JP6968628B2 - Emulsifying composition - Google Patents

Description

The present invention relates to an emulsified composition in which fine particles made of a polyvinyl polymer are adsorbed on an emulsified interface.

An emulsified composition in which an oil phase component and an aqueous phase component are mixed by an emulsifier is widely used as a dosage form of cosmetics. However, general small molecule emulsifiers may cause problems such as skin irritation and stickiness.
In recent years, various emulsification techniques using polymer emulsifiers have been proposed in order to solve such problems.

Patent Document 1 discloses an emulsified composition using hydroxyethyl cellulose as an emulsifier.
Further, Patent Document 2 discloses an emulsified composition using an alkyl-modified carboxyvinyl polymer as an emulsifier.

Japanese Unexamined Patent Publication No. 2011-231409 Japanese Unexamined Patent Publication No. 09-019631

The high molecular weight emulsifier as described above has advantages such as less irritation to the skin and less stickiness when contained in a low concentration, but is inferior in emulsifying power as compared with the conventional low molecular weight emulsifier. .. Therefore, in order to ensure the stability of the emulsified state, it is necessary to add a high molecular weight emulsifier in the emulsified composition to increase the viscosity, and as a result, there is a problem of stickiness.

In view of such a situation, it is an object of the present invention to provide a novel emulsified composition emulsified with a polymer emulsifier, which has excellent emulsification stability and less stickiness.

The present invention that solves the above problems is an emulsified composition characterized in that fine particles made of a polyvinyl-based polymer satisfying the following conditions (A) and (B) are adsorbed on the emulsified interface.
(A) Fine particles are formed when dispersed in water.
(B) The viscosity of the aqueous solution containing the polyvinyl polymer at a concentration of 0.5% by mass at 25 ° C. and 1 atm is 3000 mPa · S or less.

In the preferred embodiment of the present invention, the polyvinyl-based polymer satisfies the following condition (C).
(C) When an aqueous solution having a concentration of 0.1% by mass to 1.0% by mass is used, a concentration-dependent thickening effect is not exhibited.
According to the polyvinyl-based polymer having such a viscosity characteristic, it is possible to provide an emulsified composition which is less sticky.

In a preferred embodiment of the invention, the polyvinyl polymer has a hydrophobic side chain.
According to the polyvinyl-based polymer having a hydrophobic side chain, it is possible to provide an emulsified composition having more excellent stability.

In a preferred embodiment of the invention, the hydrophobic side chain is a saturated or unsaturated hydrocarbon chain which may have a branched chain and / or a cyclic structure.
The emulsified composition in which the polyvinyl-based polymer having a hydrocarbon chain is adsorbed on the emulsified interface is more excellent in emulsification stability.

In a preferred embodiment of the present invention, the hydrophobic side chain is a hydrocarbon group or an acyl group having 6 to 30 carbon atoms.
According to the polyvinyl-based polymer having such a hydrophobic side chain, it is possible to provide an emulsified composition having more excellent emulsification stability.

In a preferred embodiment of the present invention, the polyvinyl polymer does not have an ionizing group.
The emulsified composition in which a polyvinyl-based polymer having no ionizing group is adsorbed on the emulsified interface is not sticky but has excellent emulsification stability.

In a preferred embodiment of the present invention, the polyvinyl-based polymer has one or more configurations derived from the vinyl-based monomers represented by the following general formulas (I), (II) or (III). Includes units.

（一般式（Ｉ）において、Ａは−Ｏ−又は−ＣＯＯ−を表し、Ｒ^１は水素原子または炭素数１〜３のアルキル基を表し、Ｒ^２は炭素数６〜３０の炭化水素基を表す。） General formula (I)

(In the general formula (I), A represents -O- or -COO-, R ¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ² represents a hydrocarbon group having 6 to 30 carbon atoms. show.)

（一般式（ＩＩ）において、Ａは−Ｏ−又は−ＣＯＯ−を表し、Ｒ^３は水素原子または炭素数１〜３のアルキル基を表し、Ｒ^４，Ｒ^５は同一でも異なっていてもよく、炭素数６〜２２のアシル基を表す。Ｘは三価のアルコールからＯＨ基が脱離した基を表す。） General formula (II)

(In the general formula (II), A represents -O- or -COO-, R ³ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ⁴ and R ⁵ may be the same or different. , Represents an acyl group having 6 to 22 carbon atoms. X represents a group in which an OH group is desorbed from a trivalent alcohol.)

（一般式（ＩＩＩ）において、Ａは−Ｏ−又は−ＣＯＯ−を表し、Ｒ^６は水素原子または炭素数１〜３のアルキル基を表し、Ｒ^７、Ｒ^８、Ｒ^９は同一でも異なっていてもよく、炭素数６〜２２のアシル基を表す。Ｙは四価アルコールからＯＨ基が脱離した基を表す。） General formula (III)

(In the general formula (III), A represents -O- or -COO-, R ⁶ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ⁷ , R ⁸ and R ⁹ are the same but different. It may represent an acyl group having 6 to 22 carbon atoms. Y represents a group in which an OH group is desorbed from a tetravalent alcohol.)

In a preferred embodiment of the present invention, the polyvinyl-based polymer is a polymerizable carboxylic acid, a vinyl-based monomer represented by the following general formula (VIII), and a vinyl-based monomer represented by the following general formula (IX). One or more derived from a vinyl-based monomer selected from the vinyl-based monomer represented by the following general formula (X) or the vinyl-based monomer represented by the following general formula (XI). Includes building blocks of.

（一般式（ＶＩＩＩ）中、Ｂは−Ｏ−又は−ＣＯＯ−を表し、Ｒ^１３は水素原子または炭素数１〜３のアルキル基を表し、Ｒ^１４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^１５は水素原子、炭素数６〜１０の芳香族炭化水素基、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６〜４０の整数を表す。） General formula (VIII)

(In the general formula (VIII), B represents -O- or -COO-, R ¹³ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ¹⁴ represents a carbon number which may have a hydroxyl group. It represents 2 to 4 alkylene groups, and R ¹⁵ represents a hydrogen atom, an aromatic hydrocarbon 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 an integer of 6 to 40.)

（一般式（ＩＸ）中、ＢはＢは−Ｏ−又は−ＣＯＯ−を表し、Ｒ^１６は水素原子またはメチル基をあらわす。） General formula (IX)

(In the general formula (IX), B represents -O- or -COO-, and R ¹⁶ represents a hydrogen atom or a methyl group.)

（一般式（Ｘ）中、Ｄは−ＣＯ−又は置換基が無いことを表し、Ｒ^１７は水素原子またはメチル基を、Ｇ−Ｏ−は還元糖の１位の水酸基より水素を除いた基を表す。ｍは２又は３を、ｌは１〜５の整数を表す。） General formula (X)

(In the general formula (X), D indicates that there is no -CO- or a substituent, R ¹⁷ is a hydrogen atom or a methyl group, and GO- is a group obtained by removing hydrogen from the hydroxyl group at the 1-position of the reducing sugar. M represents 2 or 3, and l represents an integer of 1 to 5.)

（一般式（ＸＩ）中Ｒ^１８は水素原子またはメチル基を、Ｒ^１９はアミノ酸残基、ポリアミン残基又はアミノアルコール残基を表す。Ｑは酸素原子又はＮＨで表される基を表す。） General formula (XI)

(In the general formula (XI), R ¹⁸ represents a hydrogen atom or a methyl group, R ¹⁹ represents an amino acid residue, a polyamine residue or an amino alcohol residue, and Q represents an oxygen atom or a group represented by NH.)

The present invention also relates to the above-mentioned method for producing an emulsified composition. That is, the production method of the present invention comprises a step of dispersing the polyvinyl-based polymer in an aqueous phase to form fine particles made of the polyvinyl-based polymer, and an oil phase component in the aqueous phase in which the fine particles are dispersed. It is characterized by including a step of adding, stirring and mixing.
According to the production method of the present invention, an emulsified composition having excellent emulsion stability can be produced.

The present invention also relates to a polymer emulsifier composed of a polyvinyl polymer that adsorbs to the emulsified interface in the form of fine particles, which satisfy the following conditions (A) and (B).
(A) Fine particles are formed when dispersed in water.
(B) The viscosity of the aqueous solution containing the polyvinyl polymer at a concentration of 0.5% by mass at 25 ° C. and 1 atm is 3000 mPa · S or less.
According to the fine particle-forming polyvinyl-based polymer emulsifier, it is possible to provide an emulsified composition having excellent emulsification stability.

According to the present invention, it is possible to provide an emulsified composition emulsified by a polymer emulsifier, which is less sticky but has excellent emulsification stability.

The electron microscope image of the emulsification interface of the oil droplet dispersed in the emulsification composition of an Example is shown.

In the present invention, fine particles (hereinafter, also referred to as polyvinyl-based polymer fine particles) composed of a polyvinyl-based polymer (hereinafter, also referred to as fine particle-forming polyvinyl-based polymer) satisfying the conditions of (A) and (B) described later are emulsified interfaces. It is an emulsified composition adsorbed on.
The average particle size of the polyvinyl polymer fine particles adsorbed on the emulsified interface is not particularly limited, but is preferably 1 nm to 1000 nm, more preferably 5 to 500 nm, still more preferably 10 to 200 nm, still more preferably 15 to. It is 100 nm, more preferably 15 to 50 nm, still more preferably 20 to 30 nm.

The fine particle-forming polyvinyl-based polymer satisfies the conditions (A) and (B). Hereinafter, each condition will be described in detail.

(A) Fine particles are formed when dispersed in water.
Fine particle formation The polyvinyl-based polymer forms fine particles when dispersed in water. The average particle size of the fine particles is not particularly limited, but is preferably 1 nm to 1000 nm, more preferably 5 to 500 nm, still more preferably 10 to 200 nm, still more preferably 15 to 100 nm, still more preferably 15 to 50 nm, still more preferably. It is 20 to 30 nm.

The average particle size of the fine particles when dispersed in water can be measured by using a dynamic light scattering measurement method based on Zetasizer Nano-Z ZEN3600 and Malvern (laser Doppler method).

Further, the average particle size of the fine particles when dispersed in water can be estimated to be the average particle size of the polymer fine particles in a state of being adsorbed on the emulsified interface.

(B) The viscosity of the aqueous solution containing the polyvinyl polymer at a concentration of 0.5% by mass at 25 ° C. and 1 atm is 3000 mPa · S or less.

The viscosity of the aqueous solution containing the fine particle-forming polyvinyl polymer at a concentration of 0.5% by mass is more preferably 2500 mPa · S or less, still more preferably 2000 mPa · S or less at 25 ° C. and 1 atm.

Further, it is preferable that the fine particle-forming polyvinyl-based polymer satisfies the following condition (C).
(C) The fine particle-forming polyvinyl-based polymer does not show a concentration-dependent thickening effect when made into an aqueous solution having a concentration of 0.1% by mass to 1.0% by mass.

In particular, a fine particle-forming polyvinyl-based polymer having a viscosity of an aqueous solution at 25 ° C. and 1 atm at 25 ° C. and 1 atm of 3000 mPa · S or less, more preferably 2500 mPa · S or less, and further preferably 2000 mPa · S or less is used in the above concentration range. Is preferable.

An emulsified composition containing a fine particle-forming polyvinyl-based polymer having such a viscosity characteristic is less sticky.
The viscosity can be measured at 25 ° C. and 1 atm using a conventional method (for example, B-type viscometer (DIGITAL VISMETRON VDA: manufactured by Shibaura System Co., Ltd.)).

The polyvinyl-based polymer refers to a polymer having the following basic structure 2 obtained by polymerizing a vinyl-based monomer having the following basic structure 1.

（ａ〜ｄの置換基は特に限定されない）

(Substituents a to d are not particularly limited)

The fine particle-forming polyvinyl-based polymer may form fine particles adsorbed on the emulsified interface and satisfy the above conditions (A) and (B), and the structure of the main chain skeleton is not limited.
As the fine particle-forming polyvinyl-based polymer, a polyolefin-based polymer, a polyacrylic-based polymer, a polyacrylamide-based polymer, and a polystyrene-based polymer can be preferably exemplified. In particular, a polyacrylic polymer can be preferably exemplified as the fine particle-forming polyvinyl polymer.

The fine particle-forming polyvinyl-based polymer preferably has a hydrophobic side chain. Examples of the hydrophobic side chain include a hydrocarbon chain and a perfluoroalkyl chain, and a hydrocarbon chain can be preferably exemplified.

The lower limit of the number of carbon atoms in the hydrocarbon chain is not particularly limited, but is preferably 3 or more, more preferably 4 or more, still more preferably 5 or more, still more preferably 6 or more.
Further, the upper limit of the number of carbon atoms of the hydrocarbon chain is not particularly limited, but is preferably 50 or less, more preferably 40 or less, still more preferably 30 or less.
The hydrocarbon chain may be branched or linear.

The hydrocarbon chain may be saturated or unsaturated, but is preferably saturated.

More specifically, as the hydrocarbon chain, a branched hydrocarbon group having 13 to 30 carbon atoms and a hydrocarbon group having 6 to 12 carbon atoms having two or more branches can be exemplified.

Further, the hydrocarbon chain may have a ring structure, but it is more preferable that the hydrocarbon chain does not contain the ring structure.

More specifically, the hydrocarbon chain includes a branched hydrocarbon group having 13 to 30 carbon atoms and no ring structure, and a hydrocarbon group having 6 to 12 carbon atoms having two or more branches and having no ring structure. Can be exemplified.

Examples of the branched hydrocarbon group having 13 to 30 carbon atoms and not containing a ring structure include 1-methyldodecanyl group, 11-methyldodecanyl group, 3-ethylundecanyl group, 3-ethyl-4,5,6. -Trimethyloctyl group, 1-methyltridecanol group, 1-hexyloctyl group, 2-butyldecanyl group, 2-hexyloctyl group, 4-ethyl-1-isobutyloctyl group, 1-methylpentadecanol group, 2- Hexyldecanyl group, 2-octyldecanyl group, 2-hexyldodecanyl group, 16-methylheptadecanyl group, 9-methylheptadecanyl group, 7-methyl-2- (3-methylhexyl) decanyl group, Examples of 3,7,11,15-tetra-methylhexadecanyl group, 2-octyldodecanyl group, 2-decyltetradecanyl group, 2-dodecylhexadecanyl group and the like can be exemplified.

As the hydrocarbon group having 2 or more branches and having 2 or more branches and having no ring structure and having 6 to 12 carbon atoms, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, 1, 3-Dimethylbutyl group, 1,2,2-trimethylpropyl group, 1,1-dimethylpentanyl group, 1-isopropylbutyl group, 1-isopropyl-2-methylpropyl group, 1,1-diethylpropyl group, 1 -Ethyl-1-isopropylpropyl group, 2-ethyl-4-methylpentyl group, 1-propyl-2,2-dimethylpropyl group, 1,1,2-trimethyl-pentyl group, 1-isopropyl-3-methylbutyl group , 1,2-dimethyl-1-ethylbutyl group, 1,3-dimethyl-1-ethylbutyl group, 1-ethyl-1-isopropyl-propyl group, 1,1-dimethylhexyl group, 1-methyl-1-ethylpentyl Group, 1-methyl-1-propylbutyl group, 1,4-dimethylhexyl group, 1-ethyl-3-methylpentyl group, 1,5-dimethylhexyl group, 1-ethyl-6-methylheptyl group, 1, 1,3,3-Tetramethylbutyl group, 1,2-dimethyl-1-isopropylpropyl group, 3-methyl-1- (2,2-dimethylethyl) butyl group, 1-isopropylhexyl group, 3.5. 5-trimethylhexyl group, 2-isopropyl-5-methylhexyl group, 1,5-dimethyl-1-ethylhexyl group, 3,7-dimethyloctyl group, 2,4,5-trimethylheptyl group, 2,4,6 -Trimethylheptyl group, 3,5-dimethyl-1- (2,2-dimethylethyl) hexyl group and the like can be exemplified.

Further, as described above, a hydrocarbon chain can be preferably exemplified as a hydrophobic side chain, but a polyvinyl-based polymer containing a hydrocarbon chain in the form of an acyl group is also preferable.

The lower limit of the number of carbon atoms of the acyl group is not particularly limited, but is preferably 3 or more, more preferably 4 or more, still more preferably 5 or more, still more preferably 6 or more.
The upper limit of the number of carbon atoms of the acyl group is also not particularly limited, but is preferably 50 or less, more preferably 40 or less, still more preferably 30 or less, still more preferably 22 or less.

The acyl group may be linear or branched.

The acyl group may contain a cyclic structure, but may also have a cyclic structure.

Examples of the branched acyl group having 6 to 22 carbon atoms that do not contain a ring structure include 2-methylpentanoyl group, 3-methylpentanoyl group, 4-methylpentanoyl group, 2-ethylbutanoyl group, and 2-. Ethylbutanoyl group, 2,2-dimethylbutanoyl group, 3,3-dimethylbutanoyl group, 2-methylhexanoyl group, 4-methylhexanoyl group, 5-methylhexanoyl group, 2,2-dimethylpenta Noyl group, 4,4-dimethylpentanoyl group, 2-methylheptanoyl group, 2-ethylhexyl group, 2-propylpentanoyl group, 2,2-dimethylhexanoyl group, 2,2,3-trimethylpentanoyl group , 2-Methyloctanoyl group, 3,3,5-trimethylhexanoyl group, 2-methylnonanoyl group, 4-methylnonanoyl group, 8-methylnonanoyl group, 4-ethyloctanoyl group, 2-ethyloctanoyl group, 2- Butylhexanoyl group, 2-tert-butylhexanoyl group, 2,2-diethylhexanoyl group, 2,2-dimethyloctanoyl group, 3,7-dimethyloctanoyl group, neodecanoyl group, 7-methyldecanoyl group , 2-Methyl-2-ethyloctanoyl group, 2-methylundecanoyl group, 10-methylundecanoyl group, 2,2dimethyldecanoyl group, 2-ethyldecanoyl group, 2-butyloctanoyl group, Diethyloctanoyl group, 2-tert-butyl-2,2,4-trimethylpentanoyl group, 10-methyldodecanoyl group, 3-methyldodecanoyl group, 4-methyldodecanoyl group, 11-methyldodecanoyl group, 10-Ethylundecanoyl group, 12-methyltridecanoyl group, 2-butyldecanoyl group, 2-hexyloctanoyl group, 2-butyl-2-ethyloctanoyl group, 12-methyltetradecanoyl group, 14 -Methylpentadecanoyl group, 2-butyldodecanoyl group, 2-hexyldecanoyl group, 16-methylheptadecanoyl group, 2,2-dimethylhexanoyl group, 2-butylhexadecanoyl group, 2-hexyldodeca Noyl group, 2,4,10,14-tetramethylpentanoyl group, 18-methylnonadecanoyl group, 3,7,11,15-tetra-methylhexadecanoyl group, 19-methyleicosanoyl group, etc. It can be exemplified.

Further, in a preferred embodiment, as the hydrophobic side chain, an acyl group having 10 to 22 carbon atoms having a branch, or an acyl group having 6 to 9 carbon atoms having two or more branches can be exemplified.

It is preferable that the acyl group having 10 to 22 carbon atoms having a branch or the acyl group having 6 to 9 carbon atoms having two or more branches does not contain a cyclic structure.

Examples of the branched acyl group having 10 to 22 carbon atoms that do not contain a ring structure include a 2-methylnonanoyl group, a 4-methylnonanoyl group, an 8-methylnonanoyl group, a 4-ethyloctanoyl group, and a 2-ethyloctanoyl group, 2 -Butylhexanoyl group, 2-tert-butylhexanoyl group, 2,2-diethylhexanoyl group), 2,2-dimethyloctanoyl group, 3,7-dimethyloctanoyl group, neodecanoyl group), 7-methyl Decanoyl group, 2-methyl-2-ethyloctanoyl group, 2-methylundecanoyl group, 10-methylundecanoyl group, 2,2dimethyldecanoyl group, 2-ethyldecanoyl group, 2-butylocta Noyl group, diethyloctanoyl group, 2-tert-butyl-2,2,4-trimethylpentanoyl group, 10-methyldodecanoyl group, 3-methyldodecanoyl group, 4-methyldodecanoyl group, 11-methyldodeca Noyl group, 10-ethylundecanoyl group, 12-methyltridecanoyl group, 2-butyldecanoyl group, 2-hexyloctanoyl group, 2-butyl-2-ethyloctanoyl group, 12-methyltetradecanoyl Group, 14-methylpentadecanoyl group, 2-butyldodecanoyl group, 2-hexyldecanoyl group, 16-methylheptadecanoyl group, 2,2-dimethylhexanoyl group, 2-butylhexadecanoyl group, 2 -Hexyldodecanoyl group, 2,4,10,14-tetramethylpentanoyl group, 18-methylnonadecanoyyl group, 3,7,11,15-tetra-methylhexadecanoyl group, 19-methyleicosanoyl The group and the like can be exemplified.

The acyl group having two or more branches and having 6 to 9 carbon atoms, which does not contain a ring structure, includes a 2,2-dimethylbutanoyl group, a 3,3-dimethylbutanoyl group, and a 2,2-dimethylpentanoyl group. , 4,4-dimethylpentanoyl group, 2,2-dimethylhexanoyl group, 2,2,3-trimethylpentanoyl group, 3,5,5-trimethylhexanoyl group and the like can be exemplified.

As the fine particle-forming polyvinyl-based polymer, one or more structural units derived from the vinyl-based monomers represented by the following general formulas (I), (II) or (III) (hereinafter, simply referred to as simple). , "Constituent unit I" and the like) can be preferably exemplified.

General formula (I)

In the general formula (I), A represents -O- or -COO-, R ¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ² represents a hydrocarbon group having 6 to 30 carbon atoms. show.

Here, ^{examples of the alkyl group represented by R 1} include a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group and the like. In the present invention, R ¹ is preferably a hydrogen atom or a methyl group.

R ² may be branched or linear.
R ² is more specifically may be exemplified hydrocarbon groups having 6 to 12 carbon atoms having a branched hydrocarbon group, and two or more branches of 13 to 30 carbon atoms.

R ² may have a ring structure, but it is more preferable that it does not contain a ring structure.

Hydrocarbon group R ² may be saturated or unsaturated, but is preferably saturated.

As R ² does not include a branched hydrocarbon group, or a ring structure does not contain a ring structure 13 to 30 carbon atoms, hydrocarbon group having 6 to 12 carbon atoms having two or more branches are preferred.

Examples of the branched hydrocarbon group having 13 to 30 carbon atoms and not containing a ring structure include 1-methyldodecanyl group, 11-methyldodecanyl group, 3-ethylundecanyl group, 3-ethyl-4,5,6. -Trimethyloctyl group, 1-methyltridecanol group, 1-hexyloctyl group, 2-butyldecanyl group, 2-hexyloctyl group, 4-ethyl-1-isobutyloctyl group, 1-methylpentadecanol group, 2- Hexyldecanyl group, 2-octyldecanyl group, 2-hexyldodecanyl group, 16-methylheptadecanyl group, 9-methylheptadecanyl group, 7-methyl-2- (3-methylhexyl) decanyl group, Examples of 3,7,11,15-tetra-methylhexadecanyl group, 2-octyldodecanyl group, 2-decyltetradecanyl group, 2-dodecylhexadecanyl group and the like can be exemplified.

As the hydrocarbon group having 2 or more branches and having 2 or more branches and having no ring structure and having 6 to 12 carbon atoms, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, 1, 3-Dimethylbutyl group, 1,2,2-trimethylpropyl group, 1,1-dimethylpentanyl group, 1-isopropylbutyl group, 1-isopropyl-2-methylpropyl group, 1,1-diethylpropyl group, 1 -Ethyl-1-isopropylpropyl group, 2-ethyl-4-methylpentyl group, 1-propyl-2,2-dimethylpropyl group, 1,1,2-trimethyl-pentyl group, 1-isopropyl-3-methylbutyl group , 1,2-dimethyl-1-ethylbutyl group, 1,3-dimethyl-1-ethylbutyl group, 1-ethyl-1-isopropyl-propyl group, 1,1-dimethylhexyl group, 1-methyl-1-ethylpentyl Group, 1-methyl-1-propylbutyl group, 1,4-dimethylhexyl group, 1-ethyl-3-methylpentyl group, 1,5-dimethylhexyl group, 1-ethyl-6-methylheptyl group, 1, 1,3,3-Tetramethylbutyl group, 1,2-dimethyl-1-isopropylpropyl group, 3-methyl-1- (2,2-dimethylethyl) butyl group, 1-isopropylhexyl group, 3.5. 5-trimethylhexyl group, 2-isopropyl-5-methylhexyl group, 1,5-dimethyl-1-ethylhexyl group, 3,7-dimethyloctyl group, 2,4,5-trimethylheptyl group, 2,4,6 -Trimethylheptyl group, 3,5-dimethyl-1- (2,2-dimethylethyl) hexyl group and the like can be exemplified.

General formula (II)

General formula (III)

In the general formula (II) and (III), A represents -O- or ^{-COO-, R 3,} R ⁶ represents a hydrogen atom or an alkyl group having 1 to 3 carbon ^atoms, R ^{4, R} 5, R ⁷ , R ⁸ and R ⁹ may be the same or different, and represent an acyl group having 6 to 22 carbon atoms. X represents a group in which an OH group is eliminated from a trihydric alcohol. Y represents a group in which the OH group is eliminated from the tetrahydric alcohol.

Here, ^{examples of the alkyl group represented by R 3} and R ⁶ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group and the like. In the present invention, R ³ and R ⁶ are preferably hydrogen atoms or methyl groups, and particularly preferably methyl groups.

The acyl groups of the acyl groups of the general formulas (II) and (III) R ⁴ , R ⁵ , R ⁷ , R ⁸ and R ⁹ have 12 to 22, more preferably 14 to 20, and even more preferably 16 to 20. ..

^R 4 in the general formula (II) and ^{(III), R 5, R} 7, an acyl group of R 8, ^{R 9} may be linear be branched, but are preferably branched Is.

^{When R 4} , R ⁵ , R ⁷ , R ⁸ , and R ^{9 of} the general formulas (II) and (III) are branched-chain acyl groups, the number of carbon atoms in the main chain is preferably 9 to 21, It is more preferably 12 to 20, still more preferably 16 to 18.

^{When R 4} , R ⁵ , R ⁷ , R ⁸ , and R ^{9 of} the general formulas (II) and (III) are branched-chain acyl groups, the number of branches is preferably 1-3, more preferably. 1 or 2, more preferably 1.

^{Further, when R 4} , R ⁵ , R ⁷ , R ⁸ and R ^{9 of} the general formulas (II) and (III) are branched-chain acyl groups, the position number of the carbon of the main chain to which the branched chain is bonded. Is preferable. Specifically, the branched chain is bonded from the carbon at the end of the main chain to preferably the 1st to 3rd carbons, more preferably the 1st or 2nd carbon, and further preferably the 1st carbon. Is preferable.

The acyl groups of R ⁴ , R ⁵ , R ⁷ , R ⁸ and R ⁹ may contain a cyclic structure, but preferably do not contain a cyclic structure.

The hydrocarbon chain moieties of the acyl groups of R ⁴ , R ⁵ , R ⁷ , R ⁸ and R ⁹ may be saturated or unsaturated, but are preferably saturated.

Further, as the acyl group having a branch and having 6 to 22 carbon atoms, which does not include the ring structure represented by ^{R 4} , R ⁵ , R ⁷ , R ⁸ and R ^{9, 2-methylpentanoyl group and 3-methyl} Pentanoyl group, 4-methylpentanoyl group, 2-ethylbutanoyl group, 2-ethylbutanoyl group, 2,2-dimethylbutanoyl group, 3,3-dimethylbutanoyl group, 2-methylhexanoyl group, 4-Methylhexanoyl group, 5-methylhexanoyl group, 2,2-dimethylpentanoyl group, 4,4-dimethylpentanoyl group, 2-methylheptanoyl group, 2-ethylhexyl group, 2-propylpentanoyl group , 2,2-dimethylhexanoyl group, 2,2,3-trimethylpentanoyl group, 2-methyloctanoyl group, 3,3,5-trimethylhexanoyl group, 2-methylnonanoyl group, 4-methylnonanoyl group, 8 -Methylnonanoyl group, 4-ethyloctanoyl group, 2-ethyloctanoyl group, 2-butylhexanoyl group, 2-tert-butylhexanoyl group, 2,2-diethylhexanoyl group, 2,2-dimethyloctanoyl Group, 3,7-dimethyloctanoyl group, neodecanoyl group, 7-methyldecanoyl group, 2-methyl-2-ethyloctanoyl group, 2-methylundecanoyl group, 10-methylundecanoyl group, 2, 2Dimethyldecanoyl group, 2-ethyldecanoyl group, 2-butyloctanoyl group, diethyloctanoyl group, 2-tert-butyl-2,2,4-trimethylpentanoyl group, 10-methyldodecanoyl group, 3 -Methyldodecanoyl group, 4-methyldodecanoyl group, 11-methyldodecanoyl group, 10-ethylundecanoyl group, 12-methyltridecanoyl group, 2-butyldecanoyl group, 2-hexyloctanoyl group, 2-butyl-2-ethyloctanoyl group, 12-methyltetradecanoyl group, 14-methylpentadecanoyl group, 2-butyldodecanoyl group, 2-hexyldecanoyl group, 16-methylheptadecanoyl group, 2 , 2-Dimethylhexanoyl group, 2-butylhexadecanoyl group, 2-hexyldodecanoyl group, 2,4,10,14-tetramethylpentanoyl group, 18-methylnonadecanoyl group, 3,7,11 , 15-Tetra-methylhexadecanoyl group, 19-methyleicosanoyl group and the like can be exemplified.

Also in a preferred embodiment of the present invention, in the general formula (II) and ^{(III), R 4, R} 5, R 7, R 8, R 9 may be the same or different, it has a branched carbon It is an acyl group having a number of 10 to 22 or an acyl group having 6 to 9 carbon atoms having two or more branches.
In this case, the annular structure may be included, but it is preferable not to include the annular structure.

As such an acyl group having no ring structure and having a branch and having 10 to 22 carbon atoms represented by ^{R 4} , R ⁵ , R ⁷ , R ⁸ and R ⁹ in such a preferred embodiment, 2-. Methylnonanoyl group, 4-methylnonanoyl group, 8-methylnonanoyl group, 4-ethyloctanoyl group, 2-ethyloctanoyl group, 2-butylhexanoyl group, 2-tert-butylhexanoyl group, 2,2-diethylhexanoyl Group), 2,2-dimethyloctanoyl group, 3,7-dimethyloctanoyl group, neodecanoyl group), 7-methyldecanoyl group, 2-methyl-2-ethyloctanoyl group, 2-methylundecanoyl group 10,-Methylundecanoyl group, 2,2dimethyldecanoyl group, 2-ethyldecanoyl group, 2-butyloctanoyl group, diethyloctanoyl group, 2-tert-butyl-2,2,4-trimethylpenta Noyl group, 10-methyldodecanoyl group, 3-methyldodecanoyl group, 4-methyldodecanoyl group, 11-methyldodecanoyl group, 10-ethylundecanoyl group, 12-methyltridecanoyl group, 2-butyl Decanoyl group, 2-hexyl octanoyl group, 2-butyl-2-ethyl octanoyl group, 12-methyltetradecanoyl group, 14-methylpentadecanoyl group, 2-butyldodecanoyl group, 2-hexyldecanoyl Group, 16-methylheptadecanoyl group, 2,2-dimethylhexanoyl group, 2-butylhexadecanoyl group, 2-hexyldodecanoyl group, 2,4,10,14-tetramethylpentanoyl group, 18- Examples thereof include a methylnonadecanoyl group, a 3,7,11,15-tetra-methylhexadecanoyl group, a 19-methyleicosanoyl group and the like.

Further, as the acyl group having two or more branches and having no ring structure and having two or more branches represented by ^{R 4} , R ⁵ , R ⁷ , R ⁸ , and R ⁹ in the preferred embodiment, the acyl group has 6 to 9 carbon atoms. 2,2-dimethylbutanoyl group, 3,3-dimethylbutanoyl group, 2,2-dimethylpentanoyl group, 4,4-dimethylpentanoyl group, 2,2-dimethylhexanoyl group, 2,2,3 -Trimethylpentanoyl group, 3,5,5-trimethylhexanoyl group and the like can be exemplified.

The group derived from the trihydric alcohol represented by X in the general formula (II) is not particularly limited as long as it is a group in which the OH group is removed from the trihydric alcohol, but is not particularly limited, but glycerin, trimethylolpropane, and trimethylolethane. A group in which the OH group is removed from the trihydric alcohol selected from the group consisting of the above can be preferably exemplified.

The group derived from the tetrahydric alcohol represented by Y in the general formula (III) is not particularly limited as long as it is a group in which the OH group is removed from the tetrahydric alcohol, but diglycerin, pentaerythritol, and erythritol are not particularly limited. , A group in which the OH group is removed from the tetrahydric alcohol selected from the group consisting of D-threitol and L-threitol can be preferably exemplified.

In the present invention, it is particularly preferable to use the polyvinyl-based polymer containing the constituent unit II as the fine particle-forming polyvinyl-based polymer.

The fine particle-forming polyvinyl-based polymer preferably has a hydrophilic side chain.
The hydrophilic side chain, carboxyl group, hydroxy group, or a side chain having the same or hydrophilic functional group such as an amino _{group, -O -, - NH -,} - SO 2 -, - bonds such as CO-NH- Can be exemplified by a polymerizable side chain having the above.

Examples of the hydrophilic side chain include substituents represented by the general formulas (IV) to (VII) shown below.

（一般式（ＩＶ）中Ｒ^１０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^１１は水素原子、炭素数６〜１０の芳香族炭化水素基、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６〜４０の整数を表す。） General formula (IV)

(In the general formula (IV), R ¹⁰ represents an alkylene group having 2 to 4 carbon atoms which may have a hydroxyl group, and R ¹¹ is a hydrogen atom, an aromatic hydrocarbon group having 6 to 10 carbon atoms, and 1 carbon atom. Represents an aliphatic hydrocarbon group of ~ 14 or an acyl group having 1 to 12 carbon atoms. N represents an integer of 6 to 40).

Examples of the alkylene group represented by R ¹⁰ include an ethylene group, a propylene group, an isopropylene group, a 2-hydroxypropylene group, a 1-hydroxy-2-methylethylene group, a 2-hydroxy-1-methylethylene group and the like. By way of examples, among these, an ethylene group or a propylene group is preferable, and an ethylene group is more preferable.

Also, among the groups represented by R ^11, the aromatic group having 6 to 10 carbon atoms, a phenyl group, a benzyl group, methylphenyl group, can be exemplified ethylphenyl group and the like; aliphatic having 1 to 14 carbon atoms Preferable 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, a lauryl group and the like; As the acyl group of ~ 12, a formyl group, an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a valeryl group, a lauroyl group and the like can be preferably exemplified. Of these, the ^{group represented by R 11} is preferably an aliphatic hydrocarbon group having 1 to 14 carbon atoms, and more preferably an alkyl group having 1 to 12 carbon atoms.

Further, n in the general formula (IV) is in the numerical range of 6 to 40.

General formula (V)

（一般式（ＶＩ）中Ｇ−Ｏ−は還元糖の１位の水酸基より水素を除いた基を表す。ｍは２又は３を、ｌは１〜５の整数を表す。） General formula (VI)

(GO- in the general formula (VI) represents a group obtained by removing hydrogen from the hydroxyl group at the 1-position of the reducing sugar. M represents 2 or 3, and l represents an integer of 1 to 5.)

Among the substituents represented by the general formula (VI), the reducing sugars of the group obtained by removing hydrogen from the hydroxyl group at the 1-position of the reducing sugar represented by GO- are specifically glucose, mannose and galactose. , One or more selected from the group consisting of monosaccharides such as arabinose, xylose and ribose, disaccharides such as maltose, lactose and cellobiose, trisaccharides such as maltotriose and oligosaccharides such as maltooligosaccharide. However, among them, one or more selected from the group consisting of glucose, galactose, arabinose, xylose, ribose, maltose, and lactose cellobiose is preferable, and glucose is particularly preferable.

（一般式（ＶＩＩ）中Ｒ^１２はアミノ酸残基、ポリアミン残基又はアミノアルコール残基を表す。Ｑは酸素原子又はＮＨで表される基を表す。） General formula (VII)

^{(R 12 in the} general formula (VII) represents an amino acid residue, a polyamine residue or an amino alcohol residue. Q represents a group represented by an oxygen atom or NH.)

In the substituent of the general formula (VII), ^{the amino acid of the amino acid residue represented by R 12} is not particularly limited as long as it is an commonly known amino acid, and specifically, glycine, alanine, glutamine, and the like. Examples thereof include lysine and arginine. Of these, the lysine residue is particularly preferable because the obtained fine particle-forming polyvinyl-based polymer has an excellent effect of restoring the skin barrier.

Further, the ^{polyamine in the polyamine residue represented by R 12} means an amine having two or more amino groups which may be substituted with an alkyl group in the same molecule, and specifically, diamine, triamine, and the like. Examples thereof are tetraamines or amines in which the hydrogen atom of these amino groups is substituted with an alkyl group. Among these, diamine is preferable because the skin external preparation containing the obtained fine particle-forming polyvinyl polymer is particularly excellent in usability, and as a particularly preferable specific example, it is easy to obtain a raw material for synthesis. Examples thereof include ethylenediamine, 1,4-diamino-n-butane, 1,6-diamino-n-hexane and the like.

Further, the ^{amino alcohol in the amino alcohol residue represented by R 12} means a compound having an amino group and an alcoholic hydroxyl group which may be substituted with an alkyl group in the same molecule. The amino alcohol is not particularly limited as long as it is generally known, and specific examples thereof include ethanolamine and triethylaminoethanol.

The salt of the substituent represented by the general formula (VII) is not particularly limited, but specifically, a sodium salt, a potassium salt, an ammonium salt, an amine salt, etc., in which the acid moiety is neutralized with a base, and the like. , Hydrochloride, sulfate, nitrate, phosphate, citrate, oxalate, carbonate and the like in which the amino group portion is neutralized with an acid can be exemplified.

Specific examples of the substituent represented by the general formula (VII) and the salt thereof include a substituent having the following structure and a salt thereof.

As described above, the fine particle-forming polyvinyl polymer may form fine particles adsorbed on the emulsified interface and satisfy the above conditions (A) and (B), and the main clavicle to which the above-mentioned hydrophilic side chains are bonded may be satisfied. The structure of the case is not limited.

The fine particle-forming polyvinyl-based polymer may have a structural unit derived from a polymerizable carboxylic acid or a salt thereof. Specific examples of the polymerizable carboxylic acid or a salt thereof include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid and its sodium salt, potassium salt, ammonium salt, and amine salt. Among these, acrylic acid, methacrylic acid and salts thereof are particularly preferable because of their high polymerizable property. When a structural unit derived from a salt of a polymerizable carboxylic acid is introduced into a fine particle-forming polyvinyl-based polymer, the polymerizable carboxylic acid may be previously made into a salt and a polymerization reaction may be carried out, or the polymerization reaction may be carried out. The structural unit derived from the carboxylic acid may be derived into a fine particle-forming polyvinyl-based polymer and then neutralized with a base to form a salt.

Further, as the fine particle-forming polyvinyl-based polymer, a polyvinyl-based polymer containing one or more structural units derived from vinyl-based monomers represented by the following general formulas (VIII) to (XI). Can be preferably exemplified.

General formula (VIII)

In the general formula (VIII), B represents -O- or -COO-, R ¹³ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ¹⁴ represents a carbon number which may have a hydroxyl group. It represents 2 to 4 alkylene groups, and R ¹⁵ represents a hydrogen atom, an aromatic hydrocarbon 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 an integer of 6 to 40.

In the general formula (VIII), B represents —O− or −COO−, but is particularly preferably −COO−. That is, it is preferably in the form of an acrylic monomer.

The alkyl group represented by R ¹³ in the general formula (VIII), a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group can be exemplified. In the present invention, R ¹³ is preferably a hydrogen atom or a methyl group.

The ^{alkylene group represented by R 14} includes an ethylene group, a propylene group, an isopropylene group, a 2-hydroxypropylene group, a 1-hydroxy-2-methylethylene group, a 2-hydroxy-1-methylethylene group and the like. By way of examples, among these, an ethylene group or a propylene group is preferable, and an ethylene group is more preferable.

Also, among the groups represented by R ^15, the aromatic group having 6 to 10 carbon atoms, a phenyl group, a benzyl group, methylphenyl group, can be exemplified ethylphenyl group and the like; aliphatic having 1 to 14 carbon atoms Preferable 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, a lauryl group and the like; As the acyl group of ~ 12, a formyl group, an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a valeryl group, a lauroyl group and the like can be preferably exemplified. Of these, preferable as the group represented by R ¹⁵ is an aliphatic hydrocarbon group having 1 to 14 carbon atoms, more preferably an alkyl group having 1 to 12 carbon atoms.

Further, n in the general formula (VIII) is in the numerical range of 6 to 40.

Among the monomers represented by the general formula (VIII), the monomers in which R ¹⁴ is a propylene group are specifically polypropylene glycol (9) monoacrylate, polypropylene glycol (13) monoacrylate, and polypropylene glycol (9) mono. Examples thereof include methacrylate, polypropylene glycol (13) monomethacrylate and the like. The numbers in parentheses represent n. Many of these polymers are commercially available. Specific examples of these commercially available products include the trade names “Blemmer” AP-400, AP-550, AP-800, PP-500, and PP-800 (all manufactured by NOF CORPORATION).

Among the monomers represented by the general formula ^(VIII), particularly as monomers ^{R 14} is ethylene group, polyethylene glycol (10) monoacrylate, polyethylene glycol (8) monomethacrylate, polyethylene glycol (23) mono Acrylic, polyethylene glycol (23) monomethacrylate, methoxypolyethylene glycol (9) acrylate, methoxypolyethylene glycol (9) methacrylate, methoxypolyethylene glycol (23) methacrylate, oleyloxypolyethylene glycol (18) methacrylate, lauroxypolyethylene glycol (18) Examples thereof include acrylate, lauroyloxypolyethylene glycol (10) methacrylate, stearoxypolyethylene glycol (30) monomethacrylate and the like.

The above-mentioned acrylic monomer can be obtained in high yield by an esterification reaction of the corresponding polyethylene glycol, polyethylene glycol monoether, or polyethylene glycol monoester with a chloride or anhydride of acrylic acid or methacrylic acid. Moreover, since there are already many commercially available products, it is possible to use such commercially available products. Specific examples of such commercial products include NOF Corporation, AE-400, PE-350, AME-400, PME-400, PME-1000, ALE-800, PSE-1300, etc. Co., Ltd.) and the like can be exemplified.

General formula (IX)

(In the general formula (IX), B represents -O- or -COO-, and R ¹⁶ represents a hydrogen atom or a methyl group.)

In the general formula (IX), B represents −O− or −COO−, but is particularly preferably −COO−. That is, it is preferably in the form of an acrylic monomer.

Specific examples of the acrylic monomer represented by the general formula (IX) include 2-acryloyloxyethyl phosphorylcholine (APC) and 2-methacryloyloxyethylphosphorylcholine (MPC). These monomers can be synthesized, for example, by the following methods described in Polymer Journal, Vol22, No. 5.
<Synthesis method>
2-bromoethylphosphoryl dichloride is reacted with 2-hydroxyethyl methacrylate or 2-hydroxyethyl acrylate to form 2-methacryloyloxyethyl-2'-bromoethyl phosphate or 2-acryloyloxyethyl-2'-bromoethyl phosphate. After that, these compounds and triethylamine are reacted in methanol.

（一般式（Ｘ）中、Ｄは−ＣＯ−又は置換基が無いことを表し、Ｒ^１７は水素原子またはメチル基を、Ｇ−Ｏ−は還元糖の１位の水酸基より水素を除いた基を表す。ｍは２又は３を、ｌは１〜５の整数を表す。） General formula (X)

(In the general formula (X), D indicates that there is no -CO- or a substituent, R ¹⁷ is a hydrogen atom or a methyl group, and GO- is a group obtained by removing hydrogen from the hydroxyl group at the 1-position of the reducing sugar. M represents 2 or 3, and l represents an integer of 1 to 5.)

In the general formula (X), D represents -CO- or no substituent, but is particularly preferably -CO-. That is, it is preferably in the form of an acrylic monomer.

In the hydrophilic monomer represented by the general formula (X), the reducing sugar of the group obtained by removing hydrogen from the hydroxyl group at the 1-position of the reducing sugar represented by GO- is specifically glucose, mannose, or the like. One or more selected from the group consisting of monosaccharides such as galactose, arabinose, xylose, and ribose, disaccharides such as maltose, lactose, and cellobiose, trisaccharides such as maltotriose, and oligosaccharides such as malto-oligosaccharides are exemplified. However, among them, one or more selected from the group consisting of glucose, galactose, arabinose, xylose, ribose, maltose, and lactose cellobiose is preferable, and glucose is particularly preferable. Further, as the monomer represented by the general formula (X), glucosyloxyethyl methacrylate (hereinafter abbreviated as GEMA) or glucosyloxyethyl acrylate (hereinafter abbreviated as GEA) is preferable.

（一般式（ＸＩ）中Ｒ^１８は水素原子またはメチル基を、Ｒ^１９はアミノ酸残基、ポリアミン残基又はアミノアルコール残基を表す。Ｑは酸素原子又はＮＨで表される基を表す。） General formula (XI)

(In the general formula (XI), R ¹⁸ represents a hydrogen atom or a methyl group, R ¹⁹ represents an amino acid residue, a polyamine residue or an amino alcohol residue, and Q represents an oxygen atom or a group represented by NH.)

In the general formula (XI), D represents -CO- or no substituent, but is particularly preferably -CO-. That is, it is preferably in the form of an acrylic monomer.

In the monomer of the general formula (XI), ^{the amino acid of the amino acid residue represented by R 19} is not particularly limited as long as it is an commonly known amino acid, and specifically, glycine, alanine, glutamine, and lysine. , Arginine and the like are exemplified. Of these, the lysine residue is particularly preferable because the obtained fine particle-forming polyvinyl-based polymer has an excellent effect of restoring the skin barrier.

Further, the polyamine and the in polyamine residue represented by R ^19, means an amine having two or more amino group which may be substituted with an alkyl group in the same molecule include, diamines, triamines, Examples thereof are tetraamines or amines in which the hydrogen atom of these amino groups is substituted with an alkyl group. Among these, diamine is preferable because the skin external preparation containing the obtained fine particle-forming polyvinyl polymer is particularly excellent in usability, and as a particularly preferable specific example, it is easy to obtain a raw material for synthesis. Examples thereof include ethylenediamine, 1,4-diamino-n-butane, 1,6-diamino-n-hexane and the like.

Further, the ^{amino alcohol in the amino alcohol residue represented by R 19} means a compound having an amino group and an alcoholic hydroxyl group which may be substituted with an alkyl group in the same molecule. The amino alcohol is not particularly limited as long as it is generally known, and specific examples thereof include ethanolamine and triethylaminoethanol.

The salt of the monomer represented by the general formula (XI) is not particularly limited, but specifically, a sodium salt, a potassium salt, an ammonium salt, an amine salt, etc., in which the acid moiety is neutralized with a base, etc. Further, examples thereof include hydrochlorides, sulfates, nitrates, phosphates, citrates, oxalates, carbonates, etc., in which the amino group portion is neutralized with an acid. When introducing a structural unit derived from a salt of a monomer represented by the general formula (XI) into a fine particle-forming polyvinyl-based polymer, the monomer represented by the general formula (XI) is preliminarily salted. A polymerization reaction may be carried out, or the structural unit derived from the monomer represented by the general formula (XI) is induced in the fine particle-forming polyvinyl-based polymer by the polymerization reaction, and then neutralized to form no salt. You may.

Specific examples of the monomer represented by the general formula (XI) and a salt thereof include a compound having the following structure and a salt thereof.

（反応式中Ｒ^１８は水素原子またはメチル基を、Ｒ^１９はアミノ酸残基、ポリアミン残基又はアミノアルコール残基を表す。Ｑは酸素原子又はＮＨで表される基を表す。） The monomer represented by the general formula (XI) can be synthesized, for example, by an esterification reaction or an amidation reaction using (meth) acrylic acid or (meth) acrylic acid chloride as shown below.

(In the reaction formula, R ¹⁸ represents a hydrogen atom or a methyl group, R ¹⁹ represents an amino acid residue, a polyamine residue or an amino alcohol residue. Q represents an oxygen atom or a group represented by NH.)

As described above, the fine particle-forming polyvinyl-based polymer preferably has a hydrophilic side chain, but more preferably does not have an ionizing group.
By not having an ionizing group, an emulsified composition that is not sticky can be obtained.

Generally, a highly hydrophobic surfactant is suitable for forming a water-in-oil emulsified composition, whereas a highly hydrophilic surfactant is suitable for forming an oil-in-water emulsified composition. Similarly, the fine particle-forming polyvinyl-based polymer in the present invention is suitable for forming a water-in-oil emulsified composition when the proportion of the hydrophobic constituent unit (the constituent unit having a hydrophobic side chain) is high. Further, when the proportion of the hydrophilic constituent unit (the constituent unit having a hydrophilic side chain) is high, it is suitable for forming an oil-in-water emulsified composition.
As described above, the emulsified form of the emulsified composition to be formed can be adjusted by appropriately adjusting the proportions and ratios of the hydrophobic constituent units and the hydrophilic constituent units.

In the present invention, the ratio of the hydrophobic constituent unit to all the constituent units in the fine particle-forming polyvinyl-based polymer is preferably 1 to 50% by mass, more preferably 20 to 50% by mass, and 30 to 40% by mass.
By setting the proportion of the hydrophobic constituent unit in the fine particle-forming polyvinyl-based polymer in the above range, it is possible to provide an oil-in-water emulsified composition with a further reduced stickiness.

In the present invention, the ratio of the hydrophilic constituent units to all the constituent units in the fine particle-forming polyvinyl-based polymer is preferably 50 to 99% by mass, more preferably 50 to 80% by mass, and 60 to 70% by mass. ..
By setting the proportion of the hydrophilic constituent unit in the fine particle-forming polyvinyl-based polymer in the above range, it is possible to provide an oil-in-water emulsified composition with a further reduced stickiness.

In the present invention, the mass ratio of the hydrophobic constituent unit to the hydrophilic constituent unit constituting the fine particle-forming polyvinyl-based polymer is preferably 10:90 to 50:50, more preferably 20:80 to 50:50. More preferably, it is 30:70 to 40:60.

The molar ratio of the hydrophobic constituent unit to the hydrophilic constituent unit constituting the fine particle-forming polyvinyl-based polymer is preferably 15:85 to 62:38, more preferably 29:71 to 62:38, and even more preferably. It is 41:59 to 52:48, more preferably 27:73 to 38:62, and even more preferably 44:56 to 49:51.
By setting the mass ratio and molar ratio of the hydrophobic constituent unit and the hydrophilic constituent unit in the fine particle-forming polyvinyl-based polymer in the above range, it is suitable for forming an oil-in-water emulsifying composition and has excellent emulsifying power. It can be a fine particle-forming polyvinyl-based polymer.

In the present invention, the average molecular weight of the fine particle-forming polyvinyl polymer is preferably 2000 to 11000, more preferably 20000 to 80000, more preferably 30,000 to 80,000, still more preferably 40,000 to 70,000, still more preferably 50,000 to 70,000. More preferably, it is 57,000 to 66,000.
Here, the average molecular weight means a polystyrene-equivalent weight average molecular weight measured by GPC.

The contents of the aqueous phase and the oil phase in the emulsified composition of the present invention can be appropriately adjusted by changing the ratio of the hydrophobic constituent unit and the hydrophilic constituent unit in the fine particle-forming polyvinyl-based polymer.

The content of the fine particle-forming polyvinyl-based polymer in the entire emulsified composition is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass.
By setting the content of the fine particle-forming polyvinyl-based polymer in the above range, the emulsification stability of the emulsified composition can be further improved.

The emulsified composition of the present invention preferably contains substantially no emulsifier other than the fine particle-forming polyvinyl-based polymer.
Here, "substantially free of emulsifiers other than the fine particle-forming polyvinyl polymer" means that the content of the emulsifier other than the fine particle-forming polyvinyl polymer is 0.3% or less, preferably 0.1% or less. , More preferably 0.1% or less, still more preferably 0.01% or less, still more preferably 0.001% or less. Further, it is particularly preferable that the emulsifier other than the fine particle-forming polyvinyl-based polymer is not contained.

Hereinafter, the content of the oil phase and the aqueous phase when a fine particle-forming polyvinyl-based polymer containing a hydrophobic constituent unit and a hydrophilic constituent unit is used at a ratio suitable for forming the above-mentioned oil-in-water emulsified composition. Etc. will be explained.
In this specification, it is assumed that the oil phase and the oil phase component, and the aqueous phase and the aqueous phase component do not include the fine particle-forming polyvinyl-based polymer of the present invention.

The content of the oil phase component in the emulsified composition of the present invention is preferably 0.01 to 80% by mass, more preferably 0.1 to 70% by mass.
By setting the content of the oil phase component in the above range, the emulsification stability of the emulsified composition can be improved.
The oil phase component is an oil agent and a lipophilic component, and refers to a component contained in the oil phase in the emulsified composition.

In the emulsified composition of the present invention, the mass ratio of the above-mentioned fine particle-forming polyvinyl-based polymer to the oil phase component is preferably 1: 100 to 1: 0.2, more preferably 1: 70 to 1: 0.3. be.
By setting the mass ratio of the fine particle-forming polyvinyl-based polymer to the oil phase component in the above range, the emulsification stability of the emulsified composition can be improved.

In the emulsified composition of the present invention, the mass ratio of the oil phase to the aqueous phase is preferably 0.1: 99.9 to 70:30, more preferably 1: 99 to 65 to 35.
By setting the mass ratio of the oil phase to the aqueous phase within the above range, a stable oil-in-water emulsified composition can be formed.

The components contained in the oil phase and the aqueous phase are not particularly limited.
Examples of the oil agent constituting the oil phase include liquid oils and fats, solid oils and fats, waxes, hydrocarbon oils, higher fatty acids, higher alcohols, synthetic ester oils, silicone oils and the like.

Liquid fats and oils include, for example, avocado oil, camellia oil, turtle oil, macadamia nut oil, corn oil, mink oil, olive oil, rapeseed oil, egg yolk oil, sesame oil, persic oil, wheat germ oil, southern ka oil, castor oil, and flaxseed oil. , Saflower oil, cottonseed oil, eno oil, meadowfoam oil, soybean oil, peanut oil, teaseed oil, kaya oil, rice bran oil, cinnamon oil, Japanese millet oil, jojoba oil, germ oil, triglycerin, glycerin trioctanoate, Examples thereof include glycerin triisopalmitate.

Solid fats and oils include coconut oil, palm oil, horse fat, hardened palm oil, palm oil, beef tallow, sheep fat, hardened beef tallow, palm kernel oil, pork fat, beef tallow, mokuro kernel oil, hardened oil, and beef tallow. , Mokuro, hardened castor oil and the like.

Examples of waxes include honey wax, candelilla wax, cotton wax, carnauba wax, bayberry wax, ibotarou, whale wax, monttan wax, nukarou, lanolin, capoc wax, lanolin acetate, liquid lanolin, sugar cane, lanolin fatty acid isopropyl, hexyl laurate, reduced lanolin, and jojo. Examples thereof include barrow, hard lanolin, serrac wax, POE lanolin alcohol ether, POE lanolin alcohol acetate, POE cholesterol ether, lanolin fatty acid polyethylene glycol, POE hydrogenated lanolin alcohol ether and the like.

Examples of the hydrocarbon oil include liquid paraffin, zokerite, pristane, paraffin, selecin, squalene, petrolatum, microcrystalline wax and the like.

Examples of higher fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, behenic (behenic acid) acid, 12-hydroxystearic acid, undecylenic acid, tollic acid and the like.

Examples of the higher alcohol include cetyl alcohol, stearyl alcohol, behenyl alcohol, batyl alcohol, myristyl alcohol, and cetostearyl alcohol.

Synthetic ester oils include isopropyl myristate, cetyl octanate, octyldodecyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate, decyl oleate, hexyldecyl dimethyloctanoate, cetyl lactate, myristyl lactate. , Lanorin acetate, Isocetyl stearate, Isocetyl isostearate, Sculose stearate, Sculose oleate, Cholesteryl 12-hydroxystearyl acid, Ethylene glycol di-2-ethylhexylate, Dipentaerythritol fatty acid ester, N-alkyl glycol monoisostearate, Neopentylglycol dicaprate, diisostearyl malate, glycerin di-2-heptylundecanoate, trimethylolpropane tri-2-ethylhexylate, trimethylolpropane tri-2-ethylhexylate, pentaneerythritol tetra-2-ethylhexylate, tri-2 -Glycerin ethylhexylate, Trimethylolpropane triisostearate, Cetyl2-ethylhexanoate, 2-Ethylhexyl palmitate, Glycerin trimyristate, Glyceride tri-2-heptylundecanoic acid, Methyl ester of castor oil fatty acid, Oleic acid oil, Cetostearyl alcohol, acetoglyceride, 2-heptyl undesyl palmitate, cetyl palmitate, diisobutyl adipate, N-lauroyl-L-glutamic acid-2-octyldodecyl ester, di-2-heptyl undesyl adipate, ethyl laurate , Di-2-ethylhexyl sebatate, 2-hexyldecyl myristate, 2-hexyldecyl palmitate, 2-hexyldecyl adipate, diisopropyl sebatate, 2-ethylhexyl succinate, ethyl acetate, butyl acetate, amyl acetate, quen Examples thereof include triethyl acid.

Examples of the silicone oil include chain polysiloxanes such as dimethylpolysiloxane, methylphenylpolysiloxane, and methylhydrogenpolysiloxane, and cyclic polysiloxanes such as decamethylpolysiloxane, dodecamethylpolysiloxane, and tetramethyltetrahydrogenpolysiloxane. Can be mentioned.

One kind or two or more kinds of oils can be used.

The emulsified composition of the present invention may contain an optional additive component usually blended in cosmetics as long as the effects of the present invention are not impaired. Examples of such additive components include moisturizers such as polyethylene glycol, glycerin, 1,3-butylene glycol, erythritol, sorbitol, xylitol and martitol; lower alcohols such as ethanol; butyl hydroxytoluene, tocopherol and phytin. Antioxidants; Antibacterial agents such as benzoic acid, salicylic acid, sorbic acid, paraoxybenzoic acid alkyl ester, hexachlorophen, etc .; paraaminobenzoic acid (hereinafter abbreviated as "PABA"), PABA monoglycerin ester, N, N-dipropoxy PABA ethyl ester , N, N-DiethoxyPABA ethyl ester, N, N-dimethyl PABA methyl ester, N, N-dimethyl PABA ethyl ester, N, N-dimethyl PABA butyl ester, N, N-dimethyl PABA2-ethylhexyl ester and other benzoic acids. Ultraviolet absorbers; Anthranilic acid-based ultraviolet absorbers such as homomentyl-N-acetylanthranilate; salicylic acid-based such as amylsalicylate, mentylsalicylate, homomentylsalicylate, octylsalicylate, phenylsalicylate, benzylsalicylate, p-isopropanolphenylsalicylate. UV absorbers; octyl cinnamate, ethyl-4-isopropyl cinnamate, methyl-2,5-diisopropyl cinnamate, ethyl-2,4-diisopropyl cinnamate, methyl-2,4-diisopropyl cinnamate, propyl-p- Methoxysinnamate, isopropyl-p-methoxysinamate, isoamyl-p-methoxysinamate, octyl-p-methoxysinamate (2-ethylhexyl-p-methoxysinamate), 2-ethoxyethyl-p-methoxysinamate, Cyclohexyl-p-methoxysinamate, ethyl-α-cyano-β-phenylsinamate, 2-ethylhexyl-α-cyano-β-phenylsinamate, glycerylmono-2-ethylhexanoyl-diparamethoxysinamate, etc. Capacic acid-based ultraviolet absorber; [3-bis (trimethylsiloxy) methylsilyl-1-methylpropyl] -3,4,5-trimethoxycinnamate, [3-bis (trimethylsiloxy) methylsilyl-3-methylpropyl] -3,4,5-trimethoxycinnamate, [3-bis (trimethylsiloxy) methylsilylpropyl] -3,4,5-trimethoxycinnamate, [3-bis (3-bis (trimethylsiloxy) methylsilylpropyl] Trimethylsiloxy) methylsilylbutyl] -3,4,5-trimethoxycinnamate, [3-tris (trimethylsiloxy) silylbutyl] -3,4,5-trimethoxycinnamate, [3-tris (trimethylsiloxy) silylbutyl ] -3,4,5-Trimethoxycinnamate, [3-tris (trimethylsiloxy) silyl-1-methylpropyl] -3,4-dimethoxycinnamate and other silicone-based silicic acid UV absorbers; 2,4 -Dihydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'4,4'-tetrahydroxybenzophenone, 2-hydroxy-4- Methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonate, 4-phenylbenzophenone, 2-ethylhexyl-4'-phenyl-benzophenone-2- Benzophenone-based UV absorbers such as carboxylate, 2-hydroxy-4-n-octoxybenzophenone, 4-hydroxy-3-carboxybenzophenone; 3- (4'-methylbenziliden) -d, l-camfer, 3-benziliden -D, l-camper, urocanic acid ethyl ester, 2-phenyl-5-methylbenzoxazole, 2,2'-hydroxy-5-methylphenylbenzotriazole, 2- (2'-hydroxy-5'-t- Octylphenyl) benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, dibenzalazine, dianisoilmethane, 4-methoxy-4'-t-butyldibenzoylmethane, 5- (3,3' Ultraviolet absorbers such as dimethyl-2-norbornylidene) -3-pentan-2-one; organic acids such as acylsarcosic acid (eg, lauroylsarcosin sodium), glutathione, citric acid, malic acid, tartaric acid, lactic acid; vitamin A and itss. Derivatives, Vitamin B6 Hydrochloride, Vitamin B6 Tripalmitate, Vitamin B6 Dioctanoate, Vitamin B2 and Derivatives thereof, Vitamin Bs such as Vitamin B12, Vitamin B15 and Derivatives, α-Tocopherol, β-Tocopherol, γ-Tocopherol, Vitamin Vitamin E such as E acetate, Vitamin D, Vitamin H, pantothenic acid, pantetin, nicotinic acid amide , Vitamins such as benzyl nicotinate; γ-orizanol, allantin, glycyrrhizinic acid (salt), glycyrrhetinic acid and its derivatives, tranexamic acid and its derivatives [as the tranexamic acid derivative, a dimer of tranexamic acid (eg, trans hydrochloride). -4- (Trans-aminomethylcyclohexanecarbonyl) aminomethylcyclohexanecarboxylic acid, etc.), ester of tranexamic acid and hydroquinone (eg, trans-4-aminomethylcyclohexanecarboxylic acid 4'-hydroxyphenyl ester, etc.), tranexam Esters of acids and gentisic acids (eg, 2- (trans-4-aminomethylcyclohexylcarbonyloxy) -5-hydroxybenzoic acid and salts thereof, etc.), amides of tranexamic acid (eg, trans-4-aminomethyl) Sicolohexanecarboxylic acid methylamide and its salts, trans-4- (P-methoxybinzoyl) aminomethylcyclohexanecarboxylic acid and its salts, trans-4-guanidinomethylcyclohexanecarboxylic acid and its salts, etc.)], hinokithiol, bisabolol, Saponins such as eucalptone, timole, inositol, psychosaponin, carrot saponin, hetima saponin, mucrodisaponin, various drugs such as pantothenyl ethyl ether, ethynyl estradiol, tranexamic acid, arbutin, cepharanthin, placenta extract; Extracts of plants such as kohone, orange, sage, sawtooth, zeniaoi, senburi, thyme, touki, touhi, birch, sugina, hechima, marronnier, yukinoshita, arnica, lily, yomogi, shakyaku, aloe, kuchinashi, sawara; Porous and / or water-absorbent powder (eg, powders of starches obtained from corn, potatoes, etc., anhydrous silicic acid, talc, kaolin, aluminum magnesium silicate, calcium alginate, etc.); neutralizers; preservatives; fragrances ; Pigments and the like can be mentioned.

The emulsified composition of the present invention can be produced by the following production method.
That is, the fine particle-forming polyvinyl-based polymer is dispersed in the aqueous phase to form the polyvinyl-based polymer fine particles, and then the oil phase component is added to the aqueous phase in which the polyvinyl-based polymer fine particles are dispersed, and the mixture is stirred and mixed. By doing so, the emulsified composition of the present invention can be produced.

In a preferred embodiment of the present invention, it is preferable to add the oil phase after all the fine particle-forming polyvinyl-based polymers dispersed in the aqueous phase have become the polyvinyl-based polymer fine particles.

Since the emulsified composition of the present invention is mild and less sticky, it should be used as a cosmetic, a skin external preparation, a quasi-drug or a pharmaceutical product such as a milky lotion, a cream, a beauty essence, a sunscreen, and a liquid foundation. Is preferable.

The present invention also relates to a method for evaluating a polyvinyl polymer, which comprises the following steps.
(1) A step of determining whether or not fine particles are formed when the polyvinyl-based polymer to be evaluated is dispersed in water.
(2) A step of determining whether or not the polyvinyl-based polymer to be evaluated is adsorbed on the emulsified interface in the form of fine particles.
(3) A step of determining whether or not the viscosity of an aqueous solution containing a polyvinyl polymer to be evaluated at a concentration of 0.5% by mass at 25 ° C. and 1 atm is 3000 mPa · S or less.

It was confirmed that fine particles were formed in the step (1), it was confirmed that the fine particles were adsorbed on the emulsifying interface in the form of fine particles in the step (2), and the concentration was 0.5% by mass in the step (3). When it is confirmed that the viscosity of the aqueous solution contained in the above is 3000 mPa · S or less at 25 ° C. and 1 atm, it can be evaluated that the polyvinyl-based polymer to be evaluated is excellent as an emulsifier.

The present invention also relates to a method for designing an emulsified composition, which comprises a step of selecting a polyvinyl-based polymer evaluated as being excellent as an emulsifier by the above-mentioned evaluation method as an emulsifier.
According to the design method of the present invention, it is possible to easily design an emulsified composition having excellent emulsion stability while having less stickiness.

(1) Synthesis of Polyvinyl Polymer 1 A hydrophilic monomer having the following structure and a hydrophobic monomer were copolymerized at a mass ratio of 7: 3 to synthesize a polyvinyl polymer 1.

Hydrophilic monomer

Hydrophobic monomer

(2) Evaluation of Physical Properties of Polyvinyl Polymer 1 (2-1) Average Molecular Weight of Polyvinyl Polymer 1 When the polystyrene-equivalent weight average molecular weight was measured by GPC, the average molecular weight of the polyvinyl polymer 1 was 61000. ..

(2-2) Viscosity of Aqueous Solution of Polyvinyl Polymer 1 An aqueous solution containing the polyvinyl polymer 1 in an amount of 0.1% by mass, 0.5% by mass and 1.0% by mass was prepared, respectively. When the viscosity of this aqueous solution was measured with a B-type viscometer (No. 3 rotor, 6 rpm, 1 mim, 20 ° C., 1 atm), it was less than 2000 mPa · S in each case. In addition, no concentration-dependent thickening effect of the polyvinyl polymer 1 was observed.

(3) Preparation of emulsified composition Polyvinyl polymer 1 was dispersed in water (polyvinyl polymer 1: water = 1: 89). When this aqueous solution was measured by dynamic light scattering measurement based on the laser Doppler method (Zetasizer Nano-Z ZEN3600, Malvern), it was confirmed that fine particles having an average particle diameter of 20 nm were formed.

After confirming the formation of fine particles, four types of oils, squalane, tri (caprylic / capric acid) glyceryl, cetyl 2-ethylhexanoate, and dimethicone (10 cP), are added to the aqueous solution, and the mixture is stirred and mixed. Four kinds of emulsified compositions of Examples (polyvinyl polymer 1: oil: water = 1: 10: 89) were prepared. For comparison, emulsified compositions of four comparative examples of oil: water = 10:89 were also prepared.

The oil-water interfacial tension was measured by the suspension method (pendant drop method) for a total of eight emulsified compositions prepared above. The results are shown in Table 1 below.

As shown in Table 1, in the emulsified composition prepared by any of the oil agents, a decrease in the oil-water interfacial tension was observed by the addition of the polyvinyl polymer 1.
Considering this result and the result of dynamic light scattering measurement when the polyvinyl polymer 1 is dispersed in water, the polyvinyl polymer 1 is in the form of fine particles and is adsorbed on the oil-water interface by van der Waals force. It was suggested that

(4) Evaluation of Emulsified Composition (4-1) Observation with an Electron Microscope Among the emulsified compositions prepared above, the emulsified composition of Examples containing squalane as an oil agent was observed with a scanning electron microscope. An electron microscope image is shown in FIG.

As shown in FIG. 1, unevenness was observed on the surface of the oil droplets dispersed in the emulsified composition of the example. From this, it was confirmed that the polyvinyl-based polymer 1 in the form of fine particles was adsorbed on the emulsified interface of the oil droplets dispersed in the emulsified composition of the example and covered the entire surface thereof.

(4-2) Evaluation of emulsification stability (1)
The emulsified composition of Example containing squalane as an oil was allowed to stand at room temperature for 2 months. As a result, no coalescence of oil droplets, which is an indicator of emulsion destabilization, was observed. This result shows that the emulsified composition of the example is excellent in emulsification stability.

(4-3) Evaluation of emulsification stability (2)
2% of NaCl was added to the emulsified composition of the example containing squalane as an oil agent, and the emulsified state was observed, but a stable emulsified state was maintained without destabilization. The result is that the emulsified composition of the example is emulsified as shown in (4-2) above by steric repulsion rather than electrostatic repulsion of the fine particles made of the polyvinyl polymer 1 adsorbed on the emulsified interface. It shows that it exhibits stability.

(4-4) Summary As shown in (3) above, the polyvinyl polymer 1 is in a particle state in a dispersed state in water, and is adsorbed on the oil-water interface by van der Waals force in the form of fine particles. It has been suggested. As shown in (4-1) above, considering the result of observing unevenness on the surface of the oil droplets dispersed in the emulsified composition, a polyvinyl-based polymer is present at the emulsified interface of the emulsified composition of the example. It can be seen that 1 is adsorbed in the form of fine particles.

By the way, conventional polymer emulsifiers show high viscosity in the form of an aqueous solution. Therefore, the conventional emulsified composition using a polymer emulsifier has a problem that stickiness occurs when trying to achieve high stability.

On the other hand, the polyvinyl polymer 1 has a low viscosity as shown in (2-2) above, and the emulsified composition of the present example emulsified by adsorbing the polyvinyl polymer 1 to the emulsified interface in the form of fine particles also has a low viscosity. Yes, it was not sticky (see (4-3) above). Nevertheless, the emulsified composition of this example had high emulsification stability (see (4-2) and (4-3) above).

The result is that (A) fine particles are formed when dispersed in water, and (B) fine particles made of a polyvinyl polymer having a viscosity of a 0.5% by mass aqueous solution at 25 ° C. and 1 atm at 3000 mPa · S or less. It is shown that the emulsified composition adsorbed on the emulsified interface has high emulsification stability while being less sticky.

The present invention can be applied to emulsified cosmetics.

Claims (8)

Fine particles made of a polyvinyl polymer satisfying the following conditions (A) and (B) are adsorbed on the emulsification interface .
(A) Fine particles are formed when dispersed in water.
(B) The viscosity of the aqueous solution containing the polyvinyl polymer at a concentration of 0.5% by mass at 25 ° C. and 1 atm is 3000 mPa · S or less. ;
The polyvinyl-based polymer contains one or more hydrophobic building blocks derived from the vinyl-based monomer represented by the following general formula (I), (II) or (III);
The polyvinyl-based polymer is a polymerizable carboxylic acid, a vinyl-based monomer represented by the following general formula (VIII), a vinyl-based monomer represented by the following general formula (IX), and the following general formula (X). Includes one or more hydrophilic building blocks derived from a vinyl-based monomer selected from a vinyl-based monomer represented by the following or a vinyl-based monomer represented by the following general formula (XI). An emulsified composition, characterized in that.

General formula (I)

(In the general formula (I), A represents -O- or -COO-, R ¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ² represents a hydrocarbon group having 6 to 30 carbon atoms. show.)

General formula (II)

(In the general formula (II), A represents -O- or -COO-, R ³ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ⁴ and R ⁵ may be the same or different. , Represents an acyl group having 6 to 22 carbon atoms. X represents a group in which an OH group is desorbed from a trivalent alcohol.)

General formula (III)

(In the general formula (III), A represents -O- or -COO-, R ⁶ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ⁷ , R ⁸ and R ⁹ are the same but different. It may represent an acyl group having 6 to 22 carbon atoms. Y represents a group in which an OH group is desorbed from a tetravalent alcohol.)

General formula (VIII)

(In the general formula (VIII), B represents -O- or -COO-, R ¹³ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ¹⁴ represents a carbon number which may have a hydroxyl group. It represents 2 to 4 alkylene groups, and R ¹⁵ represents a hydrogen atom, an aromatic hydrocarbon 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 an integer of 6 to 40.)

General formula (IX)

(In the general formula (IX), B represents -O- or -COO-, and R ¹⁶ represents a hydrogen atom or a methyl group.)

General formula (X)

(In the general formula (X), D indicates that there is no -CO- or a substituent, R ¹⁷ is a hydrogen atom or a methyl group, and GO- is a group obtained by removing hydrogen from the hydroxyl group at the 1-position of the reducing sugar. M represents 2 or 3, and l represents an integer of 1 to 5.)

General formula (XI)

(In the general formula (XI), R ¹⁸ represents a hydrogen atom or a methyl group, R ¹⁹ represents an amino acid residue, a polyamine residue or an amino alcohol residue, and Q represents an oxygen atom or a group represented by NH.)
The emulsified composition according to claim 1, wherein the polyvinyl-based polymer satisfies the following conditions (C).
(C) When an aqueous solution having a concentration of 0.1% by mass to 1.0% by mass is used, a concentration-dependent thickening effect is not exhibited. The emulsified composition according to claim 1 or 2 , wherein the polyvinyl-based polymer has no ionizing group. The emulsified composition according to any one of claims 1 to 3, wherein the mass ratio of the hydrophobic constituent unit to the hydrophilic constituent unit is 10:90 to 50:50. The emulsified composition according to any one of claims 1 to 4, wherein the molar ratio of the hydrophobic constituent unit to the hydrophilic constituent unit is 15:85 to 62:38. The emulsified composition according to any one of claims 1 to 5, wherein the polyvinyl-based polymer has an average molecular weight of 20000 to 80000. The method for producing an emulsified composition according to any one of claims 1 to 6 , wherein the polyvinyl-based polymer is dispersed in an aqueous phase to form fine particles made of the polyvinyl-based polymer. A production method comprising a step of adding an oil phase component to an aqueous phase in which fine particles are dispersed and stirring and mixing the components. Satisfy the following conditions of (A) and (B), Ri Do from polyvinyl polymer which adsorbs to the emulsion interface in the form of fine particles,
(A) Fine particles are formed when dispersed in water.
(B) The viscosity of the aqueous solution containing the polyvinyl polymer at a concentration of 0.5% by mass at 25 ° C. and 1 atm is 3000 mPa · S or less. ;
The polyvinyl-based polymer contains one or more hydrophobic building blocks derived from the vinyl-based monomer represented by the following general formula (I), (II) or (III);
The polyvinyl-based polymer is a polymerizable carboxylic acid, a vinyl-based monomer represented by the following general formula (VIII), a vinyl-based monomer represented by the following general formula (IX), and the following general formula (X). Includes one or more hydrophilic building blocks derived from a vinyl-based monomer selected from a vinyl-based monomer represented by the following or a vinyl-based monomer represented by the following general formula (XI). A polymer emulsifier characterized by this.

General formula (I)

(In the general formula (I), A represents -O- or -COO-, R ¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ² represents a hydrocarbon group having 6 to 30 carbon atoms. show.)

General formula (II)

(In the general formula (II), A represents -O- or -COO-, R ³ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ⁴ and R ⁵ may be the same or different. , Represents an acyl group having 6 to 22 carbon atoms. X represents a group in which an OH group is desorbed from a trivalent alcohol.)

General formula (III)

(In the general formula (III), A represents -O- or -COO-, R ⁶ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ⁷ , R ⁸ and R ⁹ are the same but different. It may represent an acyl group having 6 to 22 carbon atoms. Y represents a group in which an OH group is desorbed from a tetravalent alcohol.)

General formula (VIII)

(In the general formula (VIII), B represents -O- or -COO-, R ¹³ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ¹⁴ represents a carbon number which may have a hydroxyl group. It represents 2 to 4 alkylene groups, and R ¹⁵ represents a hydrogen atom, an aromatic hydrocarbon 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 an integer of 6 to 40.)

General formula (IX)

(In the general formula (IX), B represents -O- or -COO-, and R ¹⁶ represents a hydrogen atom or a methyl group.)

General formula (X)

(In the general formula (X), D indicates that there is no -CO- or a substituent, R ¹⁷ is a hydrogen atom or a methyl group, and GO- is a group obtained by removing hydrogen from the hydroxyl group at the 1-position of the reducing sugar. M represents 2 or 3, and l represents an integer of 1 to 5.)

General formula (XI)

(In the general formula (XI), R ¹⁸ represents a hydrogen atom or a methyl group, R ¹⁹ represents an amino acid residue, a polyamine residue or an amino alcohol residue, and Q represents an oxygen atom or a group represented by NH.)

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