactured by Osaka Organic Chemical).

In the copolymer which is an essential component of the aqueous gel cosmetic according to the present invention, the structural unit (I) may be only one type, but as long as it satisfies the general formula (I), two or more types are combined. It can also be.

In the copolymer which is an essential component of the aqueous gel cosmetic of the present invention, one or more of the structural units (I) is preferably 5 to 25% by weight, preferably 5 to 25% by weight, based on all structural units constituting the copolymer. Is 5 to 20% by weight, more preferably 5 to 9.8% by weight, even more preferably 7 to 9.8% by weight.

This is because when the amount of the structural unit (I) derived from the monomer represented by the general formula (I) is too small, the persistence of the cosmetic effect when applied to the skin may not be sufficiently improved. This is because the water-solubility is reduced and the preparation cannot be suitably performed in some cases. For these reasons, the content of the structural unit (I) derived from the monomer represented by the general formula (I) 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 aqueous gel cosmetic 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), 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 a carbon 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 of R3 include a methyl group, an ethyl group, a propyl group, a 1-methylethyl group, and a cyclopropyl group. R3 is preferably a hydrogen atom or a methyl group. As the alkylene group for R4, for example, ethylene group, propylene group, 1-methylethylene group, 2-methylethylene group, 2-hydroxypropylene group, 1-hydroxy-2-methylethylene group, 2-hydroxy-1-methyl Preferred examples include an ethylene group. Among them, preferred are an ethylene group and a 2-hydroxypropylene group.

Among the groups represented by R5, examples of the aromatic group having 6 to 20 carbon atoms include a phenyl group, a benzyl group, a methylphenyl group, and an ethylphenyl group.

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.

の う ち Among these, an alkyl group having 1 to 12 carbon atoms (aliphatic hydrocarbon group) is particularly preferred as the group represented by R5. 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、Ｒ６は水素原子又は炭素数１〜３のアルキル基を表し、Ｒ７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), R6 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R7 represents a hydrogen atom, an aromatic group having 6 to 20 carbon atoms, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, Or represents 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 aqueous gel type cosmetic of the present invention, the structural unit (II) may be only one type, or two or more types may be combined as long as they satisfy the general formula (II). .

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.

If the amount of the structural unit (II) derived from the monomer represented by the general formula (II) is too small, the water solubility of the copolymer may be low and formulation may not be suitably performed. If the amount is too large, the aqueous gel of the present invention may be used. This is because the affinity between the cosmetic film formed by the cosmetic and the sweat and the like is improved, and as a result, the persistence of the cosmetic effect may not be sufficiently improved. For these reasons, the content of the structural unit (II) derived from the monomer represented by the general formula (II) is preferably determined within the above range.

3) Other Structural Units The copolymer, which is an essential component of the aqueous gel cosmetic of the present invention, can contain various structural units in addition to the above structural units (I) and (II).

か で 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), R8 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R9 represents an alkyl group having 1 to 3 carbon atoms. Among the groups represented by R8, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a 1-methylethyl group, and a cyclopropyl group. Preferred examples of R8 include a hydrogen atom and a methyl group. Examples of the alkyl group represented by R9 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 aqueous gel cosmetic of the present invention, the structural unit (IV) may be only one type, but satisfies the general formula (IV) If it is, two or more kinds can be combined.

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) in the above ratio, the strength of the film formed by the copolymer can be improved.

In the copolymer which is an essential component of the aqueous gel type cosmetic of the present invention, in addition to these structural units, those derived from monomers usually used in copolymers are optionally used as structural units and do not impair the effects of the present invention. It can be contained in the range. 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.

The copolymer which is an essential component of the aqueous gel cosmetic of the present invention is a copolymer containing the above structural units (I) and (II), and optionally the structural unit (IV) and other structural units in its skeleton. It is a union, usually a random copolymer in which its constituent units are randomly bonded, but may be a block copolymer or a graft 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 which is an essential component of the aqueous gel cosmetic of the present invention is not particularly limited, but a monomer for deriving each structural unit is mixed in a solvent, and according to a method usually used for polymerization of an acrylic monomer, It can be obtained by performing a polymerization reaction.

水性 The aqueous gel cosmetic of the present invention is composed of the above-mentioned copolymer, which is an essential component, and other optional components usually used in cosmetics.

Here, the copolymer may contain only one kind, or may contain two or more kinds in combination.

好 ま し い The preferred content of the copolymer in the aqueous gel cosmetic 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 persistence of the cosmetic effect of the cosmetic containing the fluorine-containing compound may not be sufficiently improved, and if it is too large, the formulation may be difficult. When the above-mentioned copolymer is contained in the aqueous gel of the present invention, it is preferable that the copolymer is previously dissolved in an aqueous carrier. In order to allow the copolymer to be contained in such a form, it is preferable to use a hydroalcoholic solvent as a solvent in the production process of copolymerizing the copolymer, and to use the solvent without completely removing the solvent from the resulting copolymer.

水性 In the aqueous gel type cosmetic of the present invention, it is possible to mix arbitrary components other than the above-mentioned copolymer which can be usually mixed with the aqueous gel cosmetic. 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. Here, the aqueous gel cosmetic according to the present invention refers to a cosmetic containing 50% by weight or more of water and having a gel-like viscous property. It may be in the form of a dispersion or an emulsifier. In order to impart the gel-like properties, it is preferable to include a water-soluble gelling agent, such as a carboxyvinyl polymer or an alkyl (C10-30) acrylate / methacrylate. One or two or more selected from physiologically acceptable salts can be preferably exemplified. These gelling agents are all general-purpose raw materials for cosmetics and are commercially available. The preferred content of these components in the aqueous gel cosmetic of the present invention is 0.05 to 5% by weight. As the aqueous gel cosmetic of the present invention, any of basic cosmetics, makeup cosmetics, hair cosmetics, and body cosmetics can be applied, regardless of the type, as long as they are known as cosmetics. is there. Particularly preferred among these are makeup cosmetics. This is because in make-up cosmetics, the quality of the makeup lasts as an effect.

水性 The aqueous gel cosmetic of the present invention can be produced by treating these essential and optional components according to a conventional method. The copolymer, which is an essential component of the aqueous gel cosmetic of the present invention, is essentially water-soluble. As a method for incorporating the copolymer into the aqueous gel cosmetic, an aqueous solution in which the copolymer is dissolved in advance is prepared. It is preferable to mix this with other components constituting the aqueous gel cosmetic. The aqueous gel cosmetic of the present invention thus obtained has an excellent refreshing sensation when applied to the skin, and the cosmetic film contains a fluorine copolymer to improve the persistence of the cosmetic effect.

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) 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 the aqueous gel cosmetic 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 the copolymer 1 of the present invention.

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 of the present invention.

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 the completion of the reaction, water was added to the solution, and flushing was performed to obtain an aqueous solution of the copolymer 3 of the present invention.

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 of the present invention.

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 formed precipitate was dried and dissolved in water to obtain an aqueous solution of the copolymer 5 of the present invention.

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 the completion of the reaction, water was added to this solution, and flushing was performed to obtain an aqueous solution of the copolymer 6 of the present invention.

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, isopropyl alcohol was removed with a rotary evaporator to obtain an aqueous solution of Copolymer 7 of the present invention.

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 the copolymer 8 of the present invention.

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 completion of the reaction, the ethyl alcohol was removed with a rotary evaporator to obtain an aqueous solution of the copolymer 9 of the present invention.

Production Example 21
5.6 g of 1H, 1H, 2H, 2H-heptadecafluorodecyl acrylate (“Biscoat 17F”, manufactured by Osaka Organic Chemicals) and methyl polyoxyethylene (23) methacrylate were placed in a flask equipped with a nitrogen inlet tube, a condenser and a stirrer. It consists of 24.0 g of "NK ester M-230G" manufactured by Shin-Nakamura Chemical Co., 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. The mixed solvent 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, isopropyl alcohol was removed with a rotary evaporator to obtain an aqueous solution of copolymer 10 of the present invention.

Hereinafter, the present invention will be described specifically with reference to Examples, but it is needless to say that the present invention is not limited to these Examples.

<Examples 1 to 4, Comparative Example 1>
According to the following formulation, a foundation, which is the aqueous gel cosmetic of the present invention, was prepared. That is, the mixture (a) of the components 1 to 15 in Table 3 was stirred and mixed to form a uniform solution, and then the mixture (b) of the components 16 to 19 was added, followed by vigorous stirring and mixing with a disper (high-speed disperser). A homogeneous solution (C) obtained by mixing the components 20 and 21 was added to the mixture of (A) and (B) while stirring, and the mixture was allowed to stand to obtain an aqueous gel.
Hereinafter, the numerical values in the tables describing the formulation examples and comparative examples of the aqueous gel type cosmetics represent wt%.

表中セテス−３０はＰＯＥ（３０）セチルエーテルを表し、カルボマーはカルボキシビニルポリマーを表す。

In the table, ceteth-30 represents POE (30) cetyl ether, and carbomer represents carboxyvinyl polymer.

<Examples 5 to 8, Comparative Example 2>
According to the following formulation, a UV protector (a UV protection foundation), which is the aqueous gel cosmetic of the present invention, was prepared. That is, the mixture (a) of the components 1 to 15 in Table 4 was stirred and mixed to form a uniform solution, and then the component 16 (b) was added, followed by vigorous stirring and mixing with a disper (high-speed disperser). A mixture obtained by mixing components 17 and 18 to obtain a homogeneous solution (c) was added to the mixture of (a) and (b) while stirring, and the mixture was allowed to stand to obtain an aqueous gel.

<Examples 9 to 12, Comparative Example 3>
An eye color, which is the aqueous gel cosmetic of the present invention, was prepared according to the following formulation. That is, the mixture (a) of the components 1 to 14 in Table 5 was stirred and mixed to form a uniform solution, and then the components 15 to 20 (b) were added and mixed vigorously with a disper (high-speed disperser). The mixture (C) obtained by mixing the components 21 and 22 into a homogeneous solution was added to the mixture of (A) and (B) while stirring, and the mixture was allowed to stand to obtain an aqueous gel.

<Examples 13 to 15, Comparative Example 4>
A lipstick, which is the aqueous gel cosmetic of the present invention, was prepared according to the following formulation. That is, after the mixture (a) of the components 1 to 13 in Table 6 was stirred and mixed to form a uniform solution, the components 14 to 19 (b) were added, and the mixture was vigorously stirred and mixed with a disper (high-speed disperser). A homogeneous solution (C) obtained by mixing the components 20 and 21 was added to the mixture of (A) and (B) while stirring, and the mixture was allowed to stand to obtain an aqueous gel.

<Examples 16 to 18, Comparative Example 5>
A lip gloss, which is an aqueous gel cosmetic of the present invention, was prepared according to the following formulation. That is, the mixture (a) of components 1 to 13 and the mixture (b) of components 14 and 15 in Table 7 were each stirred and mixed to form a uniform solution. After adding (b) while stirring (a), the mixture was allowed to stand to obtain an aqueous gel.

<Test Example 1: Makeup test of aqueous gel type cosmetic>
The aqueous gel cosmetics of Examples 1 to 18 and Comparative Examples 1 to 5 were applied to the inner part of the arm. After standing for 5 minutes, the application site was rubbed with a non-woven fabric while running water on the arm, and the time until the applied makeup cosmetic was completely removed was measured. Table 8 shows the results. The numerical values in the table are the time (seconds) until the applied makeup cosmetic is completely removed.

<Test Example 2: Evaluation of refreshing sensation during application of aqueous gel type cosmetic>
The aqueous gel type cosmetics of Examples 1 to 22 and Comparative Examples 1 to 5 were applied to the inner part of the arm, and the refreshing feeling felt at this time was evaluated by 20 panelists. The refreshing sensation was evaluated on a 5-point scale according to the following criteria. Table 8 shows the results. The numerical values in the table represent the average scores of 20 panelists.
1: No refreshing feeling is felt.
2: Refreshing feeling is slightly felt.
3: Refreshing feeling is slightly felt.
4: Cool feeling is clearly felt.
5: Cool feeling is felt considerably.

<Test Example 3: Evaluation of UV cut effect of aqueous gel type UV protector>
The aqueous gel type UV protectors of Examples 5 to 8 and Comparative Example 2 were applied to the inner part of the arm. After standing for 5 minutes, the application site was rubbed with a nonwoven fabric for 10 seconds while running water on the arm. After leaving the arm to dry for another 5 minutes, a UV lamp was applied to the application site.
At this time, in Comparative Example 2, the application site did not reflect UV light at all, whereas in Examples 5 to 8, the application site reflected UV light. That is, in Comparative Example 2, the UV cut effect was lost, whereas in Examples 5 to 8, the UV cut effect was maintained.
From this, it can be seen that all of the aqueous gel-type cosmetics of the present invention have excellent sustainability of the cosmetic effect while maintaining excellent refreshing feeling during use.

The present invention can be applied to an aqueous gel cosmetic having an action of improving the longevity of makeup.

Claims (8)

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 Aqueous gel cosmetic 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), R1 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R2 represents an alkyl group having 5 to 12 carbon atoms having 8 to 21 substituted fluorine atoms.)

General formula (II)
(In the 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 a carbon 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.) The aqueous gel cosmetic 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. The aqueous gel cosmetic 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), R6 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R7 represents a hydrogen atom, an aromatic group having 6 to 20 carbon atoms, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, Or represents 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) Aqueous gel type cosmetic containing a copolymer comprising 30.2 to 45% by weight of the above and 3) 50 to 60% by weight of one or more structural units derived from a monomer represented by the general formula (IV) Fees.

General formula (I)
(In the formula (I), R1 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R2 represents an alkyl group having 5 to 12 carbon atoms having 8 to 21 substituted fluorine atoms.)

General formula (II)
(In the 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 a carbon 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), R8 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R9 represents an alkyl group having 1 to 3 carbon atoms.) The aqueous gel cosmetic 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), R6 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R7 represents a hydrogen atom, an aromatic group having 6 to 20 carbon atoms, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, Or represents an acyl group having 1 to 20 carbon atoms. Q represents a numerical value of 8 to 40.) 2. The composition according to claim 1, further comprising one or more selected from carboxyvinyl polymers, alkyl (C10-30) acrylates and methacrylates, and physiologically acceptable salts thereof. The cosmetic according to any one of claims 1 to 5. The cosmetic according to any one of claims 1 to 6, which is a makeup cosmetic. The cosmetic according to any one of claims 1 to 7, which is used for summer.