JP2015101613A - Water dispersible polymer fine particle containing oil soluble compound and method for producing water dispersion of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide polymer fine particles containing an oil soluble compound which have hydrophilic polymer chains on the fine particle surfaces and good water dispersibility in an aqueous medium, and further to provide a method for producing a water dispersion of the polymer fine particles without using a dispersant or an emulsifier.SOLUTION: There are synthesized water dispersible polymer fine particles containing an oil soluble compound by radical polymerization of a hydrophilic macromonomer having a radical polymerizable reactive group and a hydrophilic radical polymerizable monomer in an aqueous medium in the presence of an oil soluble compound.

Description

The present invention relates to a novel polymer fine particle encapsulating an oil-soluble compound and a method for producing an aqueous dispersion thereof, and more specifically, has a cationic, anionic or nonionic hydrophilic polymer chain on the surface of the fine particle. The present invention also relates to a method for producing polymer fine particles in which a core is composed of a hydrophobic polymer compound and an oil-soluble compound is encapsulated in the core, and an aqueous dispersion thereof.

  Microcapsules are used in fields such as pharmaceuticals, agricultural chemicals, dyes, adhesives, fragrances, printing, and textile processing. Coacervation methods, interfacial polymerization methods, in-situ methods, etc. are known as microcapsule production methods. It has been. For example, Patent Document 1 uses arabic rubber as an emulsifier, Patent Documents 2 and 3 use melamine-formalin resin by an in-situ method using additives such as ethylene maleic anhydride copolymer and styrene maleic anhydride copolymer. A process for the production of capsules is described. The particle size of these microcapsules is on the order of several μm. However, as the microencapsulation technology is used more and more, the demand for performance has been advanced, and the refinement of the particle size is one of the important factors. One. From this point of view, Patent Document 4 describes a method for obtaining microcapsules having a small particle size by using a stirring method having a strong shearing force. The particle size of the obtained capsule is about 1 μm.

Japanese Patent Publication No. 36-9168 JP-A-53-84881 Japanese Examined Patent Publication No. 2-57985 JP 2007-283173 A

  An object of the present invention is to provide a method for producing finer polymer fine particles containing an oil-soluble compound and an aqueous dispersion thereof without using an additive such as an emulsifier and a dispersant.

As a result of intensive research, the present inventor introduced an amino group-containing hydrophilic macromonomer introduced with a vinyl group, or a carboxylic acid and / or carboxylate-containing hydrophilic macromonomer introduced with a vinyl group, or a vinyl group. Polyalkylene glycol macromonomer, amino group-containing hydrophilic macromonomer and polyalkylene glycol macromonomer, or carboxylic acid and / or carboxylate-containing hydrophilic macromonomer and polyalkylene glycol macromonomer and hydrophobic radical polymerizable monomer The polymer is radically polymerized in the presence of an oil-soluble compound in an aqueous medium, so that the surface of the fine particles has a hydrophilic polymer chain, the core is composed of a hydrophobic polymer compound, and the oil-soluble compound is encapsulated inside the core. And found that high polymer fine particles can be obtained. .

That is, the cationic oil-soluble compound-encapsulated water-dispersed polymer fine particles according to the first invention of the present invention include at least one selected from polymer compounds having an amino group-containing structural unit, and the following general formula ( An amino group-containing hydrophilic macromonomer obtained by reacting at least one selected from the compounds represented by 1) and at least one selected from the compounds represented by the following general formula (2);

[In Formula (1), R ₁ represents a hydrogen atom or a methyl group, R ₂ represents a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, or a halogen atom, and X ₁ represents a halogen atom. ]

Wherein _{(2), R 3, R} 4 are the same or different and each represents a hydrogen atom or a lower alkyl group or a halogen atom having 1 to 4 carbon atoms, _{X 2} represents a halogen atom. ]

It is obtained by radical polymerizing at least one selected from hydrophobic radical polymerizable monomers in an aqueous medium in the presence of a water-insoluble oil-soluble compound.

The anionic oil-soluble compound-encapsulated water-dispersed polymer fine particle according to the second aspect of the present invention comprises at least one selected from polymer compounds having a carboxylic acid and / or carboxylate-containing structural unit. A carboxylic acid and / or carboxylate-containing hydrophilic macromonomer obtained by reacting at least one selected from the compounds represented by the following general formula (3);

[In formula (3), R ₅ represents a hydrogen atom or a methyl group, and Q ₁ represents an oxygen atom or —NH—. ]

It is obtained by radical polymerizing at least one selected from hydrophobic radical polymerizable monomers in an aqueous medium in the presence of a water-insoluble oil-soluble compound.

The nonionic oil-soluble compound-encapsulated water-dispersed polymer fine particle according to the third aspect of the present invention is at least one polyalkylene glycol macromonomer selected from compounds represented by the following general formula (4) When,

[In the formula (4), R ₆ and R ₇ are the same or different and each represents a hydrogen atom or a methyl group, Q ₂ represents an oxygen atom or —NH—, Q ₃ represents methylene or propylene, and n represents 1 to A number of 100 is shown. ]

It is obtained by radical polymerizing at least one selected from hydrophobic radical polymerizable monomers in an aqueous medium in the presence of a water-insoluble oil-soluble compound.

The oil-soluble compound-encapsulated water-dispersed polymer fine particles according to the fourth aspect of the present invention are the amino group-containing hydrophilic macromonomer, the polyalkylene glycol macromonomer, and the hydrophobic radical polymerizable monomer. It is obtained by radical polymerization in an aqueous medium in the presence of a water-insoluble oil-soluble compound.

The oil-soluble compound-encapsulated water-dispersed polymer fine particle according to the fifth aspect of the present invention comprises the carboxylic acid and / or carboxylate-containing hydrophilic macromonomer and the polyalkylene glycol macromonomer, and hydrophobic radical polymerization. It is obtained by radical polymerization of at least one selected from water-soluble monomers in an aqueous medium in the presence of a water-insoluble oil-soluble compound.

The method for producing an aqueous dispersion of fine polymer particles encapsulating the oil-soluble compound of the present invention is synthesized by radical polymerization of each hydrophilic macromonomer and hydrophobic monomer in an aqueous medium as described above. It is characterized by that.

According to the invention, a hydrophilic polymer chain having primary and / or secondary and / or tertiary amino groups, or a hydrophilic polymer chain having carboxylic acid and / or carboxylate, or a polyalkylene glycol chain, Alternatively, a hydrophilic polymer chain having an amino group and a polyalkylene glycol chain, or a hydrophilic polymer chain having a carboxylic acid and / or carboxylate salt and / or a polyalkylene glycol chain on the surface of the fine particle, and a hydrophobic polymer inside The oil-soluble compound-encapsulated water-dispersed polymer fine particles composed of the oil-soluble compound can be easily produced as an aqueous dispersion having a particle size of about 100 nm without using a dispersant or an emulsifier in an aqueous medium. Since the oil-soluble compound-encapsulated water-dispersed polymer fine particles of the present invention have finer particle diameters than capsules made of conventional resins such as melamine resin, polyurea, and polyurethane urea, pharmaceuticals, agricultural chemicals, dyes, adhesives, fragrances, printing Further enhancement of functionality is expected in fields such as textile processing.

Hereinafter, the present invention will be described in detail. The oil-soluble compound-encapsulated water-dispersed polymer fine particle of the present invention is composed of a hydrophilic polymer chain localized on the surface of the fine particle, a hydrophobic polymer compound that forms the core of the fine particle, and an oil-soluble compound. First, the cationic oil-soluble compound-encapsulated water-dispersed polymer fine particles of the present invention and the method for producing the polymer fine particle aqueous dispersion will be described.

Examples of the monomer constituting the primary amine-containing structural unit include allylamine, and examples of the monomer constituting the secondary amine-containing structural unit include methylallylamine and diallylamine. Examples of the monomer include dimethylallylamine, methyldiallylamine, acryloyloxyethyldimethylamine, methacryloyloxyethyldimethylamine, acryloylaminoethyldimethylamine, methacryloylaminoethyldimethylamine, and the like, which can be appropriately combined. Further, these monomers may be appropriately combined with a monomer containing a quaternary ammonium group copolymerizable with a monomer constituting a structural unit containing a primary amine, a secondary amine and a tertiary amine. Examples of the monomer containing a group include diallyldimethylammonium chloride, diallylmethylethylammonium chloride, diallyldiethylammonium chloride, diallyldimethylammonium bromide, acryloyloxyethyltrimethylammonium chloride, methacryloyloxyethyltrimethylammonium chloride, acryloylaminoethyltrimethylammonium chloride. And methacryloylaminoethyltrimethylammonium chloride. Furthermore, a nonionic water-soluble monomer may be appropriately combined with a nonionic water-soluble monomer copolymerizable with the monomer constituting the primary amine, secondary amine, or tertiary amine-containing structural unit. Examples thereof include acrylamide, methacrylamide, and n-isopropylacrylamide. A homopolymer or copolymer of a monomer constituting the primary amine, secondary amine or tertiary amine-containing structural unit, or a monomer containing a quaternary ammonium group or a nonionic water-soluble monomer An appropriately combined polymer can be prepared by a conventionally known polymerization method. Examples of the polymer compound containing a primary amine include polyvinylamine, and examples of the polymer compound containing a primary amine, secondary amine, and tertiary amine include polyethyleneimine and polypropyleneimine. These polymer compounds having an amino group-containing structural unit can be used alone or in appropriate combination, but polyethyleneimine is particularly preferred.

The proportion of the amino group-containing structural unit in the polymer compound having an amino group-containing structural unit is preferably 60% or more, more preferably 80% or more of the total polymer structural unit, Is particularly preferably an amino group-containing structural unit.

  The molecular weight of the polymer compound having an amino group-containing structural unit is not particularly limited as long as it is a molecular weight obtained by a known polymerization method, but is preferably 500 to 500,000.

Examples of the lower alkyl group having 1 to 4 carbon atoms represented by R ₂ in the compound represented by the general formula (1) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the halogen atom represented by X ₁ in the compound represented by the general formula (1) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the compound represented by the general formula (1) include chloromethylstyrene, bromomethylstyrene, iodomethylstyrene, and the like, and chloromethylstyrene is particularly preferable.

These compounds can be used alone or in appropriate combination.

Examples of the lower alkyl group having 1 to 4 carbon atoms represented by R ₃ and R ₄ in the compound represented by the general formula (2) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the halogen atom represented by X ₂ in the compound represented by the general formula (2) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the compound represented by the general formula (2) include benzyl chloride, benzyl bromide and benzyl iodide, and benzyl chloride is particularly preferable.

These compounds can be used alone or in appropriate combination.

  An amino group and / or a quaternary obtained by reacting a polymer compound having an amino group-containing structural unit with a vinylbenzyl halide represented by the general formula (1) and a benzyl halide represented by the general formula (2) Synthesis of an ammonium group-containing hydrophilic macromonomer includes a polymer compound having an amino group-containing structural unit in an aqueous medium, a vinylbenzyl halide represented by the general formula (1), and a benzyl halide represented by the general formula (2) Can be carried out by reacting at 10 ° C to 80 ° C, more preferably 20 ° C to 60 ° C.

  The ratio of the polymer compound having an amino group-containing structural unit to the vinyl benzyl halide represented by the general formula (1) and the benzyl halide represented by the general formula (2) is not particularly limited. The vinyl benzyl halide is in the range of 40 mol to 1 mol and the benzyl halide is preferably in the range of 60 mol to 5 mol, more preferably the vinyl benzyl halide is in the range of 35 mol to 1 mol, and the benzyl halide is 100 mol. A range of 40 mol to 5 mol, a range of 10 to 1 mol of vinylbenzyl halide, and a range of 30 to 5 mol of benzyl halide are particularly preferred.

  The reaction between the polymer compound having an amino group-containing structural unit, the vinyl benzyl halide represented by the general formula (1) and the benzyl halide represented by the general formula (2) is a secondary reaction of a primary amine or 3 A quaternization reaction, a quaternization reaction, a tertiary amine quaternization reaction or a quaternization reaction, or a tertiary amine quaternization reaction.

An amino group-containing hydrophilic macromonomer obtained by reacting a polymer compound having an amino group-containing structural unit with a vinylbenzyl halide represented by the general formula (1) and a benzyl halide represented by the general formula (2) Is preferably a polyethyleneimine polymer compound having an amino group-containing structural unit. As an example of the structure, the following formula (5a)

(Wherein R ₁ , R ₂ , R ₃ , R ₄ and X ₁ , X ₂ are the same as described above, and a, b, c, d, e, f, g, h are integers representing the number of repeating units. And the following formula (5b):

(Wherein, X ₁ and X ₂ are the same as defined above, and a, b, c, d, e, f, g and h are integers representing the number of repeating units), and further, The following formula (5c)

(Wherein, a, b, c, d, e, f, g, and h are integers representing the number of repeating units).

  As the hydrophobic radical polymerizable monomer in the present invention, a known hydrophobic monomer capable of binding to an ethylenically unsaturated bond group can be used, for example, styrene, methylstyrene, dimethylstyrene, chlorostyrene, dichloromethane. Styrene monomers such as styrene, chloromethylstyrene, 4-methoxystyrene, 4-acetoxystyrene, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate , Hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, (meth) acrylic acid Phenyl, benzyl (meth) acrylate, 2-hydro (meth) acrylate (Meth) acrylic acid esters such as ciethyl, vinyl monomers such as vinyl acetate, vinyl propionate, vinyl caproate, vinyl laurate, vinyl cyclohexanecarboxylate, vinyl benzoate, N-butylacrylamide, acrylonitrile, vinyl chloride be able to. These monomers can be polymerized alone or two or more monomers may be copolymerized.

It is also possible to introduce a crosslinked structure into the core part of the polymer fine particles. For this purpose, a bifunctional hydrophobic radical polymerizable monomer such as divinylbenzene or ethylene glycol dimethacrylate is used. Is preferred. The bifunctional hydrophobic radical polymerizable monomer can be used in the range of 0.01 to 20% by weight with respect to the total radical polymerizable monomer constituting the core of the fine polymer particles, and 0.1 to 10% by weight. % Is more preferable.

  The oil-soluble compound in the present invention is not particularly limited as long as it is a compound that is insoluble in water and dissolves in a hydrophobic radical polymerizable monomer that forms the core of polymer fine particles. For example, tetradecane, hexadecane , Hydrocarbon compounds such as octadecane, higher fatty acids such as lauric acid, palmitic acid, stearic acid, oleic acid, esterified oils such as methyl laurate, methyl palmitate, methyl stearate, methyl oleate, lauryl alcohol, stearyl alcohol And higher alcohols such as limonene, hinokitiol, and benzyl acetate, repellents such as N, N-diethyl-m-toluamide, animal and vegetable oils, silicone oils, agricultural chemicals, bioactive substances, deodorants, and coloring agents. It is done.

  The amount of the oil-soluble compound used in the present invention is not particularly limited, but it is 5 to 200% by weight, preferably 10 to 150% by weight, based on the total amount of the polymer fine particle core and the hydrophilic polymer chain disposed on the fine particle surface. %, More preferably 20 to 100% by weight.

  At least one amino group-containing hydrophilic macromonomer obtained as described above and at least one selected from hydrophobic radical polymerizable monomers are used as an oil-soluble compound, a polymerization initiator, and necessary. The cationic oil-soluble compound-encapsulated water-dispersed polymer fine particles of the present invention can be obtained by copolymerization in an aqueous medium in the presence of a molecular weight modifier. Dispersions can be produced.

  The polymerization temperature is preferably 50 ° C. to 100 ° C., and water alone is preferably used as the solvent, but alcohols such as methanol, ethanol and propanol, ketones such as acetone and methyl ethyl ketone, dimethylformamide and the like can be used. Mixed solvents such as alcohols / water or ketones / water can also be used. Examples of the polymerization initiator include ammonium persulfate, potassium persulfate, hydrogen peroxide, benzoyl peroxide, t-butyl hydroperoxide, azobisisobutyronitrile, azobis (2-aminodipropane) hydrochloride, and the like. It is done. A preferable amount of the polymerization initiator is about 0.1 to 10 mol with respect to 100 mol of the hydrophobic radical polymerizable monomer. The polymerization time varies depending on the type and amount of the polymerization initiator used, the polymerization temperature, etc., but is usually 30 minutes to 10 hours, and is a hydrophobic radical polymerizable monomer that contributes to the formation of the core part of the fine particles and the amino group. The polymerization is preferably carried out until the contained hydrophilic macromonomer is consumed by the polymerization.

In the synthesis of the cationic oil-soluble compound-encapsulated water-dispersed polymer fine particles of the present invention, the ratio of the amino group-containing hydrophilic macromonomer and the hydrophobic radical polymerizable monomer is not particularly limited. The ratio of the repeating unit of the hydrophilic macromonomer and the hydrophobic radical polymerizable monomer is preferably in the range of 1: 100 to 0.01, more preferably in the range of 1:10 to 0.1, and 1: 5 to 0 .2 is particularly preferred.

  In the synthesis of the cationic oil-soluble compound-encapsulated water-dispersed polymer fine particles of the present invention, polyethyleneimine as the polymer compound having an amino group-containing structural unit, chloromethylstyrene as the compound represented by the general formula (1), A combination containing benzyl chloride as the compound represented by the general formula (2) is particularly preferable.

The cationic oil-soluble compound-encapsulated water-dispersed polymer fine particles of the present invention include a polymer compound having an amino group-containing structural unit as described above, the vinylbenzyl halide represented by the general formula (1), and the general formula ( 2) At least one amino group-containing hydrophilic macromonomer obtained by reacting with the benzyl halide represented by 2) and at least one hydrophobic radical polymerizable monomer in an aqueous medium in the presence of an oil-soluble compound. And a hydrophilic polymer chain having primary and / or secondary and / or tertiary amino groups localized on the surface of the fine particles, and the core of the fine particles, obtained by copolymerization with An aqueous dispersion of fine particles composed of a hydrophobic polymer compound and an oil-soluble compound encapsulated in the core can be produced.

Next, an anionic oil-soluble compound-encapsulated water-dispersed polymer fine particle of the present invention and a method for producing the polymer fine particle aqueous dispersion will be described.

The monomer constituting the polymer compound having a carboxylic acid and / or carboxylate-containing structural unit is a monomer that essentially contains a carbon-carbon unsaturated double bond and a carboxyl group and / or a salt thereof, for example, (Meth) acrylic acid, crotonic acid, α-hydroxyacrylic acid, α-hydroxymethylacrylic acid and unsaturated monocarboxylic acids and their salts thereof, itaconic acid, fumaric acid, maleic acid, 2-methyleneglutaric acid And unsaturated dicarboxylic acids such as these and their salts. These can be combined as appropriate.

  Examples of the salt include metal salts, ammonium salts, and organic amine salts. Examples of the metal salts include alkali metal salts such as lithium salts, sodium salts, and potassium salts, alkaline earth metal salts such as magnesium salts and calcium salts, and aluminum. , And salts such as iron, and organic amine salts include monoethanolamine salts, diethanolamine salts, alkanolamine salts such as triethanolamine salts, monoethylamine salts, diethylamine salts, alkylamine salts such as triethylamine salts, ethylenediamine salts, Examples include organic amine salts such as polyamines such as triethylenediamine salts. These can be combined as appropriate.

Further, a nonionic water-soluble monomer that can be copolymerized with a monomer that forms a polymer compound having the carboxylic acid and / or carboxylate-containing structural unit may be appropriately combined. Examples of the monomer include acrylamide, methacrylamide, and n-isopropylacrylamide. A homopolymer or copolymer of a monomer constituting a polymer compound having a carboxylic acid and / or carboxylate-containing structural unit, or a polymer obtained by appropriately combining nonionic water-soluble monomers is known in the art. It can be produced by a polymerization method. These polymer compounds having a carboxylic acid and / or carboxylate-containing structural unit can be used alone or in appropriate combination, but polyacrylic acid is preferred, and sodium polyacrylate is particularly preferred.

The proportion of the carboxylic acid and / or carboxylate-containing structural unit in the polymer compound having a carboxylic acid and / or carboxylate-containing structural unit is preferably 60% or more of the total polymer structural unit, and 80 % Is more preferable, and it is particularly preferable that all the structural units are carboxylic acid and / or carboxylate-containing structural units.

  The molecular weight of the polymer compound having a carboxylic acid and / or carboxylate-containing structural unit is not particularly limited as long as it is a molecular weight obtained by a known polymerization method, but is preferably 500 to 500,000.

Examples of the compound represented by the general formula (3) include glycidyl acrylate, glycidyl methacrylate, glycidyl acrylamide, and glycidyl methacrylamide, and these compounds can be used alone or in appropriate combination.

  Carboxylic acid and / or carboxylate-containing hydrophilic macro formed by reacting a polymer compound having a carboxylic acid and / or carboxylate-containing structural unit with a glycidyl group-containing vinyl monomer represented by the general formula (3) In the synthesis of the monomer, a polymer compound having a carboxylic acid and / or carboxylate-containing structural unit and a glycidyl group-containing vinyl monomer represented by the general formula (3) in an aqueous medium are more preferably 10 ° C to 80 ° C. It can carry out by making it react at 20 to 60 degreeC.

  The ratio of the polymer compound having a carboxylic acid and / or carboxylate-containing structural unit and the glycidyl group-containing vinyl monomer represented by the general formula (3) is not particularly limited, but the carboxylic acid and / or carboxylate-containing structure The glycidyl group-containing vinyl monomer is preferably in the range of 40 mol to 1 mol, more preferably in the range of 35 mol to 1 mol, and particularly preferably in the range of 10 mol to 1 mol with respect to 100 mol of the unit.

  The reaction between the polymer compound having a carboxylic acid and / or carboxylate-containing structural unit and the glycidyl group-containing vinyl monomer represented by the general formula (3) is a nucleophilic reaction on the glycidyl group of the carboxyl group.

Carboxylic acid and / or carboxylate-containing hydrophilic macro formed by reacting a polymer compound having a carboxylic acid and / or carboxylate-containing structural unit with a glycidyl group-containing vinyl monomer represented by the general formula (3) As the monomer, polyacrylic acid salt is preferably used as a polymer compound having a carboxylic acid and / or carboxylate-containing structural unit, and glycidyl methacrylate is preferably used as a glycidyl group-containing vinyl monomer. (6a)

(Wherein, M represents an alkali metal ion, an alkaline earth metal ion, an ammonium ion, or an organic amine, and l and m are integers representing the number of repeating units), and the following formula ( 6b)

(Wherein, l and m are integers representing the number of repeating units).

The hydrophobic radical polymerizable monomer, bifunctional hydrophobic radical polymerizable monomer, and oil-soluble compound in the present invention are the same as described above.

  An oil-soluble compound comprising at least one carboxylic acid and / or carboxylate-containing hydrophilic macromonomer obtained as described above and at least one selected from hydrophobic radical polymerizable monomers The anionic oil-soluble compound-encapsulated water-dispersed polymer fine particles of the present invention can be obtained by copolymerization in an aqueous medium in the presence of a polymerization initiator and, if necessary, a molecular weight regulator. An aqueous dispersion of the polymer fine particles can be produced.

  The above polymerization temperature, solvent, polymerization initiator, and polymerization time are the same as described above.

In the synthesis of the anionic oil-soluble compound-encapsulated water-dispersed polymer fine particles of the present invention, the ratio of the carboxylic acid and / or carboxylate-containing hydrophilic macromonomer to the hydrophobic radical polymerizable monomer is particularly limited. However, the ratio of the repeating unit of the carboxylic acid and / or carboxylate-containing hydrophilic macromonomer to the hydrophobic radical polymerizable monomer is preferably in the range of 1: 100 to 0.01, and 1:10 to 0.00. The range of 1 is more preferable, and 1: 5 to 0.2 is particularly preferable.

  In the synthesis of the anionic oil-soluble compound-encapsulated water-dispersed polymer fine particles of the present invention, polyacrylic acid as the polymer compound having a carboxylic acid and / or carboxylate-containing structural unit is represented by the general formula (3). As the compound, a combination of glycidyl methacrylate is particularly preferable.

The anionic oil-soluble compound-encapsulated water-dispersed polymer fine particles of the present invention include a polymer compound having a carboxylic acid and / or carboxylate-containing structural unit as described above and a glycidyl represented by the general formula (3) ( In the presence of an oil-soluble compound, an aqueous medium containing at least one carboxylic acid and / or carboxylate-containing hydrophilic macromonomer containing meth) acrylate and at least one hydrophobic radical polymerizable monomer. Hydrophobic polymer compound obtained by copolymerization in a hydrophilic polymer chain having a carboxylic acid and / or carboxylate localized on the surface of the fine particles by the production method of the present invention and a core of the fine particles And the water dispersion of the fine particle comprised from the oil-soluble compound included in the core can be manufactured.

Next, the nonionic oil-soluble compound-encapsulated water-dispersed polymer fine particles of the present invention and the method for producing the polymer fine particle aqueous dispersion will be described.

Among the compounds represented by the general formula (4), polyethylene glycol (meth) acrylate, polyethylene glycol (meth) acrylamide, methoxypolyethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylamide, and polypropylene glycol (meth) acrylate , Polypropylene glycol (meth) acrylamide, and the like. These compounds can be used alone or in appropriate combination. As an example of the structure, the following formula (7a)

(Wherein R ₆ and R ₇ are the same or different and each represents a hydrogen atom or a methyl group, Q ₂ represents an oxygen atom or —NH—, and n is an integer representing the number of repeating units). Furthermore, the following equation (7b)

(Wherein, R ₆ and R ₇ are the same or different and each represents a hydrogen atom or a methyl group, and n is an integer representing the number of repeating units), and the following formula (7c):

(Wherein n is an integer representing the number of repeating units).

The hydrophobic radical polymerizable monomer, bifunctional hydrophobic radical polymerizable monomer, and oil-soluble compound in the present invention are the same as described above.

  The presence of an oil-soluble compound, a polymerization initiator, and, if necessary, a molecular weight modifier, at least one of the polyalkylene glycol macromonomer and at least one selected from hydrophobic radical polymerizable monomers Then, the nonionic oil-soluble compound-encapsulated water-dispersed polymer fine particles of the present invention can be obtained by copolymerization in an aqueous medium, and further, an aqueous dispersion of the polymer fine particles can be produced. .

  The above polymerization temperature, solvent, polymerization initiator, and polymerization time are the same as described above.

In the synthesis of the nonionic oil-soluble compound-encapsulated water-dispersed polymer fine particles of the present invention, the ratio of the polyalkylene glycol macromonomer and the hydrophobic radical polymerizable monomer is not particularly limited. The ratio with the polymerizable radical polymerizable monomer is preferably in the range of 1: 100 to 0.01, more preferably in the range of 1:10 to 0.1, and particularly preferably in the range of 1: 5 to 0.2.

  In the synthesis of the nonionic oil-soluble compound-encapsulated water-dispersed polymer fine particles of the present invention, methoxypolyethylene glycol methacrylate is particularly preferable as the compound represented by the general formula (4).

The nonionic oil-soluble compound-encapsulated water-dispersed polymer fine particles of the present invention include at least one polyalkylene glycol macromonomer represented by the general formula (4) and a hydrophobic radical polymerizable monomer as described above. Which is obtained by copolymerizing in an aqueous medium in the presence of an oil-soluble compound, and forms a fine particle core with a polyalkylene glycol chain localized on the fine particle surface by the production method of the present invention. An aqueous dispersion of fine particles composed of the above polymer compound and an oil-soluble compound encapsulated in the core can be produced.

Next, an oil-soluble compound-encapsulated water-dispersed polymer fine particle having an amino group-containing hydrophilic polymer chain and a polyalkylene glycol chain on the fine particle surface of the present invention and a method for producing the polymer fine particle aqueous dispersion will be described.

The hydrophobic radical polymerizable monomer, bifunctional hydrophobic radical polymerizable monomer, and oil-soluble compound in the present invention are the same as described above.

An oil-soluble compound comprising at least one amino group-containing hydrophilic macromonomer and at least one polyalkylene glycol macromonomer, and at least one selected from hydrophobic radical polymerizable monomers. Then, by copolymerization in an aqueous medium in the presence of a polymerization initiator and, if necessary, a molecular weight regulator, the oil-soluble compound-encapsulated water-dispersed polymer fine particles of the present invention can be obtained, and further the polymer A fine particle aqueous dispersion can be produced.

  The above polymerization temperature, solvent, polymerization initiator, and polymerization time are the same as described above.

In the synthesis of the oil-soluble compound-encapsulated water-dispersed polymer fine particles having the amino group-containing hydrophilic polymer chain and the polyalkylene glycol chain on the fine particle surface of the present invention, the amino group-containing hydrophilic macromonomer and the polyalkylene glycol macro The ratio of the monomer is not particularly limited. Further, the ratio of the total amount of the amino group-containing hydrophilic macromonomer and the polyalkylene glycol macromonomer and the hydrophobic radical polymerizable monomer is not particularly limited, but the repeating unit of the amino group-containing hydrophilic macromonomer And the ratio of the total of the alkylene glycol units and the hydrophobic radical polymerizable monomer is preferably in the range of 1: 100 to 0.01, more preferably in the range of 1:10 to 0.1, and 1: 5 to 0.00. 2 is particularly preferred.

  In the synthesis of the oil-soluble compound-encapsulated water-dispersed polymer fine particles of the present invention, the polymer compound having an amino group-containing structural unit is polyethyleneimine, the compound represented by the general formula (1) is chloromethylstyrene, the general formula A combination containing benzyl chloride is particularly preferred as the compound represented by (2), and methoxypolyethylene glycol methacrylate is particularly preferred as the compound represented by the general formula (4).

The oil-soluble compound-encapsulated water-dispersed polymer fine particles of the present invention include a polymer compound having an amino group-containing structural unit as described above, a vinylbenzyl halide represented by the general formula (1), and the general formula (2). At least one amino group-containing hydrophilic macromonomer obtained by reacting with a benzyl halide represented by the formula and at least one polyalkylene glycol macromonomer represented by the general formula (4) as described above, It is obtained by copolymerizing at least one radical polymerizable monomer in an aqueous medium in the presence of an oil-soluble compound, and is classified into primary and / or secondary and localized on the surface of fine particles by the production method of the present invention. Hydrophilic polymer chain having tertiary amino group and / or alkylene glycol chain, hydrophobic polymer compound forming core of fine particles, and encapsulated in core It is possible to produce an aqueous dispersion of composed particulates from the oil-soluble compound.

Next, oil-soluble compound-encapsulated water-dispersed polymer particles having the carboxylic acid and / or carboxylate-containing hydrophilic polymer chain and polyalkylene glycol chain of the present invention on the surface of the particles, and a method for producing the polymer particle aqueous dispersion Will be described.

The hydrophobic radical polymerizable monomer, bifunctional hydrophobic radical polymerizable monomer, and oil-soluble compound in the present invention are the same as described above.

At least one selected from the above-mentioned carboxylic acid and / or carboxylate-containing hydrophilic macromonomer, at least one polyalkylene glycol macromonomer, and a hydrophobic radical polymerizable monomer. Can be obtained in the presence of an oil-soluble compound, a polymerization initiator and, if necessary, a molecular weight regulator in an aqueous medium to obtain the oil-soluble compound-encapsulated water-dispersed polymer fine particles of the present invention. Furthermore, an aqueous dispersion of the polymer fine particles can be produced.

  The above polymerization temperature, solvent, polymerization initiator, and polymerization time are the same as described above.

In the synthesis of oil-soluble compound-encapsulated water-dispersed polymer fine particles having a carboxylic acid and / or carboxylate-containing hydrophilic polymer chain and a polyalkylene glycol chain on the fine particle surface of the present invention, the carboxylic acid and / or carboxylate described above is synthesized. The ratio of the containing hydrophilic macromonomer and the polyalkylene glycol macromonomer is not particularly limited. Further, the ratio of the total amount of the carboxylic acid and / or carboxylate-containing hydrophilic macromonomer and the polyalkylene glycol macromonomer to the hydrophobic radical polymerizable monomer is not particularly limited. Alternatively, the ratio of the total of repeating units of the carboxylate-containing hydrophilic macromonomer, the alkylene glycol unit, and the hydrophobic radical polymerizable monomer is preferably in the range of 1: 100 to 0.01, and 1:10 to 0.1. Is more preferable, and 1: 5 to 0.2 is particularly preferable.

  In the synthesis of the oil-soluble compound-encapsulated water-dispersed polymer fine particles of the present invention, as a polymer compound having a carboxylic acid and / or carboxylate-containing structural unit, polyacrylic acid, a compound represented by the general formula (3) A combination of glycidyl methacrylate is particularly preferable, and methoxypolyethylene glycol methacrylate is particularly preferable as the compound represented by the general formula (4).

The oil-soluble compound-encapsulated water-dispersed polymer fine particles of the present invention include a polymer compound having a carboxylic acid and / or carboxylate-containing structural unit as described above and a glycidyl (meth) acrylate represented by the general formula (3). Hydrophobic radical polymerization with at least one kind of a carboxylic acid and / or carboxylate-containing hydrophilic macromonomer and a polyalkylene glycol macromonomer represented by the general formula (4) The carboxylic acid and / or the carboxylate salt obtained by copolymerizing at least one kind of a monomer in an aqueous medium in the presence of an oil-soluble compound and localized on the surface of fine particles by the production method of the present invention Hydrophobic polymer chain and polyalkylene glycol chain, hydrophobic polymer compound that forms fine particle core, and oil soluble in core It is possible to produce an aqueous dispersion of composed particulates from compound.

FIG. 1 shows, for example, an oil-soluble compound-encapsulated water-dispersed polymer obtained by copolymerizing an amino group-containing hydrophilic macromonomer represented by 5c and a hydrophobic radical polymerizable monomer in the presence of an oil-soluble compound. It is a schematic representation of a typical mechanism for obtaining fine particles. The amino group-containing hydrophilic macromonomer 1 comprises an ethyleneimine unit 1a and a vinylbenzyl group 1b. First, when the amino group-containing hydrophilic macromonomer 1, the hydrophobic radical polymerizable monomer 2 and the water-insoluble oil-soluble compound 3 are mixed (step A), and the hydrophobic radical polymerizable monomer is polymerized. Polymerization of the hydrophobic radical polymerizable monomer (step B) partially occurs, but copolymerization with the vinylbenzyl group 1b (step C) occurs simultaneously. As a result of the copolymerization, a polymer having a structure as if an amino group-containing hydrophilic macromonomer is grafted to a polymer of a hydrophobic radical polymerizable monomer is obtained. Since the reaction is carried out in an aqueous medium, the polymer of hydrophobic radically polymerizable units and the oil-soluble compound are selectively accumulated on the inner side, and the amino group-containing hydrophilic macromonomer 1 is selectively accumulated on the outer side (Step D). When the polymerization is completed in this manner, the oil-soluble compound in which the amino group-containing hydrophilic polymer chain 5 is located on the surface of the core portion 4 composed of the polymer of the hydrophobic radical polymerizable monomer and the oil-soluble compound. The encapsulated water-dispersed polymer fine particles 6 are obtained (Step E).

Hereinafter, the features of the present invention will be made clearer by giving examples and comparative examples, but the present invention is not limited to the following examples. In addition, the weight average molecular weight of the polymer in a comparative manufacture example and a manufacture example was measured in accordance with the following method.
<Measurement of polymer weight average molecular weight and polymerization yield>
It was measured by GPC method using Tosoh CO-8020 for the column thermostat, Tosoh RI-8020 for the detector, Tosoh PX-8020 for the eluent flow path pump, and Tosoh SD-8022 for the degasser. . The column used was a Tosoh water-based SEC column TSKgelG3000PWXL (exclusion limit molecular weight 2 × 10 ⁵ ) and TSKgelG2500PWXL (exclusion limit molecular weight 5 × 10 ³ ). The sample was prepared to a concentration of 2 g / 100 ml with an eluent and used for measurement. As an eluent, an aqueous solution adjusted to 0.5 mol / liter each of acetic acid and sodium acetate was used. The column temperature was 40 ° C. and the flow rate was 1.0 ml / min. A calibration curve was determined using six types of polyethylene glycol having molecular weights of 700, 1065, 2560, 5000, 10750, and 14600 as standard samples, and the weight average molecular weight of the polymer was determined based on the calibration curve. The particle size of the hydrophilic polymer fine particles according to the present invention was measured by a dynamic light scattering method (Malvern: Zetasizer Nano ZS) or a laser diffraction / scattering method (Nikkiso: Microtrack MT3300EX).

[Synthesis Example 1]
Synthesis of limonene-encapsulated cationic polymer fine particle aqueous dispersion <1>
In a reaction vessel equipped with a stirrer, an air-cooled tube, a dropping funnel, and a thermometer, 40.00 g of water and 31.73 g of polyethyleneimine (ethyleneimine unit 721 mmol, weight average molecular weight 950) were charged and heated to a temperature of 40. The temperature was raised to ° C. A mixed solution of 24.86 g (196 mmol) of benzyl chloride and 3.41 g (22 mmol) of p-chloromethylstyrene was added dropwise over 1 hour. After completion of dropping, the mixture was kept at 40 ° C. for 2 hours to obtain a polyethyleneimine macromonomer solution having a vinylbenzyl group (solid content concentration 60%). After completion of the reaction, the polyethyleneimine macromonomer was purified by reprecipitation with acetone several times. The weight average molecular weight determined from GPC (liquid chromatography) of the obtained polyethyleneimine macromonomer was 1,900.

  Next, in a reaction vessel equipped with a stirrer, a reflux condenser, and a thermometer, 22.06 g of the polyethyleneimine macromonomer solution [160 mmol as ethyleneimine unit repeating unit (obtained from pre-charging)], 16.66 g of styrene (160 mmol) ), 12.00 g of limonene and 47.78 g of water were charged and the temperature was raised to 70 ° C. 1.50 g (1.31 mmol) of a 20% by weight aqueous solution of ammonium persulfate was added and copolymerized for 6 hours to obtain a pale horizontal milky white dispersion (solid content concentration 42%). The average particle size of the cationic limonene-containing water-dispersed polymer fine particles obtained in this manner was 110 nm.

[Synthesis Example 2]
Synthesis of lauryl alcohol-containing cationic polymer fine particle aqueous dispersion <2>
A pale horizontal milky white dispersion (solid content concentration 42%) was obtained in the same manner as in Synthesis Example 1 except that limonene of Synthesis Example 1 was changed to lauryl alcohol. The average particle diameter of the thus obtained cationic lauryl alcohol-encapsulated water-dispersed polymer fine particles was 140 nm.

[Synthesis Example 3]
Synthesis of N, N-diethyl-m-toluamide-containing cationic polymer fine particle aqueous dispersion <3>
A pale horizontal milky white dispersion (solid content concentration 42%) was obtained in the same manner as in Synthesis Example 1 except that limonene of Synthesis Example 1 was changed to N, N-diethyl-m-toluamide. The average particle size of the cationic N, N-diethyl-m-toluamide-encapsulated water-dispersed polymer fine particles obtained in this manner was 130 nm.

[Synthesis Example 4]
Synthesis of aqueous dispersion of limonene-encapsulated anionic polymer particles <4>
In a reaction vessel equipped with a stirrer, an air cooling tube and a thermometer, water 18.00 g, polyacrylic acid 40% aqueous solution 53.20 g (acrylic acid unit 295 mmol, weight average molecular weight 6,000), sodium hydroxide 48% Aqueous solution 24.60 g and glycidyl methacrylate 4.20 g (29.5 mmol) were charged and heated to raise the temperature to 40 ° C. By maintaining at 40 ° C. for 6 hours, a sodium polyacrylate macromonomer solution having a methacryloyl group (solid content concentration: 32%) was obtained. After completion of the reaction, polyacrylic acid macromonomer was purified by reprecipitation with acetone several times. The weight average molecular weight calculated | required from GPC (liquid chromatography) of the obtained sodium polyacrylate macromonomer was 7,000.

  Next, in a reaction vessel equipped with a stirrer, a reflux condenser and a thermometer, 22.16 g of the above-mentioned sodium polyacrylate macromonomer solution [65 mmol as acrylic acid unit repeating unit (determined from pre-charging)], 7.78 g of styrene (75 mmol), 6.00 g of limonene and 62.56 g of water were charged and the temperature was raised to 70 ° C. 1.50 g (1.31 mmol) of a 20% by weight aqueous solution of ammonium persulfate was added and copolymerized for 6 hours to obtain a milky white dispersion (solid content concentration 20%). The average particle size of the anionic limonene-containing water-dispersed polymer fine particles obtained in this manner was 100 nm.

[Synthesis Example 5]
Synthesis of an aqueous dispersion of anionic polymer fine particles encapsulating lauryl alcohol <5>
A milky white dispersion (solid content concentration 20%) was obtained in the same manner as in Synthesis Example 4 except that limonene of Synthesis Example 4 was changed to lauryl alcohol. The average particle size of the anionic lauryl alcohol-containing water-dispersed polymer fine particles obtained in this manner was 120 nm.

[Synthesis Example 6]
Synthesis of N, N-diethyl-m-toluamide encapsulating anionic polymer fine particle aqueous dispersion <6>
A milky white dispersion (solid concentration 20%) was obtained in the same manner as in Synthesis Example 4 except that limonene of Synthesis Example 4 was changed to N, N-diethyl-m-toluamide. The average particle diameter of the anionic N, N-diethyl-m-toluamide-encapsulated water-dispersed polymer fine particles thus obtained was 110 nm.

[Synthesis Example 7]
Synthesis of limonene-encapsulated nonionic polymer fine particle aqueous dispersion <7>
In a reaction vessel equipped with a stirrer, a reflux condenser and a thermometer, 10.00 g of methoxypolyethylene glycol methacrylate [227 mmol as ethylene glycol unit repeating unit, weight average molecular weight is 4,000], 10.00 g (96 mmol) of styrene, Limonene (8.00 g) and water (70.50 g) were charged and the temperature was raised to 70 ° C. 1.50 g (1.31 mmol) of a 20% by weight aqueous solution of ammonium persulfate was added and copolymerized for 6 hours to obtain a milky white dispersion (solid content concentration 28%). The average particle size of the nonionic limonene-containing water-dispersed polymer fine particles obtained in this manner was 150 nm.

[Synthesis Example 8]
Synthesis of lauryl alcohol-encapsulated nonionic polymer fine particle aqueous dispersion <8>
A milky white dispersion (solid content concentration 20%) was obtained in the same manner as in Synthesis Example 7 except that limonene of Synthesis Example 7 was changed to lauryl alcohol. The average particle size of the nonionic lauryl alcohol-containing water-dispersed polymer fine particles obtained in this manner was 170 nm.

[Synthesis Example 9]
Synthesis of N, N-diethyl-m-toluamide-encapsulated nonionic polymer fine particle aqueous dispersion <9>
A milky white dispersion (solid concentration 20%) was obtained in the same manner as in Synthesis Example 7 except that limonene of Synthesis Example 7 was changed to N, N-diethyl-m-toluamide. The average particle size of the nonionic N, N-diethyl-m-toluamide-encapsulated water-dispersed polymer fine particles obtained in this manner was 160 nm.

Synthesis of Limonene-Encapsulated Cation / Nonionic Polymer Fine Particle Water Dispersion <10>
In a reaction vessel equipped with a stirrer, a reflux condenser and a thermometer, 12.06 g of the polyethyleneimine macromonomer solution of Synthesis Example 1 [87 mmol as an ethyleneimine unit repeating unit (obtained from the previous preparation)], methoxypolyethyleneglycol methacrylate 10.00 g [227 mmol as ethylene glycol unit repeating unit, weight average molecular weight is 4,000], 16.66 g (160 mmol) of styrene, 12.00 g of limonene and 47.78 g of water were charged and the temperature was raised to 70 ° C. 1.50 g (1.31 mmol) of a 20% by weight aqueous solution of ammonium persulfate was added and copolymerized for 6 hours to obtain a pale horizontal milky white dispersion (solid content concentration 46%). The average particle size of the cation / nonionic limonene-containing water-dispersed polymer fine particles obtained in this manner was 120 nm.

Synthesis of limonene encapsulated anion / nonionic polymer fine particle aqueous dispersion <11>
In a reaction vessel equipped with a stirrer, a reflux condenser, and a thermometer, 17.16 g of the sodium polyacrylate macromonomer solution of Synthesis Example 4 [51 mmol as an acrylic acid unit repeating unit (determined from the previous preparation)], methoxypolyethylene Glycol methacrylate 5.00 g [114 mmol as ethylene glycol unit repeating unit, weight average molecular weight is 4,000], 7.78 g (75 mmol) of styrene, 6.00 g of limonene and 62.56 g of water were charged and the temperature was raised to 70 ° C. 1.50 g (1.31 mmol) of a 20 wt% aqueous solution of ammonium persulfate was added and copolymerized for 6 hours to obtain a milky white dispersion (solid content concentration 25%). The average particle size of the anionic limonene-containing water-dispersed polymer fine particles obtained in this manner was 105 nm.

[Comparative Synthesis Example 1]
In a reaction vessel equipped with a stirrer, an air-cooled tube, a dropping funnel and a thermometer, 64.86 g of water and 31.73 g of polyethyleneimine (ethyleneimine unit 721 mmol, weight average molecular weight 950) are charged and heated to a temperature of 40. The temperature was raised to ° C. A liquid mixture of 3.41 g (22 mmol) of p-chloromethylstyrene was added dropwise over 1 hour and then kept at 40 ° C. for 2 hours to obtain a polyethyleneimine macromonomer solution having a vinylbenzyl group (solid content concentration: 35%). . After completion of the reaction, the polyethyleneimine macromonomer was purified by reprecipitation with acetone several times. The weight average molecular weight obtained from GPC (liquid chromatography) of the obtained polyethyleneimine macromonomer was 1,100.

  Next, in a reaction vessel equipped with a stirrer, a reflux condenser, and a thermometer, 22.06 g of the polyethyleneimine macromonomer solution [160 mmol as ethyleneimine unit repeating unit (obtained from pre-charging)], 16.66 g of styrene (160 mmol) ), 12.00 g of limonene and 47.78 g of water were charged and the temperature was raised to 70 ° C. When 1.50 g (1.31 mmol) of a 20% by weight aqueous solution of ammonium persulfate was added and copolymerized for 6 hours, aggregates having a particle size of about 1 mm were formed.

[Comparative Synthesis Example 2]
In a reaction vessel equipped with a stirrer, an air-cooled tube, a dropping funnel, and a thermometer, 40.00 g of water and 31.73 g of polyethyleneimine (ethyleneimine unit 721 mmol, weight average molecular weight 950) were charged and heated to a temperature of 40. The temperature was raised to ° C. After 24.86 g (196 mmol) of benzyl chloride was added dropwise over 1 hour, the solution was kept at 40 ° C. for 2 hours to obtain an aqueous solution of polyethylenimine / benzyl chloride adduct (solid content concentration 57%). After completion of the reaction, reprecipitation with acetone was performed several times to purify the polyethylenimine / benzyl chloride quaternized product. The weight average molecular weight calculated | required from GPC (liquid chromatography) of the obtained refinement | purification was 1,700.

  Next, in a reaction vessel equipped with a stirrer, a reflux condenser and a thermometer, 22.06 g of the above-mentioned aqueous solution of polyethyleneimine / benzyl chloride adduct [160 mmol as ethyleneimine unit repeating unit (determined from previous preparation)], styrene 16 .66 g (160 mmol), limonene 12.00 g, and water 47.78 g were charged and the temperature was raised to 70 ° C. When 1.50 g (1.31 mmol) of a 20% by weight aqueous solution of ammonium persulfate was added and copolymerized for 6 hours, aggregates having a particle size of about 1 mm were formed.

[Comparative Synthesis Example 3]
In a container equipped with a stirrer, 22.20 g of water, 53.20 g of polyacrylic acid 40% aqueous solution (acrylic acid unit 295 mmol, weight average molecular weight 6,000), and sodium hydroxide 48% aqueous solution 24.60 g were charged. A sodium polyacrylate solution (solid content concentration 28%) was obtained.

  Next, in a reaction vessel equipped with a stirrer, a reflux condenser and a thermometer, 22.16 g of the above-mentioned sodium polyacrylate solution [65 mmol as acrylic acid unit repeating unit (obtained from pre-charging)], 7.78 g (75 mmol) of styrene ), 6.00 g of limonene and 62.56 g of water were charged and the temperature was raised to 70 ° C. When 1.50 g (1.31 mmol) of a 20 wt% aqueous solution of ammonium persulfate was added and copolymerized for 6 hours, an aggregate having a particle size of about 1 mm was formed.

[Comparative Synthesis Example 4]
In a reaction vessel equipped with a stirrer, a reflux condenser and a thermometer, 10.00 g of polyethylene glycol [227 mmol as ethylene glycol unit repeating unit, weight average molecular weight is 4,000], 10.00 g of styrene (96 mmol), limonene 8 0.000 g and 70.50 g of water were charged and the temperature was raised to 70 ° C. When 1.50 g (1.31 mmol) of a 20 wt% aqueous solution of ammonium persulfate was added and copolymerized for 6 hours, an aggregate having a particle size of about 1 mm was formed.

[Comparative Synthesis Example 5]
In a reaction vessel equipped with a stirrer, a reflux condenser, and a thermometer, 12.06 g of the polyethyleneimine macromonomer solution of Comparative Synthesis Example 1 [87 mmol as an ethyleneimine unit repeating unit (obtained from the previous preparation)], polyethylene glycol 10 0.000 g [227 mmol as ethylene glycol unit repeating unit, weight average molecular weight: 4,000], 16.66 g (160 mmol) of styrene, 12.00 g of limonene and 47.78 g of water were charged and the temperature was raised to 70 ° C. When 1.50 g (1.31 mmol) of a 20% by weight aqueous solution of ammonium persulfate was added and copolymerized for 6 hours, aggregates having a particle size of about 1 mm were formed.

[Comparative Synthesis Example 6]
In a reaction vessel equipped with a stirrer, a reflux condenser, and a thermometer, 17.16 g of a sodium polyacrylate solution of Comparative Synthesis Example 3 [51 mmol as an acrylic acid unit repeating unit (obtained from pre-charging)], polyethylene glycol 5 0.000 g [114 mmol as ethylene glycol unit repeating unit, weight average molecular weight is 4,000], 7.78 g (75 mmol) of styrene, 6.00 g of limonene and 62.56 g of water were charged and the temperature was raised to 70 ° C. When 1.50 g (1.31 mmol) of a 20 wt% aqueous solution of ammonium persulfate was added and copolymerized for 6 hours, an aggregate having a particle size of about 1 mm was formed.

  Table 1 shows the composition and particle size of each synthesis example of the oil-soluble compound-containing water-dispersed polymer fine particles of the present invention.

The following abbreviations mean the following compounds:
PEI: polyethyleneimine BC: benzyl chloride CMSt: chloromethylstyrene St: styrene PAAcNa: sodium polyacrylate GMA: glycidyl methacrylate PEG-MA: methoxypolyethylene glycol methacrylate PEG: polyethylene glycol L-OH: lauryl alcohol DEET: N, N- Diethyl-m-toluamide

  By the method of the present invention, an aqueous dispersion having a hydrophilic polymer chain on the particle surface and encapsulating an oil-soluble compound was obtained. In the method according to the comparative synthesis example, the polymerized polymer aggregated, and the oil-soluble compound floated in the upper layer.

It is the schematic showing the mechanism in which polymer microparticles are obtained.

DESCRIPTION OF SYMBOLS 1 ... Amino group containing hydrophilic macromonomer 1a ... Ethyleneimine unit 1b ... Vinylbenzyl group 2 ... Hydrophobic radical polymerizable monomer 3 ... Water-insoluble oil-soluble compound 4 ... Core part 5 composed of a polymer of a hydrophobic radical polymerizable monomer and an oil-soluble compound 5... Amino group-containing hydrophilic polymer chain 6...

Claims (6)

At least one selected from polymer compounds having an amino group-containing structural unit, at least one selected from compounds represented by the following general formula (1), and the following general formula (2) An amino group-containing hydrophilic macromonomer obtained by reacting at least one selected from compounds;
[In Formula (1), R ₁ represents a hydrogen atom or a methyl group, R ₂ represents a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, or a halogen atom, and X ₁ represents a halogen atom. ]
Wherein _{(2), R 3, R} 4 are the same or different and each represents a hydrogen atom or a lower alkyl group or a halogen atom having 1 to 4 carbon atoms, _{X 2} represents a halogen atom. ]
Cationic oil obtained by radical polymerizing at least one selected from hydrophobic radical polymerizable monomers in an aqueous medium in the presence of a water-insoluble oil-soluble compound Water-dispersed polymer fine particles containing soluble compounds. Reacting at least one selected from polymer compounds having a carboxylic acid and / or carboxylate-containing structural unit with at least one selected from compounds represented by the following general formula (3): A carboxylic acid and / or carboxylate-containing hydrophilic macromonomer comprising:
[In formula (3), R ₅ represents a hydrogen atom or a methyl group, and Q ₁ represents an oxygen atom or —NH—. ]
An anionic oil obtained by radical polymerizing at least one selected from hydrophobic radical polymerizable monomers in an aqueous medium in the presence of a water-insoluble oil-soluble compound Water-dispersed polymer fine particles containing soluble compounds. At least one polyalkylene glycol macromonomer selected from compounds represented by the following general formula (4);
[In the formula (4), R ₆ and R ₇ are the same or different and each represents a hydrogen atom or a methyl group, Q ₂ represents an oxygen atom or —NH—, Q ₃ represents methylene or propylene, and n represents 1 to A number of 100 is shown. ]
Nonionic oil obtained by radical polymerization in an aqueous medium in the presence of a water-insoluble oil-soluble compound with at least one selected from hydrophobic radical polymerizable monomers Water-dispersed polymer fine particles containing soluble compounds.   The amino group-containing hydrophilic macromonomer according to claim 1 and the polyalkylene glycol macromonomer according to claim 3 and at least one selected from hydrophobic radical polymerizable monomers are water-insoluble and oil-soluble. Oil-soluble compound-encapsulated water-dispersed polymer fine particles obtained by radical polymerization in an aqueous medium in the presence of a compound.   The carboxylic acid and / or carboxylate-containing hydrophilic macromonomer according to claim 2, the polyalkylene glycol macromonomer according to claim 3, and at least one selected from hydrophobic radical polymerizable monomers. An oil-soluble compound-encapsulated water-dispersed polymer fine particle obtained by radical polymerization in an aqueous medium in the presence of a water-insoluble oil-soluble compound. A method for producing a polymer fine particle dispersion encapsulating an oil-soluble compound, which is synthesized by the method according to claim 1.