JP4426859B2 - Polymer composition for film formation - Google Patents

Description

  The present invention relates to a film-forming polymer composition that forms a film that is flexible, strong, and excellent in water resistance. More specifically, the solvent is an aqueous solvent, which is highly safe, has little impact on the environment, and forms a film with excellent flexibility and film strength and high bending strength when mixed with solids such as powder. The present invention relates to a film-forming polymer composition.

  The present invention also relates to a film-forming polymer composition capable of forming a cosmetic film that is not destroyed by the movement of the skin when it is used as a cosmetic, particularly a powder excellent in this characteristic when a powder is blended. .

  Various hydrophilic monomers have been widely used in the past as a polymer or copolymer and used as an aqueous coating material or a thickening / gelling agent. For example, it is known that a polymer of polyoxyalkylene glycol mono (meth) acrylate is suitable as a base for hair cosmetics because it has moderate moisturizing and viscous properties and good setting power on hair (for example, , See Patent Document 1). Further, it is known that a copolymer of polyoxyalkylene glycol mono (meth) acrylate and an ethylenically unsaturated monomer is an excellent aqueous thickener (see, for example, Patent Document 2).

  However, such a polymer or copolymer is a linear polymer and lacks flexibility when a film is formed. For this reason, there is a disadvantage that the coating strength is remarkably lowered when the coated body is thickly coated or when a solid content such as powder is present in the coating forming composition. Furthermore, since the obtained coating film is water-based, it has a drawback of poor water resistance.

On the other hand, as a measure to solve the drawbacks that such linear polymers generally have, the water resistance of the coating is improved by copolymerizing a fluoroalkyl (meth) acrylate component and a water-soluble vinyl compound component under a specific ratio. However, the film strength was still inferior (see, for example, Patent Document 3). In addition, as a measure for solving the drawbacks generally possessed by such linear polymers, it is conceivable to form a copolymer using a bifunctional monomer such as EDMA as a crosslinking agent. However, there is a drawback that a film-forming composition blended at such a high concentration as to be used as a film agent cannot be prepared. Therefore, it is currently used mainly as an aqueous thickener or gelling agent.
Japanese Examined Patent Publication No. 2-4571 JP 58-27771 A Japanese Patent Laid-Open No. 11-158039

  The present invention has been made under such circumstances, and has a sufficient solubility in water, is excellent in water resistance, flexibility and coating strength, and can form a coating with high bending strength. It is an object to provide a forming polymer composition. Moreover, this invention makes it a subject to provide the polymer composition for film formation suitable for the cosmetics which can give the cosmetic film which is not destroyed especially by the motion of skin.

  As a result of intensive studies to solve the above problems, the present inventors copolymerize a specific hydrophobic monomer, hydrophilic monomer, hydrophilic bifunctional monomer, and fluoroalkyl group-containing monomer under a specific composition ratio. Thus, it was found that a film-forming polymer composition having the above characteristics was obtained, and the present invention was completed based on this finding.

That is, the present invention is as follows.
(1) One or more structural units derived from a hydrophobic monomer represented by the following general formula (I), one or more structural units derived from a hydrophilic monomer represented by the following general formula (II) , One or more structural units derived from a hydrophilic bifunctional monomer represented by the following general formula (III), and one kind derived from a fluoroalkyl group-containing monomer represented by the following general formula (IV) It is a water-soluble copolymer that has the above structural units as essential structural units and may have other structural units,
The ratio of one or more structural units derived from the hydrophobic monomer represented by the general formula (I) to the total structural units is 30 to 60% by mass, and the hydrophilicity represented by the general formula (II) One type derived from the hydrophilic bifunctional monomer represented by the general formula (III) , wherein the proportion of one or more types of structural units derived from the functional monomer in the total structural units is 30 to 60% by mass One or more structural units derived from the fluoroalkyl group-containing monomer represented by the general formula (IV), wherein the proportion of the structural units in the total structural units is 0.1 to 5.0% by mass. A film-forming polymer composition comprising: a water-soluble copolymer having a proportion of 0.1 to 5.0% by mass in all of the structural units; and water.

（一般式（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は炭素数１〜３個のアルキル基を表す。）

(In general 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 1 to 3 carbon atoms.)

（一般式（II）中、Ｒ^３は水素原子又は炭素数１〜３のアルキル基を表し、Ｒ^４は水酸基を有していてもよい炭素数２〜４のアルキレン基を表し、Ｒ^５は水素原子、炭素数６〜１０の芳香族基、炭素数１〜１４の脂肪族炭化水素基又は炭素数１〜１２のアシル基を表す。ｎは４〜４０の数値を表す。）

(In general formula (II), R ³ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ⁴ represents an alkylene group having 2 to 4 carbon atoms which may have a hydroxyl group, and R ⁵ represents A hydrogen atom, an aromatic group having 6 to 10 carbon atoms, an aliphatic hydrocarbon group having 1 to 14 carbon atoms, or an acyl group having 1 to 12 carbon atoms, n represents a numerical value of 4 to 40.)

（一般式（III）中、Ｒ^６及びＲ^８はそれぞれ独立に水素原子又は炭素数１〜３のアルキル基を表し、Ｒ^７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、ｍは
４〜４０の数値を表す。）

(In general formula (III), R ⁶ and R ⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ⁷ is an alkylene group having 2 to 4 carbon atoms which may have a hydroxyl group. M represents a numerical value of 4 to 40.)

（一般式（IV）中、Ｒ^９は水素原子又は炭素数１〜３のアルキル基を表し、Ｒ^１０は３〜２１個の置換フッ素原子を有する炭素数２〜１２のアルキル基を表す。）

(In general formula (IV), R ⁹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ¹⁰ represents an alkyl group having 2 to 12 carbon atoms having 3 to 21 substituted fluorine atoms.)

Hereinafter, the “water-soluble copolymer” of the present invention is referred to as “aqueous copolymer”.

(2) The polymer composition for film formation according to ( 1), wherein the hydrophilic monomer represented by the general formula (II) is a hydrophilic monomer represented by the following general formula (V).

（一般式（Ｖ）中、Ｒ^１１は水素原子又は炭素数１〜３のアルキル基を表し、Ｒ^１２は水素原子、炭素数６〜１０の芳香族基、炭素数１〜１４の脂肪族炭化水素基又は炭素数１〜１２のアシル基を表す。ｑは４〜４０の数値を表す。）

(In General Formula (V), R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ¹² represents a hydrogen atom, an aromatic group having 6 to 10 carbon atoms, or an aliphatic carbon atom having 1 to 14 carbon atoms. Represents a hydrogen group or an acyl group having 1 to 12 carbon atoms, and q represents a numerical value of 4 to 40.)

( 3 ) The hydrophilic bifunctional monomer represented by the general formula (III) is a hydrophilic bifunctional monomer represented by the following general formula (VI) (1) or (2 ) The polymer composition for film formation as described in 1) .

（一般式（VI）中、Ｒ^１３及びＲ^１４はそれぞれ独立して水素原子又は炭素数１〜３のアルキル基を表し、ｒは４〜４０の数値を表す。）

(In general formula (VI), R ¹³ and R ¹⁴ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and r represents a numerical value of 4 to 40.)

( 4 ) The polymer composition for film formation according to any one of (1) to ( 3 ), wherein the aqueous copolymer further has one or more structural units derived from methacrylic acid, acrylic acid or a salt thereof. object.

( 5 ) The film-forming polymer according to ( 4 ), wherein the proportion of one or more structural units derived from methacrylic acid, acrylic acid or a salt thereof in the total structural units is 2 to 30% by mass. Composition.

( 6 ) The polymer composition for film formation according to any one of (1) to ( 5 ), which is a cosmetic.

  ADVANTAGE OF THE INVENTION According to this invention, the polymer composition for film formation which has sufficient solubility with respect to water, is excellent in water resistance, a softness | flexibility, and film strength, and forms a film with high bending strength can be provided. Moreover, according to this invention, the polymer composition for film formation suitable for the cosmetics which give the cosmetic film which is not destroyed especially by movement of skin can be provided.

Hereinafter, the present invention will be described in detail.
(1) One or more structural units derived from the hydrophobic monomer represented by the general formula (I) used in the present invention The aqueous copolymer constituting the film-forming polymer composition of the present invention has the following general formula ( One or more structural units derived from the hydrophobic monomer represented by I) (hereinafter also referred to as “structural unit (I)”) are included as essential structural units.

（一般式（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は炭素数１〜３個のアルキル基を表す。）

(In general 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 1 to 3 carbon atoms.)

Here, examples of the alkyl group represented by R ¹ include a methyl group, an ethyl group, a propyl group, a 1-methylethyl group, and a cyclopropyl group. In the present invention, R ¹ is preferably a hydrogen atom or a methyl group. Examples of the alkyl group represented by R ² include a methyl group, an ethyl group, a propyl group, a 1-methylethyl group, and a cyclopropyl group. Among these, a methyl group is preferable.

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

  In the present invention, the “structural unit derived from a monomer” refers to a structural unit formed by cleavage of a carbon-carbon unsaturated bond of a corresponding monomer by a polymerization reaction.

Although the structural unit (I) contained in the aqueous copolymer used in the present invention may be only one type, it has a combination of two or more types of structural units (I) as long as the general formula (I) is satisfied. May be. In the present invention, the total amount of one or more of the structural units (I) is preferably 30 to 60% by mass, more preferably 35 to 55% by mass, based on all the structural units constituting the aqueous copolymer. More preferably, it has 40 to 55 mass%.

The structural unit derived from the monomer represented by the general formula (I) affects the strength of the film formed by the aqueous copolymer, and the content of the structural unit (I) with respect to all the structural units of the aqueous polymer is within the above range. By doing so, an aqueous copolymer capable of forming a film having excellent strength can be produced. If the content of the structural unit (I) is too small than the above range, the strength of the film is not sufficient. On the other hand, if the content is too large, the water solubility of the resulting copolymer may be lowered, and a film-forming composition may not be prepared. .

(2) One or more structural units derived from the hydrophilic monomer represented by the general formula (II) used in the present invention. The aqueous copolymer constituting the film-forming polymer composition of the present invention is represented by the following general formula: One or more structural units derived from the hydrophilic monomer represented by the formula (II) (hereinafter also referred to as “structural unit (II)”) are included as essential structural units.

（一般式（II）中、Ｒ^３は水素原子又は炭素数１〜３のアルキル基を表し、Ｒ^４は水酸基を有していてもよい炭素数２〜４のアルキレン基を表し、Ｒ^５は水素原子、炭素数６〜１０の芳香族基、炭素数１〜１４の脂肪族炭化水素基、又は炭素数１〜１２のアシル基を表す。ｎは４〜４０の数値を表す。）

(In general formula (II), R ³ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ⁴ represents an alkylene group having 2 to 4 carbon atoms which may have a hydroxyl group, and R ⁵ represents A hydrogen atom, an aromatic group having 6 to 10 carbon atoms, an aliphatic hydrocarbon group having 1 to 14 carbon atoms, or an acyl group having 1 to 12 carbon atoms, and n represents a numerical value of 4 to 40.)

Here, examples of the alkyl group represented by R ³ include a methyl group, an ethyl group, a propyl group, a 1-methylethyl group, and a cyclopropyl group. In the present invention, R ³ is preferably a hydrogen atom or a methyl group. Examples of the alkylene group represented by R ⁴ include an ethylene group, a propylene group, an isopropylene group, a 2-hydroxypropylene group, a 1-hydroxy-2-methylethylene group, and a 2-hydroxy-1-methylethylene group. Of these, ethylene group or propylene group is preferable, and ethylene group is more preferable.

Among the groups represented by R ⁵ , examples of the aromatic group having 6 to 10 carbon atoms include a phenyl group, a benzyl group, a methylphenyl group, and an ethylphenyl group; an aliphatic group having 1 to 14 carbon atoms Preferred examples of the hydrocarbon group include a methyl group, an ethyl group, a butyl group, a tertiary butyl group, a hexyl group, a cyclohexyl group, an octyl group, a 2-ethylhexyl group, and a lauryl group; Preferable examples of the ˜12 acyl group include a formyl group, an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a valeryl group, and a lauroyl group. Among these, the group represented by R ⁵ is preferably an aliphatic hydrocarbon group having 1 to 14 carbon atoms, and more preferably an alkyl group having 1 to 12 carbon atoms.

  Here, it is important that n is in the numerical range of 4-40. In the present invention, by using the structural unit (II) in which n is in the above range for the aqueous copolymer constituting the film-forming polymer composition, an aqueous copolymer capable of forming a film having excellent strength can be produced. When n is less than 4, the water solubility of the resulting copolymer is lowered, and the film-forming composition may not be prepared. On the other hand, if n is larger than 40, the strength of the film formed by the copolymer is lowered, which is not preferable.

Among the monomers represented by the above general formula (II), specific examples of the monomer in which R ⁴ is a propylene group include polypropylene glycol (6) monoacrylate, polypropylene glycol (9) monoacrylate, and polypropylene glycol (13) mono Examples thereof include acrylate, polypropylene glycol (9) monomethacrylate, polypropylene glycol (13) monomethacrylate and the like. Many of these polymers are commercially available. As an example, there are trade names “Blemmer” AP-400, AP-550, AP-800, PP-500, PP-800 (all manufactured by NOF Corporation) and the like. A specific example of the monomer in which R ⁴ is an ethylene group will be described later.

  Among the structural units derived from the hydrophilic monomer represented by the general formula (II), structural units derived from the hydrophilic monomer represented by the following general formula (V) are particularly preferable.

（一般式（Ｖ）中、Ｒ^１１は水素原子又は炭素数１〜３のアルキル基を表し、Ｒ^１２は水素原子、炭素数６〜１０の芳香族基、炭素数１〜１４の脂肪族炭化水素基、又は炭素数１〜１２のアシル基を表す。ｑは４〜４０の数値を表す。）

(In General Formula (V), R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ¹² represents a hydrogen atom, an aromatic group having 6 to 10 carbon atoms, or an aliphatic carbon atom having 1 to 14 carbon atoms. Represents a hydrogen group or an acyl group having 1 to 12 carbon atoms, and q represents a numerical value of 4 to 40.)

  Specific examples of the monomer represented by the general formula (V) include polyethylene glycol (4.5) monoacrylate, polyethylene glycol (4.5) monomethacrylate, polyethylene glycol (10) monoacrylate, polyethylene. Glycol (8) monomethacrylate, polyethylene glycol (23) monoacrylate, polyethylene glycol (23) monomethacrylate, methoxypolyethylene glycol (9) acrylate, methoxypolyethylene glycol (4) methacrylate, methoxypolyethylene glycol (9) methacrylate, methoxypolyethylene glycol (23) Methacrylate, oleyloxypolyethylene glycol (18) Methacrylate, lauroxypolyethylene glycol (4) Aqua Rate, lauroxypolyethylene glycol (18) acrylate, lauroxypolyethylene glycol (4) methacrylate, lauroyl acetoxyphenyl polyethylene glycol (10) methacrylate, and the like. The numbers in parentheses indicate the value of q.

  In addition, as described in the general formula (II), in the general formula (V) as well, q is in the numerical range of 4 to 40 in order to produce an aqueous copolymer capable of forming a film having excellent strength. This is very important.

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

Although the structural unit (II) contained in the aqueous copolymer used in the present invention may be only one type, it has a combination of two or more types of structural units (II) as long as the general formula (II) is satisfied. May be. In the present invention, the total amount of one or more of the structural units (II) is preferably 30 to 60% by mass, more preferably 35 to 55% by mass, based on all the structural units constituting the aqueous copolymer. More preferably, it has 40 to 55 mass%.

  The structural unit derived from the monomer represented by the general formula (II) is responsible for water solubility of the aqueous copolymer, and the content of the structural unit (II) with respect to all the structural units of the aqueous polymer is within the above range. As a result, a coating having excellent strength can be formed, and an aqueous copolymer having excellent water solubility can be produced. If the content of the structural unit (II) is less than the above range, sufficient solubility of the aqueous copolymer in water cannot be ensured. On the other hand, if the content is more than the above range, the strength of the coating formed by the aqueous copolymer is reduced. This is not preferable.

(3) One or more structural units derived from the hydrophilic difunctional monomer represented by the general formula (III) used in the present invention. The aqueous copolymer constituting the film-forming polymer composition of the present invention is: 1 type or more structural units (henceforth "structural unit (III)") derived from the hydrophilic bifunctional monomer represented by the following general formula (III) as an essential structural unit.

（一般式（III）中、Ｒ^６及びＲ^８はそれぞれ独立に水素原子又は炭素数１〜３のアルキル基を表し、Ｒ^７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、ｍは４〜４０の数値を表す。）

(In general formula (III), R ⁶ and R ⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ⁷ is an alkylene group having 2 to 4 carbon atoms which may have a hydroxyl group. M represents a numerical value of 4 to 40.)

Here, examples of the alkyl group represented by R ⁶ and R ⁸ include a methyl group, an ethyl group, a propyl group, a 1-methylethyl group, and a cyclopropyl group. In the present invention, R ⁶ and R ⁸ are each preferably a hydrogen atom or a methyl group. Examples of the alkylene group represented by R ⁷ include an ethylene group, a propylene group, an isopropylene group, a 2-hydroxypropylene group, a 1-hydroxy-2-methylethylene group, and a 2-hydroxy-1-methylethylene group. Although it can illustrate, Preferably it is an ethylene group or a propylene group, More preferably, it is an ethylene group.

Among the monomers represented by the general formula (III), those in which R ⁷ is an ethylene group will be described later. Specific examples of the monomer having a propylene group include polypropylene glycol (4) diacrylate, polypropylene glycol (7 ) Diacrylate, polypropylene glycol (9) dimethacrylate and the like, and these monomers are commercially available. As an example, there are trade names “Blemmer” ADP-250, ADP-400, and PDP-400 (all manufactured by NOF Corporation). The monomer represented by the general formula (III) can also be obtained in high yield by an esterification reaction between the corresponding alkylene glycol and acrylic acid or methacrylic acid chloride or anhydride.

  Among the structural units (III) derived from the hydrophilic bifunctional monomer represented by the general formula (III), particularly preferred are structural units derived from the monomer represented by the general formula (VI). It is done.

（一般式（VI）中、Ｒ^１３及びＲ^１４はそれぞれ独立して水素原子又は炭素数１〜３のアルキル基を表し、ｒは４〜４０の数値を表す。）

(In general formula (VI), R ¹³ and R ¹⁴ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and r represents a numerical value of 4 to 40.)

Here, examples of the alkyl group represented by R ¹³ and R ¹⁴ include a methyl group, an ethyl group, a propyl group, a 1-methylethyl group, and a cyclopropyl group. In the present invention, R ¹³ and R ¹⁴ are each preferably a hydrogen atom or a methyl group.

  The monomer represented by the general formula (VI) can be obtained in a high yield by an esterification reaction between polyethylene glycol having a corresponding polymerization degree and a chloride or anhydride of acrylic acid or methacrylic acid. Moreover, since a commercial item already exists, it is also possible to utilize this commercial item. For example, there are trade names “Blemmer” ADE-200, ADE-400, PDE-200, PDE-400, PDE-600, and PDE-1000 (all manufactured by NOF Corporation).

  Although the structural unit (III) contained in the aqueous copolymer used in the present invention may be only one type, it has a combination of two or more types of structural units (III) as long as the general formula (III) is satisfied. May be.

The structural unit (III) is required to have a numerical value range of 4 to 40 in the general formula (III) or the general formula (VI). In the present invention, by using the structural unit (III) in which m or r is in the above range for the aqueous copolymer constituting the film-forming polymer composition, a film having excellent strength and flexibility can be formed and water-soluble. Excellent aqueous copolymers can be produced. Regardless of the length of R ⁷ in the structural unit (III), when m or r is less than 4, the water solubility of the copolymer may be significantly reduced. In some cases, sufficient film strength and flexibility cannot be imparted to the coating film.

The water solubility of the aqueous copolymer varies depending on the length of R ⁷ in the structural unit (III), and the water solubility of the aqueous copolymer tends to decrease as R ⁷ increases. In the general formula (III) or the general formula (VI), this tendency becomes stronger as m or r becomes smaller. Therefore, if the ratio of the structural unit (III) to all the structural units constituting the aqueous copolymer is too high, the water-soluble property of the aqueous copolymer cannot be ensured. However, when m or r is large, even if the ratio of the structural unit (III) to all the structural units constituting the aqueous copolymer is relatively high, it is sufficient for the film formed by the aqueous copolymer while ensuring water solubility. Film strength and flexibility can be imparted.

  That is, in the present invention, the proportion of the structural unit (III) is, as described above, from the viewpoint of obtaining an aqueous copolymer that can form a film excellent in strength and flexibility while ensuring hydrophilicity. It is also important that the total amount is 0.1 to 5% by mass, preferably 0.2 to 4% by mass, and more preferably 0.4 to 3% by mass with respect to all constituent units.

Further, when the structural unit (III) is a structural unit derived from the hydrophilic bifunctional monomer represented by the formula (VI), that is, when R ⁷ is an ethylene group in the formula (III), r There the constituent unit at the time of 15 or more (III) 0.1 to 5.0 mass% in total, preferably 0.2 to 4.5%, more preferably from 0.4 to 3.5 mass% Included as a percentage. In case the above, r is the constitutional unit when less than 15 (III) is 0.1 to 3.5 mass% in total, preferably 0.2 to 3.0%, more preferably 0.4 to 2 It is contained at a ratio of 5% by mass.

(4) One or more structural units derived from the fluoroalkyl group-containing monomer represented by the general formula (IV) used in the present invention. The aqueous copolymer constituting the film-forming polymer composition of the present invention further includes: One or more structural units derived from a hydrophilic bifunctional monomer represented by the following general formula (IV) (hereinafter also referred to as “structural unit (IV)”) are included as essential structural units.

（一般式（IV）中、Ｒ^９は水素原子又は炭素数１〜３のアルキル基を表し、Ｒ^１０は３〜２１個の置換フッ素原子を有する炭素数２〜１２のアルキル基を表す。）

(In general formula (IV), R ⁹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ¹⁰ represents an alkyl group having 2 to 12 carbon atoms having 3 to 21 substituted fluorine atoms.)

Here, examples of the alkyl group represented by R ⁹ include a methyl group, an ethyl group, a propyl group, a 1-methylethyl group, and a cyclopropyl group. In the present invention, R ⁹ is preferably a hydrogen atom or a methyl group.

In the general formula (IV), R ¹⁰ represents an alkyl group having 2 to 12 carbon atoms having 3 to 21 substituted fluorine atoms. Examples of such an alkyl group having a substituted fluorine atom include 2,2,2-trifluoroethyl group, 2,2,3,3-tetrafluoropropyl group, 1,1,1,3,3,3-hexa Fluoroisopropyl group, 2,2,3,3,4,4,5,5-octafluoropentyl group, 1H, 1H, 2H, 2H-nonafluorohexyl group, 1H, 1H, 7H-dodecafluoroheptyl group, 1H , 1H-tridecafluoroheptyl group, 1H, 1H-pentadecafluorooctyl group, 1H, 1H, 2H, 2H-heptadecafluorodecyl group, 1H, 1H, 11H-eicosafluoroundecyl group and the like can be preferably exemplified. . Among the alkyl groups represented by R ⁹ , those having 3 to 10 carbon atoms are preferable, and those having 6 to 17 substituted fluorine atoms are preferable.

  Such a fluoroalkyl group-containing monomer represented by the general formula (IV) is 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. Can be obtained. Some of the fluoroalkyl group-containing monomers represented by the general formula (IV) are already available on the market and can be used. As an example, there are biscoat 3F, 3FM, 4F, 4FM, 6FM, 8F, 8FM, 17F, and 17FM (all manufactured by Osaka Organic Chemical Industry Co., Ltd.).

  Although the structural unit (IV) contained in the aqueous copolymer used in the present invention may be only one type, it has a combination of two or more types of structural units (IV) as long as the general formula (IV) is satisfied. May be.

In the present invention, the proportion of the structural unit (IV) is 0.1 to 5.0% by weight, preferably 0.2 to 4.0% by weight, based on all the structural units constituting the aqueous copolymer. Preferably 0.
It is important that the content is 3 to 3.5% by mass. The structural unit (IV) derived from the monomer represented by the general formula (IV) gives water resistance to the film formed by the aqueous copolymer, and the proportion of the structural unit (IV) is within the above range. Thus, sufficient water resistance can be imparted to the formed film while maintaining the water solubility of the aqueous copolymer. If the proportion of the structural unit (IV) is too smaller than the above range, the water-soluble copolymer can be ensured in water solubility, but the water resistance may be significantly lowered. On the other hand, if the amount is more than the above range, the water-soluble copolymer may not have sufficient water solubility.

(5) Other optional structural units that can be included in the aqueous copolymer The aqueous copolymer in the present invention is derived from monomers that are usually used in the copolymer in addition to the above-described essential structural units (I) to (IV). Can be included as any constituent unit. Among them, it is preferable to have one or more structural units derived from acrylic acid, methacrylic acid, or a salt thereof (hereinafter also referred to as “structural unit (VII)”).

  In this case, the structural unit (VII) possessed by the aqueous copolymer may be only one type, or may be a combination of two or more types. Moreover, when an aqueous copolymer has structural unit (VII), the preferable ratio is 2-30 mass% in total with respect to all the structural units which comprise an aqueous copolymer. By containing the structural unit (VII) in the above ratio, the adhesion between the film formed by the copolymer and the film-forming surface can be improved.

  In addition to the essential structural units (I) to (IV) described above, the aqueous copolymer used in the present invention may contain any structural unit derived from a monomer that can usually constitute a copolymer for film formation of the present invention. It can have in the range which does not impair the function and effect of a composition. Such arbitrary structural units include (meth) acrylic acid amides such as acrylic acid amide, methacrylic acid amide, acrylic acid monoalkylamide, and methacrylic acid monoalkylamide; acrylic acid-n-butyl, (meth) acrylic acid isobutyl, etc. (Meth) acrylic acid alkyl ester having an alkyl group having 4 or more carbon atoms; (meth) acrylic such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate Acid hydroxyalkyl esters; (meth) acrylic acid aryl esters such as benzyl (meth) acrylate; (meth) acrylic acid alkoxyalkyl esters such as methoxymethyl (meth) acrylate and methoxyethyl (meth) acrylate; vinyl acetate; Vinyl pyrrolide ; Styrene; alpha-methyl styrene acrylonitrile and the like. Most of these monomers are commercially available.

(6) Aqueous copolymer used in the present invention The aqueous copolymer used in the present invention comprises the above structural units (I), (II), (III) and (IV), and, if necessary, the structural unit (VII) and others. Is a copolymer containing any of the structural units in its skeleton. The aqueous copolymer is usually a random copolymer in which structural units are bonded at random, but may be a block copolymer or a graft copolymer.

  The method for producing the aqueous copolymer in the present invention is not particularly limited. For example, the aqueous copolymer can be obtained by a method in which a monomer for deriving each structural unit is mixed in a solvent and a polymerization reaction is performed according to a method usually used for polymerization of acrylic monomers. .

(7) Polymer composition for film formation of this invention The polymer composition for film formation of this invention contains the said aqueous copolymer and water. Moreover, the said aqueous copolymer may contain only 1 type, and may contain it in combination of 2 or more type. Furthermore, if necessary, polyhydric alcohols such as ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, 1,3 butylene glycol, isoprene glycol, 1,2 pentanediol, glycerin, polyglycerin, thickener, pH adjuster, It may contain a plasticizer, preservative, antioxidant and the like.

  The content of the aqueous copolymer in the film-forming polymer composition is not particularly limited, but is preferably 40% by mass or less, more preferably 1 to 35% by mass in order to maintain good fluidity. When the aqueous copolymer of 40% by mass or more is contained in the polymer composition for film formation, the fluidity may be impaired and handling may be difficult.

(8) Cosmetics of this invention The cosmetics of this invention contain the polymer for film formation of the said invention, ie, 1 type, or 2 or more types of the said aqueous copolymer, and water. The cosmetic of the present invention containing the above-described polymer for forming a film of the present invention can form a cosmetic film having excellent strength that is not destroyed even by the movement of the skin, so that the initial cosmetic finish is maintained for a long time. can do. The content of the aqueous copolymer in the cosmetic of the present invention is preferably 0.1 to 50% by mass, more preferably 1 to 40% by mass in total. If the content of the aqueous copolymer is too small, it may not be possible to sufficiently impart a good feeling of use to the decorative coating to be formed, and if it is too large, formulation may be difficult.

In addition to the aqueous copolymer and water, the cosmetic of the present invention can be blended with any component that can be usually blended in cosmetics. Examples of these optional components include hydrocarbons such as squalane, liquid paraffin, light liquid isoparaffin, heavy liquid isoparaffin, microcrystalline wax, and solid paraffin; dimethicone, femethicone, cyclomethicone, amodimethicone, polyether-modified silicone Silicones such as jojoba oil, carnauba wax, owl, beeswax, gallow, octyldodecyl oleate, isopropyl myristate, neopentyl glycol diisostearate, diisostearate malate; stearic acid, laurin Fatty acids such as acid, myristic acid, palmitic acid, isostearic acid, isopalmitic acid, behenic acid, oleic acid; behenyl alcohol, cetanol, oleyl alcohol, octadec Higher alcohols such as alcohol, castor oil, coconut oil, hydrogenated coconut oil, coconut oil, wheat germ oil, triglycerides such as isostearic acid triglyceride, isooctanoic acid triglyceride, olive oil; 1,3-butanediol, glycerin, diglycerin , Dipropylene glycol, polyethylene glycol, 1,2-pentanediol, 1,2-hexylene glycol, isoprene glycol, and other polyhydric alcohols; sorbitan sesquioleate, sorbitan monooleate, sorbitan trioleate, sorbitan sesquistearate, sorbitan mono Stearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan monostearate, polyoxyethylene stearate, polyoxyethylene oleate, poly Polyoxyethylene glyceryl fatty acid esters, polio alkoxy polyoxyethylene alkyl ether, nonionic surfactants such as polyoxyethylene hydrogenated castor oil; sodium lauryl stearate, polyoxyethylene alkyl sulfates, anionic surfactants such as sulfosuccinic acid ester salt Cationic surfactants such as quaternary alkyl ammonium salts; Amphoteric surfactants such as alkyl betaines; Organic powders such as crystalline cellulose, cross-linked methylpolysiloxane, polyethylene powder, acrylic resin powder; talc, mica , Sericite, magnesium carbonate, calcium carbonate, titanium dioxide, iron oxide, bitumen, ultramarine, titanium mica, titanium sericite, silica, etc., powders that may be surface-treated; acrylic acid / alkyl methacrylate copolymers and / Or its salt, carbo Thickeners such as xylvinyl polymer and / or salts thereof, xanthan gum or hydroxypropyl cellulose; vitamins such as retinol, retinoic acid, tocopherol, riboflavin, pyridoxine, ascorbic acid, ascorbic acid phosphate ester, glycyrrhizinate, glycyrrhetin, Active ingredients such as terpenes such as ursolic acid and oleanolic acid, steroids such as estradiol, ethinylestradiol, and estriol; preservatives such as phenoxyethanol, parabens, hibitengluconate, benzalkonium chloride, dimethylaminobenzoic acid esters Preferred examples include UV absorbers such as cinnamic acid esters and benzophenones. These are appropriately selected according to the application.

  EXAMPLES The present invention will be specifically described below with reference to examples, but it goes without saying that the present invention is not limited to these examples.

<Production Example 1 of hydrophilic monomer represented by general formula (II) for deriving structural unit (II)>
103 g of polyethylene glycol # 1000 as a polyethylene glycol compound and 50 g of triethylamine were dissolved in 500 ml of tetrahydrofuran. While the resulting solution was ice-cooled and stirred, a solution prepared by dissolving 5.2 g of methacrylic acid chloride as an acid chloride in 100 ml of tetrahydrofuran was added dropwise to this solution over 2 hours. After completion of dropping, the produced white precipitate was filtered, and tetrahydrofuran and triethylamine were removed from the filtrate using a rotary evaporator to obtain a product. NMR measurement confirmed that the obtained compound was polyethylene glycol (23) monomethacrylate, which is a hydrophilic monomer represented by the above general formula (II).

<Production Examples 2 and 3 of hydrophilic monomer represented by general formula (II) for deriving structural unit (II)>
In the manufacturing example 1 of a hydrophilic monomer, it represents with the said general formula (II) by the method similar to the said manufacturing example 1 except having changed the kind and quantity of a polyethyleneglycol compound and an acid chloride as shown in Table 1. A hydrophilic monomer was produced.

<Production Example 1 of fluoroalkyl group-containing monomer represented by formula (VI) for deriving structural unit (VI)>
1H, 1H, 2H, 2H-nonafluoro-1-hexanol 52.8 g as fluoroalcohol and 50 g of triethylamine were dissolved in 500 ml of tetrahydrofuran. While the resulting solution was ice-cooled and stirred, a solution prepared by dissolving 18.1 g of acrylic acid chloride as an acid chloride in 100 ml of tetrahydrofuran was added dropwise to this solution over 2 hours. After completion of dropping, the produced white precipitate was filtered, and tetrahydrofuran and triethylamine were removed from the filtrate using a rotary evaporator to obtain a product. NMR measurement confirmed that the obtained compound was 1H, 1H, 2H, 2H-nonafluorohexyl acrylate.

<Production Examples 2 to 5 of fluoroalkyl group-containing monomer represented by formula (IV) for deriving structural unit (IV)>
In Production Example 1 of the fluoroalkyl group-containing monomer, it is represented by the above general formula (IV) by the same method as in Production Example 1 except that the types and amounts of fluoroalcohol and acid chloride are changed as shown in Table 2. A fluoroalkyl group-containing monomer was produced.

<Example 1>
In a flask equipped with a nitrogen inlet tube, a cooler, and a stirrer, 54.0 g of methyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), methoxypolyethylene glycol (9) methacrylate (manufactured by NOF Corporation), trade name “Blemmer PME” -400 ") 56.1 g, polyethylene glycol (23) dimethacrylate (manufactured by NOF Corporation, trade name" Blenmer PDE-1000 ") 1.0 g, 2,2,3,3,4,4,5, 2.9 g of 5-octafluoropentyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name “Biscoat 8F”), 6.0 g of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 300 ml of isopropyl alcohol and 300 ml of water The mixed solvent consisting of was taken and mixed with stirring. While stirring was continued, nitrogen gas substitution was performed for 1 hour. A solution prepared by dissolving 2.0 g of ammonium persulfate in 20 ml of water was added thereto, and the reaction was continued at 65 ° C. for 16 hours while continuing stirring. After completion of the reaction, the pH was adjusted to 7.0, and isopropyl alcohol was removed with a rotary evaporator. Furthermore, 72 g of 1,3-butylene glycol was added to obtain a composition 1 which is a film-forming polymer composition of the present invention containing 25% by mass of an aqueous copolymer.

(Coating strength test)
The composition 1, talc and water were mixed so that the copolymer concentration was 10% by mass and the talc concentration was 20% by mass to prepare a coating composition. This coating composition was applied onto a slide glass using a brush and dried at 60 ° C. for 8 hours to obtain a test coating film. A coarse linen was placed on the obtained test coating film, and weights of various weights were placed on the linen in order from light to light. Under such load conditions, the linen was moved on the coating film, and the load at which the coating film was damaged was determined to be the coating strength. The results are shown in Table 3.

(Coating flexibility test)
The composition 1, talc and water were mixed so that the copolymer concentration was 10% by mass and the talc concentration was 30% by mass to prepare a coating composition. Using a brush, this coating composition was applied twice on a styrene film having a thickness of 0.2 mm and dried at 40 ° C. for 12 hours to obtain a test coating film. The operation of bending or stretching the test coating film was repeated, and the number of bendings until a crack occurred on the coating surface on the styrene film was determined. The results are shown in Table 3. The greater the number of times until the coating film cracks, the higher the flexibility of the coating film.

(Water resistance test of coating)
The test was performed using the same test coating film used in the above-described strength test of the coating film. While rubbing the test coating film with a finger under running water, the number of rubbing times until the coating film completely disappeared was determined, and the water resistance of the coating film was evaluated. The results are shown in Table 3. It shows that the water resistance of a film is so high that there are many frequency | counts of rubbing until a film lose | disappears.

<Example 2>
In a flask equipped with a nitrogen inlet tube, a condenser and a stirrer, 34.0 g of methyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), polypropylene glycol (6) monoacrylate (manufactured by NOF Corporation, trade name “Blemmer AP” -400 ") 54.0 g, polypropylene glycol (7) diacrylate (manufactured by NOF Corporation, trade name" Blenmer ADP-400 ") 0.2 g, 2,2,3,3-tetrafluoropropyl methacrylate (Osaka) 4.0 g of organic chemical industry, trade name “Biscoat 4FM”), 7.8 g of acrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 200 ml of ethyl alcohol and 300 ml of water were taken and mixed with stirring. . While stirring was continued, nitrogen gas substitution was performed for 1 hour. A solution obtained by dissolving 1.5 g of ammonium persulfate in 20 ml of water was added thereto, and the reaction was performed at 70 ° C. for 12 hours while continuing stirring. After completion of the reaction, the pH was adjusted to 7.0, and isopropyl alcohol was removed with a rotary evaporator to obtain a composition 2 which is a film-forming polymer composition of the present invention containing 25% by mass of an aqueous copolymer. The obtained composition 2 was subjected to a coating strength test, a flexibility test, and a water resistance test in the same manner as in Example 1. The results are shown in Table 3.

<Example 3>
In a flask equipped with a nitrogen inlet tube, a condenser and a stirrer, 27.0 g of ethyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), methoxypolyethylene glycol (23) methacrylate (manufactured by NOF Corporation, trade name “Blemmer PME”) -1000 ") 29.5 g, polyethylene glycol (9) diacrylate (manufactured by NOF Corporation, trade name" Blenmer ADE-400 ") 0.2 g, 1H, 1H, 2H, 2H-heptadecafluorodecyl acrylate ( 0.9 g of Osaka Organic Chemical Industry Co., Ltd., trade name “Biscoat 17F”), 2.4 g of styrene (manufactured by Tokyo Chemical Industry Co., Ltd.) and 150 ml of isopropyl alcohol and 150 ml of water were mixed with stirring. . While stirring was continued, nitrogen gas substitution was performed for 1 hour. A solution prepared by dissolving 0.2 g of ammonium persulfate in 10 ml of water was added thereto, and the reaction was performed at 70 ° C. for 18 hours while continuing stirring. After completion of the reaction, the pH is adjusted to 7.0, isopropyl alcohol is removed by a rotary evaporator, 72 g of 1,2 pentanediol is further added, and the coating film of the present invention containing 20% by mass of an aqueous copolymer is added. A composition 3 which is a polymer composition was obtained. The obtained composition 3 was subjected to the same strength test, flexibility test and water resistance test as in Example 1. The results are shown in Table 3.

<Example 4>
In a flask equipped with a nitrogen introduction tube, a condenser and a stirrer, 48.6 g of methyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), methoxypolyethylene glycol (4) methacrylate (manufactured by NOF Corporation, trade name “Blemmer PME”) -200 ") 19.0 g, methoxy polyethylene glycol (9) methacrylate (Nippon Yushi Co., Ltd., trade name" Blenmer PME-400 ") 44.0 g, polyethylene glycol (13) dimethacrylate (Nippon Yushi Co., Ltd.) , Trade name “Blemmer PDE-600”) 3.6 g, 2,2,2-trifluoroethyl methacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name “Biscoat 3FM”) 4.2 g, 1,1,1 , 3,3,3-hexafluoroisopropyl methacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd. Coat 6FM ") 0.6 g, and were mixed with stirring takes a mixed solvent consisting of isopropyl alcohol 300ml of water 300ml. While stirring was continued, nitrogen gas substitution was performed for 1 hour. A solution prepared by dissolving 2.0 g of ammonium persulfate in 20 ml of water was added thereto, and the reaction was continued at 65 ° C. for 16 hours while continuing stirring. After completion of the reaction, the pH was adjusted to 7.0, and isopropyl alcohol was removed with a rotary evaporator to obtain Composition 4 which is a film-forming polymer composition of the present invention containing 25% by mass of an aqueous copolymer. The obtained composition 4 was subjected to the same strength test, flexibility test and water resistance test as in Example 1. The results are shown in Table 3.

<Example 5>
In a flask equipped with a nitrogen inlet tube, a condenser and a stirrer, 47.6 g of isopropyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), polyethylene glycol (10) monoacrylate (manufactured by NOF Corporation, trade name “Blemmer AE” -400 ") 49.0 g, polyethylene glycol (23) dimethacrylate (manufactured by NOF Corporation, trade name" Blenmer PDE-1000 ") 2.4 g, 1H, 1H, 7H-dodecafluoroheptyl methacrylate (fluoroalkyl group) 1.0 g of the compound obtained in Production Example 2 of monomer containing) and 300 ml of ethyl acetate were taken and mixed with stirring. While stirring was continued, nitrogen gas substitution was performed for 1 hour. A solution obtained by dissolving 0.2 g of benzoyl peroxide in 10 ml of ethyl acetate was added thereto, and the reaction was carried out by refluxing for 8 hours while continuing stirring. After completion of the reaction, water was added to the solution, and subjected to flushing to obtain a composition 5 which is film-forming polymer composition of the present invention containing 25 wt% of the aqueous copolymer. The obtained composition 5 was subjected to the coating strength test, the flexibility test, and the water resistance test in the same manner as in Example 1. The results are shown in Table 3.

<Example 6>
In a flask equipped with a nitrogen inlet tube, a condenser and a stirrer, 53.5 g of ethyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), polypropylene glycol (13) monomethacrylate (manufactured by NOF Corporation, trade name “Blemmer PP” -800 ") 36.0 g, polyethylene glycol (4.5) monoacrylate (Nippon Yushi Co., Ltd., trade name" Blenmer AE-200 ") 14.4 g, polypropylene glycol (9) dimethacrylate (Nippon Yushi Co., Ltd.) ), Trade name “Blemmer PDP-400”) 0.5 g, 1H, 1H, 2H, 2H-nonafluorohexyl acrylate (compound obtained in Production Example 1 of fluoroalkyl group-containing monomer) 3.6 g, methacrylic acid 12.0 g (manufactured by Tokyo Chemical Industry Co., Ltd.) and 300 ml of ethyl alcohol and 300 ml of water Ranaru mixed solvent was stirred and mixed take. While stirring was continued, nitrogen gas substitution was performed for 1 hour. A solution prepared by dissolving 2.0 g of potassium persulfate in 20 ml of water was added thereto, and further reacted at 65 ° C. for 20 hours while continuing to stir. After completion of the reaction, the pH was adjusted to 7.0, and isopropyl alcohol was removed with a rotary evaporator to obtain a composition 6 that is a film-forming polymer composition of the present invention containing 25% by mass of an aqueous copolymer. The obtained composition 6 was subjected to a coating strength test, a flexibility test, and a water resistance test in the same manner as in Example 1. The results are shown in Table 3.

<Example 7>
In a flask equipped with a nitrogen introduction tube, a condenser and a stirrer, 4.5 g of methyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), 50.0 g of ethyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), polyethylene glycol (23) Monomethacrylate (compound obtained in Production Example 1 of hydrophilic monomer) 34.5 g, polyethylene glycol (9) diacrylate (manufactured by NOF Corporation, trade name “Blemmer ADE-400”) 0.8 g, 2, 1.2 g of 2,3,3-tetrafluoropropyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name “Biscoat 4F”), 1H, 1H-tridecafluoroheptyl acrylate (Production Example 3 of fluoroalkyl group-containing monomer) 1.0 g, n-butyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) 8.0 g, and A mixed solvent consisting of propyl alcohol 180ml and water 120ml were mixed and stirred take. While stirring was continued, nitrogen gas substitution was performed for 1 hour. A solution prepared by dissolving 0.5 g of ammonium persulfate in 10 ml of water was added thereto, and the reaction was performed at 70 ° C. for 12 hours while continuing stirring. After completion of the reaction, the pH was adjusted to 7.0, isopropyl alcohol was removed with a rotary evaporator, 72 g of isoprene glycol was added, and the film-forming polymer composition of the present invention containing 25% by mass of an aqueous copolymer was used. A composition 7 was obtained. The obtained composition 7 was subjected to a coating strength test, a flexibility test, and a water resistance test in the same manner as in Example 1. The results are shown in Table 3.

<Example 8>
In a flask equipped with a nitrogen inlet tube, a condenser and a stirrer, 50.5 g of methyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), oleyloxypolyethylene glycol (18) methacrylate (obtained in Production Example 2 of hydrophilic monomer) Compound) 58.8 g, polyethylene glycol (13) dimethacrylate (manufactured by NOF Corporation, trade name “Blenmer PDE-600”) 0.7 g, 1H, 1H, 11H-eicosafluoroundecyl methacrylate (fluoroalkyl group) (Compound obtained in Production Example 5 of monomer containing monomer) 1.0 g, 9.0 g of acrylic acid, and 360 ml of ethyl alcohol and 240 ml of water were taken and mixed with stirring. While stirring was continued, nitrogen gas substitution was performed for 1 hour. A solution prepared by dissolving 2.0 g of potassium persulfate in 20 ml of water was added thereto, and further reacted at 65 ° C. for 20 hours while continuing to stir. After completion of the reaction, the pH was adjusted to 7.0, and isopropyl alcohol was removed with a rotary evaporator to obtain a composition 8 which is a film-forming polymer composition of the present invention containing 25% by mass of an aqueous copolymer. The obtained composition 8 was subjected to a coating strength test, a flexibility test, and a water resistance test in the same manner as in Example 1. The results are shown in Table 3.

<Example 9>
In a flask equipped with a nitrogen introduction tube, a condenser and a stirrer, 14.8 g of ethyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), lauryloxypolyethylene glycol (10) acrylate (obtained in Production Example 3 of hydrophilic monomer) 21.8 g, polyethylene glycol (23) dimethacrylate (manufactured by NOF Corporation, trade name “Blenmer PDE-1000”) 1.6 g, 2,2,2-trifluoroethyl acrylate (Osaka Organic Chemical Industry) (Product name, “Biscoat 3F”) 1.8 g and 200 ml of toluene were taken and mixed with stirring. While stirring was continued, nitrogen gas substitution was performed for 1 hour. A solution prepared by dissolving 0.2 g of azobisisobutyronitrile in 10 ml of toluene was added thereto, and the reaction was continued at 70 ° C. for 8 hours while continuing stirring. After completion of the reaction, water was added to this solution and flushed to obtain a composition 9, which is a film-forming polymer composition of the present invention containing 25% by mass of an aqueous copolymer. The obtained composition 9 was subjected to the coating strength test, the flexibility test, and the water resistance test in the same manner as in Example 1. The results are shown in Table 3.

<Example 10>
In a flask equipped with a nitrogen inlet tube, a cooler, and a stirrer, 30.0 g of methyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), methoxypolyethylene glycol (4) methacrylate (manufactured by NOF Corporation, trade name “Blemmer PME” -200 ") 9.4 g, methoxypolyethylene glycol (23) methacrylate (Nippon Yushi Co., Ltd., trade name" Blenmer PME-1000 ") 14.0 g, polyethylene glycol (13) dimethacrylate (Nippon Yushi Co., Ltd.) , 0.6 g, 2,2,3,3,4,4,5,5-octafluoropentyl methacrylate (“Biscoat 8FM” manufactured by Osaka Organic Chemical Co., Ltd.) 2 g, 4.8 g of 2-hydroxyethyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), and isopropyl A mixed solvent consisting of alcohol 180ml and water 120ml were mixed and stirred take. While stirring was continued, nitrogen gas substitution was performed for 1 hour. A solution prepared by dissolving 0.5 g of ammonium persulfate in 10 ml of water was added thereto, and the reaction was continued at 70 ° C. for 9 hours while further stirring. After completion of the reaction, the pH was adjusted to 7.0, and isopropyl alcohol was removed with a rotary evaporator to obtain a composition 10 which is a film-forming polymer composition of the present invention containing 25% by mass of an aqueous copolymer. The obtained composition 10 was subjected to the coating strength test, the flexibility test, and the water resistance test in the same manner as in Example 1. The results are shown in Table 3.

<Example 11>
29.4 g of ethyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) and polyethylene glycol (23) monomethacrylate (the compound obtained in Production Example 1 of hydrophilic monomer) were placed in a flask equipped with a nitrogen inlet tube, a condenser and a stirrer. ) 26.7 g, polyethylene glycol (4) diacrylate (manufactured by NOF Corporation, trade name “Blenmer ADE-200”) 0.3 g, 1H, 1H-pentadecafluorooctyl methacrylate (manufacture of fluoroalkyl group-containing monomer) Compound obtained in Example 4) 0.6 g, 2,2,2-trifluoroethyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name “Biscoat 3F”) 1.2 g, acrylic acid (Tokyo Chemical Industry ( Co., Ltd.)) 1.8 g, and a mixed solvent consisting of 180 ml of isopropyl alcohol and 120 ml of water was taken and stirred. Engaged. While stirring was continued, nitrogen gas substitution was performed for 1 hour. A solution prepared by dissolving 0.5 g of ammonium persulfate in 10 ml of water was added thereto, and the mixture was further reacted at 65 ° C. for 12 hours while continuing stirring. After completion of the reaction, the pH was adjusted to 7.0, and isopropyl alcohol was removed with a rotary evaporator to obtain a composition 11 which is a film-forming polymer composition of the present invention containing 25% by mass of an aqueous copolymer. The obtained composition 11 was subjected to the same strength test, flexibility test and water resistance test as in Example 1. The results are shown in Table 3.

<Example 12>
In a flask equipped with a nitrogen introduction tube, a condenser and a stirrer, 59.2 g of methyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), lauroxy polyethylene glycol (18) acrylate (manufactured by NOF Corporation, trade name “Blemmer”) ALE-800 ") 57.0 g, polyethylene glycol (9) diacrylate (manufactured by NOF Corporation, trade name" Blemmer ADE-400 ") 0.8 g, 1,1,1,3,3,3-hexa A mixed solvent composed of 3.0 g of fluoroisopropyl methacrylate (“Biscoat 6FM” manufactured by Osaka Organic Chemical Industry Co., Ltd.) and 360 ml of isopropyl alcohol and 240 ml of water was taken and mixed with stirring. While stirring was continued, nitrogen gas substitution was performed for 1 hour. A solution prepared by dissolving 1.8 g of ammonium persulfate in 10 ml of water was added thereto, and the mixture was further reacted at 70 ° C. for 9 hours while continuing stirring. After completion of the reaction, the pH was adjusted to 7.0, and isopropyl alcohol was removed with a rotary evaporator to obtain Composition 12, which is a film-forming polymer composition of the present invention containing 25% by mass of an aqueous copolymer. The obtained composition 12 was subjected to the coating strength test, the flexibility test, and the water resistance test in the same manner as in Example 1. The results are shown in Table 3.

<Comparative example 1>
In a flask equipped with a nitrogen inlet tube, a condenser and a stirrer, 56.4 g of methyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), methoxypolyethylene glycol (23) methacrylate (manufactured by NOF Corporation), trade name “Blemmer PME” -1000 ") 59.0 g, diethylene glycol dimethacrylate (manufactured by NOF Corporation, trade name" Blenmer PDE-100 ") 1.0 g, 2,2,3,3,4,4,5,5-octafluoro A mixed solvent consisting of 3.6 g of pentyl methacrylate (“Biscoat 8FM” manufactured by Osaka Organic Chemical Industry Co., Ltd.) and 300 ml of isopropyl alcohol and 300 ml of water was taken and mixed with stirring. While stirring was continued, nitrogen gas substitution was performed for 1 hour. A solution prepared by dissolving 2.0 g of ammonium persulfate in 20 ml of water was added thereto, and the reaction was continued at 65 ° C. for 16 hours while continuing stirring. After completion of the reaction, the pH was adjusted to 7.0 and isopropyl alcohol was removed with a rotary evaporator, but the whole solidified and a film-forming composition was not obtained.

<Comparative example 2>
100 g of polyethylene glycol # 2000 as a polyethylene glycol compound and 50 g of triethylamine were dissolved in 500 ml of tetrahydrofuran. While the resulting solution was ice-cooled and stirred, a solution prepared by dissolving 9.5 g of acrylic acid chloride as an acid chloride in 100 ml of tetrahydrofuran was added dropwise to this solution over 2 hours. After completion of the dropwise addition, the white precipitate formed was filtered, and tetrahydrofuran and triethylamine were removed from the filtrate using a rotary evaporator to obtain a product. NMR measurement confirmed that the resulting compound was polyethylene glycol (45) dimethacrylate.

  In a flask equipped with a nitrogen introduction tube, a condenser and a stirrer, 60.0 g of methyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), methoxypolyethylene glycol (23) methacrylate (manufactured by NOF Corporation, trade name “Blemmer PME” -1000 ") 59.0 g, 1.0 g of the above polyethylene glycol (45) dimethacrylate, and a mixed solvent of 300 ml of isopropyl alcohol and 300 ml of water were taken and mixed with stirring. While stirring was continued, nitrogen gas substitution was performed for 1 hour. A solution prepared by dissolving 2.0 g of ammonium persulfate in 20 ml of water was added thereto, and the reaction was continued at 65 ° C. for 16 hours while continuing stirring. After completion of the reaction, the pH was adjusted to 7.0, and isopropyl alcohol was removed with a rotary evaporator to obtain a film-forming composition 13 containing 25% by mass of the copolymer. With respect to the obtained composition 13, the coating strength test, the flexibility test, and the water resistance test were conducted in the same manner as in Example 1. The results are shown in Table 3.

  As shown in Table 3, it was clear that the film-forming composition of the present invention was excellent in all of the film strength, flexibility and water resistance.

<Example 13>
A make-up base cream, which is a cosmetic of the present invention, was prepared according to the formulation shown below. That is, the component Nos. 1-8 mixture (I) and component no. The mixture (ii) of 9 to 20 was heated to 80 ° C., and (ii) was added to (ii) to emulsify, followed by stirring and cooling to obtain a makeup base cream 1. In addition, although prescription of cosmetics is shown in the following Table 4, all the numerical values in the table are mass%.

(Affinity evaluation between cosmetics and skin)
The obtained cream 1 was applied to the inside of the wrist. The state of the cosmetic film on the skin was observed with an enlarged video scope while the wrist flexed and stretched vigorously. From this, the number of times the wrist bends and stretched until the decorative film on the skin was cracked or the decorative film began to be unevenly distributed in the wrinkle portion was determined. The more this number, the decorative film is rich in robust and flexible, indicates that the movement of the skin thus hard to be destroyed. The results are shown in Table 7.

(Water resistance evaluation of cosmetics)
The obtained cream 1 was applied to the inner side of the upper arm. While the applied cream was rubbed with palms under running water, the number of times of rubbing until the cosmetic film was completely washed was determined to evaluate the water resistance of the cosmetic. The results are shown in Table 7. It shows that the water resistance of cosmetics is so high that there are many frequency | counts of rubbing until a cosmetic film lose | disappears.

<Examples 14 to 16>
Except having changed the prescription as shown in Table 4, make base creams 2 to 4 which are the cosmetics of the present invention were prepared using the same method as in Example 13 above. The obtained creams 2 to 4 were subjected to skin affinity evaluation and water resistance evaluation in the same manner as in Example 13. The results are shown in Table 7.

<Comparative Example 3>
A make-up base cream 5 for comparison was prepared using the same method as in Example 13 except that the formulation was changed as shown in Table 4. About the obtained cream 5, affinity evaluation with a skin and water resistance evaluation were performed similarly to Example 13. The results are shown in Table 7.

<Example 17>
According to the prescription shown below, the foundation which is the cosmetics of this invention was produced. That is, the component Nos. 1-8 mixture (I) is heated to 80 ° C. 9-12 (B) was added and mixed vigorously with a disper (high-speed disperser). While maintaining the temperature at 80 ° C., component No. 1 was added to the mixture of (i) and (b). A 13 to 20 mixture (C) heated to 80 ° C. was gradually added to emulsify, stirred and cooled to obtain a creamy foundation 1. The obtained foundation 1 was subjected to affinity evaluation with the skin and water resistance evaluation in the same manner as in Example 13. The results are shown in Table 7.

<Examples 18 to 20>
Except having changed the prescription as shown in Table 5, foundations 2 to 4, which are the cosmetics of the present invention, were prepared using the same method as in Example 17. The obtained foundations 2 to 4 were subjected to skin affinity evaluation and water resistance evaluation in the same manner as in Example 13. The results are shown in Table 7.

<Comparative example 4>
A comparative foundation 5 was prepared using the same method as in Example 17 except that the formulation was changed as shown in Table 5. The obtained foundation 5 was subjected to an affinity evaluation with the skin and a water resistance evaluation in the same manner as in Example 13. The results are shown in Table 7.

<Example 21>
An eye color, which is a cosmetic of the present invention, was produced according to the formulation shown below. That is, the component no. After stirring and mixing the mixture (i) of 1 to 14 to obtain a uniform solution, component no. 15 to 20 (B) was added, and the mixture was vigorously stirred and mixed with a disper (high-speed disperser). Ingredient No. A mixture obtained by mixing 21 and 22 into a uniform solution (c) was added to the mixture of (a) and (b) while stirring, and then allowed to stand to obtain an aqueous gel eye color 1. About the obtained eye color 1, affinity evaluation with a skin and water resistance evaluation were performed similarly to Example 13. The results are shown in Table 7.

<Examples 22 to 24>
Eye colors 2 to 4, which are the cosmetics of the present invention, were prepared using the same method as in Example 21 except that the formulation was changed as shown in Table 6. For the obtained eye colors 2 to 4, affinity evaluation with the skin and water resistance evaluation were performed in the same manner as in Example 13. The results are shown in Table 7.

<Comparative Example 5>
A comparative eye color 5 was produced using the same method as in Example 21 except that the formulation was changed as shown in Table 6. About the obtained eye color 5, affinity evaluation with a skin and water resistance evaluation were performed similarly to Example 13. The results are shown in Table 7.

  As shown in Table 7, it was clear that the cosmetic of the present invention has a high affinity with the skin of the cosmetic film, is not destroyed by the movement of the skin, and is excellent in water resistance. It was.

Claims (6)

One or more structural units derived from a hydrophobic monomer represented by the following general formula (I), one or more structural units derived from a hydrophilic monomer represented by the following general formula (II), One or more structural units derived from a hydrophilic bifunctional monomer represented by the formula (III), and one or more structural units derived from a fluoroalkyl group-containing monomer represented by the following general formula (IV) A water-soluble copolymer having a unit as an essential constituent unit and optionally having other constituent units,
The ratio of one or more structural units derived from the hydrophobic monomer represented by the general formula (I) to the total structural units is 30 to 60% by mass, and the hydrophilicity represented by the general formula (II) One type derived from the hydrophilic bifunctional monomer represented by the general formula (III) , wherein the proportion of one or more types of structural units derived from the functional monomer in the total structural units is 30 to 60% by mass One or more structural units derived from the fluoroalkyl group-containing monomer represented by the general formula (IV), wherein the proportion of the structural units in the total structural units is 0.1 to 5.0% by mass. A film-forming polymer composition comprising: a water-soluble copolymer having a proportion of 0.1 to 5.0% by mass in all of the structural units; and water.

(In general 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 1 to 3 carbon atoms.)

(In General Formula (II), R ³ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ⁴ represents an alkylene group having 2 to 4 carbon atoms which may have a hydroxyl group, and R ⁵ represents A hydrogen atom, an aromatic group having 6 to 10 carbon atoms, an aliphatic hydrocarbon group having 1 to 14 carbon atoms, or an acyl group having 1 to 12 carbon atoms, n represents a numerical value of 4 to 40.)

(In general formula (III), R ⁶ and R ⁸ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ⁷ is an alkylene group having 2 to 4 carbon atoms which may have a hydroxyl group. M represents a numerical value of 4 to 40.)

(In general formula (IV), R ⁹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ¹⁰ represents an alkyl group having 2 to 12 carbon atoms having 3 to 21 substituted fluorine atoms.) The polymer composition for film formation according to claim 1 , wherein the hydrophilic monomer represented by the general formula (II) is a hydrophilic monomer represented by the following general formula (V).

(In general formula (V), R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ¹² represents a hydrogen atom, an aromatic group having 6 to 10 carbon atoms, or an aliphatic carbon atom having 1 to 14 carbon atoms. Represents a hydrogen group or an acyl group having 1 to 12 carbon atoms, and q represents a numerical value of 4 to 40.) The coating film according to claim 1 or 2 , wherein the hydrophilic bifunctional monomer represented by the general formula (III) is a hydrophilic bifunctional monomer represented by the following general formula (VI). Forming polymer composition.

(In general formula (VI), R ¹³ and R ¹⁴ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and r represents a numerical value of 4 to 40.) The polymer composition for film formation according to any one of claims 1 to 3 , wherein the aqueous copolymer further comprises one or more structural units derived from methacrylic acid, acrylic acid or a salt thereof. . 5. The polymer composition for film formation according to claim 4 , wherein the proportion of one or more structural units derived from methacrylic acid, acrylic acid or a salt thereof in the total structural units is 2 to 30% by mass. . It is a cosmetic, The polymer composition for film formation of any one of Claims 1-5 characterized by the above-mentioned.