JP4317941B2 - Aperture fine particles and method for producing the same - Google Patents

Description

  The present invention relates to hollow fine particles having openings and used for assisting dispersion of fine powder in a medium, and a method for producing the same.

  When very fine liquid droplets or solid particles having a particle diameter of the order of 10 μm or less are dispersed in a liquid, they may aggregate and be difficult to uniformly disperse. Also, when liquid droplets or solid particles are dispersed in a medium having a high viscosity such as a molten film, uniform dispersion is difficult due to the high viscosity of the medium. In particular, in the former case, there is a concern that evaporation may occur in the dispersion step, and a high temperature, long time dispersion step cannot be taken.

  In such a case, it is convenient if fine particles having a hollow portion that can accommodate the target substance and having an opening that can be rapidly released later can be used. Such fine particles are required to have a particle size corresponding to the size to be dispersed.

  However, if such a small fine particle is formed and then an attempt is made to open a hole mechanically, the fine particle itself is crushed and the hole cannot be formed.

In addition, in the patent documents 1 and 2, the present applicant discloses a simple method for producing hollow polymer fine particles.
JP-A-8-20604 JP 2002-80503 A

  An object of the present invention is to provide a hollow fine particle having an opening and a simple production method thereof.

The inventors of the present invention have made researches to solve the above problems, and have obtained the following knowledge.
(1) In the following hydrophilic solvent (f), the following (a) to (e)
(A) A poorly water-soluble monomer containing a monomer having two or more polymerizable reactive groups.
(B) Seed polymer particles which are dissolved in the poorly water-soluble monomer (a) or swell by absorbing it.
(C) A poorly water-soluble organic solvent that dissolves or swells the polymer formed from the poorly water-soluble monomer (a) and the seed polymer particles (b).
(D) A dispersion stabilizer having an ionic or nonionic surface active ability with a molecular weight of 20000 or less.
(E) An oil-soluble polymerization initiator.
(F) A hydrophilic solvent that dissolves the poorly water-soluble monomer (a) and does not dissolve the polymer formed from the monomer (a) and the seed polymer particles (b).
A step of preparing a dispersion by dispersing the above; a water-insoluble monomer (a), a water-insoluble organic solvent (c), and an oil-soluble polymerization initiator (e) among (a) to (e) constituting the dispersion A step of causing the seed polymer particles (b) to absorb the poorly water-soluble monomer (a), the poorly water-soluble organic solvent (c), and the oil-soluble polymerization initiator (e) by reducing the solubility of the seed polymer particles; (B) by selectively polymerizing the hardly water-soluble monomer (a), hollow fine particles having a shell mainly composed of the hardly water-soluble monomer (a) and a hollow portion, An opening is obtained.
(2) Polymerization of (A) a crosslinkable monomer or a crosslinkable monomer and a monofunctional monomer in an aqueous solution of a dispersion stabilizer having an ionic or nonionic surfactant having a molecular weight of 20000 or less, and (B) the above monomer. Alternatively, the polymer obtained by copolymerization or a copolymer having low compatibility with a poorly water-soluble solvent and (C) a mixture containing an initiator is dispersed and subjected to suspension polymerization to perform crosslinking. A hollow fine particle having a shell and a hollow portion composed of a polymer or copolymer of a functional monomer, or a copolymer of a crosslinkable monomer and a monofunctional monomer, and having an open shell is obtained.
(3) In the methods (1) and (2), when the dispersion stabilizer concentration is in a specific range, an opening is easily formed, and the higher the dispersion stabilizer concentration is within this range, the larger the opening area is. Will increase.
(4) In each method of Patent Documents 1 and 2, a polymer dispersion stabilizer is used as a dispersion stabilizer. However, when a low molecular weight surfactant is used, this is not limited to polymerization in oil droplets but in an aqueous phase. This is because it was thought that by-emulsion polymerization occurred together and by-product fine particles were easily formed. In the present invention, it was surprisingly found that by using a surfactant having a molecular weight of 20000 or less, hollow fine particles having an opening can be obtained. However, in that case, the concurrent occurrence of by-product fine particles is suppressed.

  The present invention has been completed based on the above findings, and provides the following open hollow fine particles and a method for producing the same.

  Item 1. A shell having an opening and a hollow portion, wherein the shell is a polymer or copolymer of a polyfunctional monomer and a polymer or copolymer of a monofunctional monomer, or a polyfunctional monomer and a monofunctional Open hollow microparticles composed of a copolymer of a functional monomer and a polymer or copolymer of a monofunctional monomer.

Item 2. Item 2. The open hollow fine particle according to Item 1, wherein the surface area of the opening occupies 10 ^{−3 to} 20% of the shell surface area when it is assumed that there is no opening.

  Item 3. Item 3. The open hollow fine particles according to Item 1 or 2, wherein the average particle size is 0.1 to 50 µm.

Item 4. A step of preparing a dispersion by dispersing the following (a) to (e) in the following hydrophilic solvent (f):
Seed polymer particles by reducing the solubility of the poorly water-soluble monomer (a), the poorly water-soluble organic solvent (c), and the oil-soluble polymerization initiator (e) among (a) to (e) constituting the dispersion system. (B) absorbing the poorly water-soluble monomer (a), the poorly water-soluble organic solvent (c), and the oil-soluble polymerization initiator (e);
A step of selectively polymerizing the poorly water-soluble monomer (a) in the seed polymer particles (b).
(A) A poorly water-soluble monomer containing a monomer having two or more polymerizable reactive groups.
(B) Seed polymer particles which are dissolved in the poorly water-soluble monomer (a) or swell by absorbing it.
(C) A poorly water-soluble organic solvent that dissolves or swells the polymer and seed polymer particles (b) formed from the poorly water-soluble monomer (a).
(D) A dispersion stabilizer having an ionic or nonionic surface active ability with a molecular weight of 20000 or less.
(E) An oil-soluble polymerization initiator.
(F) A hydrophilic solvent that dissolves the poorly water-soluble monomer (a) and does not dissolve the polymer formed from the monomer (a) and the seed polymer particles (b).

  Item 5. Item 5. The method according to Item 4, wherein the dispersion stabilizer (d) comprises an anionic surfactant.

Item 6. Item 6. The method according to Item 4 or 5, wherein the concentration of the dispersion stabilizer (d) with respect to the hydrophilic solvent is 0.1 to 10 g / m ² per unit oil droplet total area.

Item 7. A step of preparing a dispersion by dispersing the following (a), (b), (c), (d ′) and (e) in the following hydrophilic solvent (f):
Among the (a), (b), (c), (d ′) and (e) constituting the dispersion, the poorly water-soluble monomer (a), the poorly water-soluble organic solvent (c), and the oil-soluble polymerization initiator ( e) absorbing the poorly water-soluble monomer (a), the poorly water-soluble organic solvent (c), and the oil-soluble polymerization initiator (e) into the seed polymer particles (b) by reducing the solubility of e);
The following step (d) adding a dispersion stabilizer;
A step of selectively polymerizing the poorly water-soluble monomer (a) in the seed polymer particles (b).
(A) A poorly water-soluble monomer containing a monomer having two or more polymerizable reactive groups.
(B) Seed polymer particles which are dissolved in the poorly water-soluble monomer (a) or swell by absorbing it.
(C) A poorly water-soluble organic solvent that dissolves or swells the polymer and seed polymer particles (b) formed from the poorly water-soluble monomer (a).
(D) A dispersion stabilizer having an ionic or nonionic surface active ability with a molecular weight of 20000 or less.
(D ′) A dispersion stabilizer.
(E) An oil-soluble polymerization initiator.
(F) A hydrophilic solvent that dissolves the poorly water-soluble monomer (a) and does not dissolve the polymer formed from the monomer (a) and the seed polymer particles (b).

  Item 8. Item 8. The method according to Item 7, wherein the dispersion stabilizer (d) comprises an anionic surfactant.

Item 9. Item 9. The method according to Item 7 or 8, wherein the concentration of the dispersion stabilizer (d) with respect to the hydrophilic solvent is 0.1 to 10 g / m ² per unit oil droplet total area.

  Item 10. An open hollow microparticle comprising a shell having an opening and a hollow portion, wherein the shell is composed of a polymer or copolymer of a crosslinkable monomer, or a copolymer of a crosslinkable monomer and a monofunctional monomer.

Item 11. Item 11. The open hollow fine particle according to Item 10, wherein the surface area of the opening occupies 10 ^{−3 to} 20% of the surface area of the shell when it is assumed that there is no opening.

  Item 12. Item 12. The open hollow fine particle according to Item 10 or 11, wherein the average particle size is 0.1 to 50 μm.

  Item 13. Item 13. The open hollow fine particle according to any one of Items 10 to 12, wherein the shell is composed of a polymer or copolymer of a crosslinkable monomer.

  Item 14. (A) a crosslinkable monomer, or a crosslinkable monomer and a monofunctional monomer, and (B) the above monomer is polymerized or co-polymerized in an aqueous solution of a dispersion stabilizer having an ionic or nonionic surfactant having a molecular weight of 20000 or less. A method for producing open hollow microparticles, in which a mixture containing a solvent having low compatibility with a polymer or copolymer obtained by polymerization and poorly water-soluble and (C) an initiator is dispersed and suspension polymerization is performed. .

  Item 15. Item 15. The method according to Item 14, wherein the dispersion stabilizer comprises an anionic surfactant.

Item 16. Item 16. The method according to Item 14 or 15, wherein the concentration of the dispersion stabilizer is 0.1 to 10 g / m ² per unit oil droplet total area.

Item 17. As the solvent, the interfacial tension (γ ^x ) (mN / m) between the solvent and water and the interfacial tension (γ ^y ) (mN / m) between the polymer obtained by polymerizing or copolymerizing the monomers and water. The method according to any one of Items 14 to 16, wherein a solvent having a relationship of γ ^x ≧ γ ^y is used.

Item 18. (A) a crosslinkable monomer or a crosslinkable monomer and a monofunctional monomer, (B ′) a hardly water-soluble solvent, (D ) Low compatibility with polymers obtained by polymerizing or copolymerizing monomers, and obtained by polymerizing or copolymerizing monomers with interfacial tension (γ ^p ) (mN / m) between auxiliary polymer and water Suspension polymerization is performed by dispersing a mixture containing an auxiliary polymer in which the relationship between the interfacial tension (γ ^q ) (mN / m) between the polymer and water is γ ^p ≧ γ ^q and (C) the initiator. Open hollow method.

  Item 19. Item 19. The method according to Item 18, wherein the dispersion stabilizer comprises an anionic surfactant.

Item 20. Item 20. The method according to Item 18 or 19, wherein the concentration of the dispersion stabilizer is 0.1 to 10 g / m ² per unit oil droplet total area.

Item 21. As the solvent, the interfacial tension (γ ^x ) (mN / m) between the solvent and water and the interfacial tension (γ ^y ) (mN / m) between the polymer obtained by polymerizing or copolymerizing the monomers and water. The method according to any one of Items 18 to 20, wherein a solvent having a relationship of γ ^x ≧ γ ^y is used.

  According to the present invention, the dispersion stabilizer for the polymerizable mixture is substantially the same as the dynamic swelling method reported in Patent Document 1 and the microsuspension polymerization method reported in Patent Document 2, respectively. As an example, a hollow fine particle having an average particle size of 0.1 to 50 μm having an opening by using an ionic or nonionic surfactant having a molecular weight of 20000 or less instead of the polymer dispersion stabilizer Is obtained.

Hereinafter, the present invention will be described in detail. First, the first production method of the present invention and the open hollow fine particles obtained thereby will be described, and then the second production method of the present invention and the open hollow fine particles obtained thereby will be described.
(I) Method for Producing First Open Hollow Fine Particles of the Present Invention The first method for producing hollow hollow fine particles of the present invention involves dispersing (a) to (e) above in a hydrophilic solvent (f). The solubility of the poorly water-soluble monomer (a), the poorly water-soluble organic solvent (c), and the oil-soluble polymerization initiator (e) among the steps (a) to (e) constituting the dispersion system is reduced. And causing the seed polymer particles (b) to absorb the poorly water-soluble monomer (a), the poorly water-soluble organic solvent (c), and the oil-soluble polymerization initiator (e), and in the seed polymer particles (b) And a step of selectively polymerizing the poorly water-soluble monomer (a) (first aspect).

  Moreover, the manufacturing method of the 1st open hollow microparticles | fine-particles of this invention may also have the following aspects (2nd aspect).

A step of preparing a dispersion by dispersing the following (a), (b), (c), (d ′) and (e) in the following hydrophilic solvent (f):
Among the (a), (b), (c), (d ′) and (e) constituting the dispersion, the poorly water-soluble monomer (a), the poorly water-soluble organic solvent (c), and the oil-soluble polymerization initiator ( e) absorbing the poorly water-soluble monomer (a), the poorly water-soluble organic solvent (c), and the oil-soluble polymerization initiator (e) into the seed polymer particles (b) by reducing the solubility of e);
The following step (d) adding a dispersion stabilizer;
A step of selectively polymerizing the poorly water-soluble monomer (a) in the seed polymer particles (b).
(A) A poorly water-soluble monomer containing a monomer having two or more polymerizable reactive groups.
(B) Seed polymer particles which are dissolved in the poorly water-soluble monomer (a) or swell by absorbing it.
(C) A poorly water-soluble organic solvent that dissolves or swells the polymer and seed polymer particles (b) formed from the poorly water-soluble monomer (a).
(D) A dispersion stabilizer having an ionic or nonionic surface active ability with a molecular weight of 20000 or less.
(D ′) A dispersion stabilizer.
(E) An oil-soluble polymerization initiator.
(F) A hydrophilic solvent that dissolves the poorly water-soluble monomer (a) and does not dissolve the polymer formed from the monomer (a) and the seed polymer particles (b).
Dispersion stabilizer (d)
The dispersion stabilizer (d) may be any ionic surfactant (anionic surfactant, cationic surfactant, amphoteric surfactant) having a molecular weight of 20000 or less and a nonionic surfactant. Can be used without restriction. Such surfactants include commercially available low molecular surfactants and oligomer surfactants. A dispersion stabilizer can be used individually by 1 type or in combination of 2 or more types.

  If the molecular weight is too large, hollow fine particles having no opening are formed. The molecular weight is preferably 5000 or less.

  Examples of the anionic surfactant having a molecular weight of 20000 or less include higher fatty acid salts having 12 to 20 carbon atoms (hereinafter, “higher” means 12 to 30 carbon atoms), secondary higher fatty acid salts, and higher alkyl dicarboxylic acids. Carboxylic acid type anionic surfactant such as acid salt; primary higher alcohol sulfate ester salt, sulfate type anionic surfactant such as primary higher alcohol sulfate ester salt; primary higher alkyl Sulfate ester type anionic surfactants such as sulfate esters and secondary higher alkyl sulfates; primary higher alkyl sulfonates, secondary higher alkyl sulfonates, higher alkyl disulfonic acids Sulfonic acid type anionic surfactants such as salts, sulfated fats and sulfated fatty salts, sulfonated higher fatty acid salts; higher alkyl phosphates Phosphate-type anionic surfactants such as: alkylbenzene sulfonates, alkylphenol sulfonates, alkylnaphthalene sulfonates, alkylallylsulfonates such as alkyltetralin sulfonates; higher fatty acids Examples include amide sulfonated anionic surfactants such as alkylated sulfate esters of amides and alkylated sulfonates of higher fatty acid amides.

  In particular, an anionic surfactant is preferred. Among the anionic surfactants, alkyl sulfate ester type anionic surfactants are preferable, and alkyl sulfate ester type anionic surfactants having 8 to 30 carbon atoms, particularly 12 to 20 carbon atoms, are more preferable. preferable. Examples of such alkyl sulfate ester type anionic surfactants include sodium decyl sulfate, sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium cetyl sulfate and the like. Most preferred is dodecyl sulfate (typically the sodium salt).

The dispersion stabilizer (d) is oil droplets total area per 0.1 to 10 g / ^{m 2,} preferably about may be used so that 1 to 5 g / ^{m 2} approximately. If the dispersion stabilizer (d) concentration is too low, openings will not be formed. Conversely, if the dispersion stabilizer (d) concentration is too high, emulsion polymerization will occur simultaneously and by-product fine particles will be easily formed. Absent.

The higher the concentration of the dispersion stabilizer (d) within the above range, the higher the ratio of the opening area to the shell surface area.
Dispersion stabilizer (d ')
In the second aspect of the first method of the present invention, a dispersion stabilizer (d ′) is used in the dispersion preparation step. The dispersion stabilizer (d ′) at this time is not limited to those having a molecular weight of 20000 or less, and any dispersion stabilizer can be used. For example, polymer dispersion stabilizers such as polyvinyl alcohol, methyl cellulose, ethyl cellulose, polyacrylic acid, polyacrylimide, polyethylene oxide, poly (hydroxystearic acid-g-methyl methacrylate-co-methacrylic acid) copolymer, nonion -Based surfactants, anionic surfactants, amphoteric surfactants and the like.

  The amount of the dispersion stabilizer used is about 0.005 to 1 part by weight, particularly 0.01 to 0 part per 1 part by weight of the homogeneous solution comprising the above (a), (b), (c) and (e). It is preferably about 1 part by weight.

Further, in the dispersion stabilizer solution, the concentration of the dispersion stabilizer may be appropriately selected so as to be a concentration at which the droplets do not coalesce. In general, the concentration of the dispersion stabilizer solution is preferably adjusted to a range of about 0.05 to 5 parts by weight, particularly about 0.1 to 1 part by weight.
Water-insoluble monomer (a)
The poorly water-soluble monomer (a) is an olefinic unsaturated monomer having radical polymerizability, and is a polyfunctional monomer having two or more polymerizable reactive groups, or such a polyfunctional monomer and a polymerizable reactive group. It is a mixture with monofunctional monomers.
<Multifunctional monomer>
A polyfunctional monomer can be used individually by 1 type or in combination of 2 or more types.
Examples of the polyfunctional monomer include a polymerizable reactive group, particularly a polyfunctional monomer having two or more polymerizable double bonds (particularly 2 to 4). In particular, a polyfunctional monomer having two or more polymerizable C═C double bonds (particularly 2 to 4) is preferred. Examples thereof include divinylbenzene, divinylbiphenyl, divinylnaphthalene, diallyl phthalate, triallyl cyanurate, ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, and the like.

When only the polyfunctional monomer is used as the poorly water-soluble monomer (a), divinylbenzene is particularly preferable.
<Monofunctional monomer>
A monofunctional monomer can be used individually by 1 type or in combination of 2 or more types.
Examples of the monofunctional monomer include a monovinyl aromatic monomer, an acrylic monomer, a vinyl ester monomer, a vinyl ether monomer, a monoolefin monomer, a halogenated olefin monomer, and a diolefin.

  Examples of the monovinyl aromatic monomer include a monovinyl aromatic hydrocarbon represented by the following general formula (1), a vinylbiphenyl optionally substituted with a lower (1 to 4 carbon) alkyl group, and a lower (1 to 1 carbon atom). 4) Vinyl naphthalene which may be substituted with an alkyl group.

[Wherein, R ¹ is a hydrogen atom, a lower (1 to 4 carbon atoms) alkyl group or a halogen atom, and R ² is a hydrogen atom, a lower (1 to 4 carbon atoms) alkyl group, a halogen atom, —SO 2 _{3 represents a} Na group, a lower (C1-4) alkoxy group, an amino group or a carboxyl group. ]
In the general formula (1), R ¹ is preferably a hydrogen atom, a methyl group or a chlorine atom, and R ² is preferably a hydrogen atom, a chlorine atom, a methyl group or a —SO ₃ Na group.

  Specific examples of the monovinyl aromatic hydrocarbon represented by the general formula (1) include styrene, α-methylstyrene, vinyltoluene, α-chlorostyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, Examples thereof include sodium styrene sulfonate.

  Furthermore, vinyl biphenyl which may be substituted with a lower alkyl group, and vinyl naphthalene which may be substituted with a lower alkyl group include vinyl biphenyl substituted with a lower alkyl group such as vinyl biphenyl, methyl group and ethyl group. And vinylnaphthalene substituted with a lower alkyl group such as vinylnaphthalene, methyl group, and ethyl group. These monovinyl aromatic monomers can be used alone or in combination of two or more.

  Moreover, as said acrylic monomer, the acrylic monomer represented by following General formula (2) is mentioned.

Wherein, ^{R 3} represents a hydrogen atom or a lower (1-4 carbon atoms) alkyl group, ^{R 4} is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group, a hydroxy 1 to 6 carbon atoms alkyl, lower (1-4 carbon atoms) amino alkyl group or a di _(C 1 -C ₄ alkyl) amino - _(C 1 -C ₄₎ an alkyl group. ]
In the general formula (2), R ³ is preferably a hydrogen atom or a methyl group, and R ⁴ is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a phenyl group, or lower (1 to 4 carbon atoms) hydroxy. An alkyl group and a lower (C1-4) aminoalkyl group are preferred.

  Specific examples of the acrylic monomer include acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylexyl acrylate, cyclohexyl acrylate, phenyl acrylate, methyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, β-hydroxyethyl acrylate, γ-hydroxybutyl acrylate, δ-hydroxybutyl acrylate, β-hydroxyethyl methacrylate, γ-aminopropyl acrylate, γ-N, N-diethylamino acrylate And propyl.

  Examples of the vinyl ester monomer include those represented by the following general formula (3).

[Wherein, R ⁵ represents a hydrogen atom or a lower (1 to 4 carbon atoms) alkyl group. ]
Specific examples of the vinyl ester monomer include vinyl formate, vinyl acetate, vinyl propionate and the like.

  Examples of the vinyl ether monomer include vinyl ether monomers represented by the following general formula (4).

[R ⁶ represents an alkyl group having 1 to 12 carbon atoms, a phenyl group, or a cyclohexyl group. ]
Specific examples of the vinyl ether monomer include vinyl methyl ether, vinyl ethyl ether, vinyl n-butyl ether, vinyl phenyl ether, vinyl cyclohexyl ether and the like.

  Examples of the monoolefin monomer include those represented by the following general formula (5).

[In formula, R < ⁷ > and R < ⁸ > is a hydrogen atom or a lower (C1-C4) alkyl group, and may differ or may be the same respectively. ]
Specific examples of the monoolefin monomer include ethylene, propylene, butene-1, pentene-1, 4-methylpentene-1, and the like.

  Examples of the halogenated olefin-based monomer include vinyl chloride and vinylidene chloride.

  Furthermore, diolefins such as butadiene, isoprene, chloroprene and the like can also be included in the monofunctional monomer.

  As the monofunctional monomer copolymerized with the crosslinkable monomer, a monovinyl aromatic monomer and a vinyl ester monomer are preferable.

  Suitable combinations of the crosslinkable monomer and the monofunctional monomer include the following combinations.

When a polyfunctional monomer and a monofunctional monomer are used in combination, the mixing ratio of the polyfunctional monomer may be 5% by weight or more, preferably 10% by weight or more, more preferably 50% by weight or more. If the amount of the polyfunctional monomer used is too small, the hollow portions of the formed hollow polymer particles may not be spherical and the porosity may be low. Does not occur.
Seed polymer particles (b)
The seed polymer particles (b) used in the present invention are soluble in the monomer (a) or have a property of absorbing and swelling the monomer. In this seed polymer particle (b), “to” means the property of being soluble in the monomer (a) or having the property of at least absorbing the monomer (a) and swelling without reaching the solubility. It means stuff.

  This seed polymer particle (b) is a polymer particle obtained by polymerizing one or two or more of the monomers mentioned in the explanation of the monomer (a). The monomer which comprises seed polymer particle (b) should just use the monofunctional monomer illustrated above.

  In this seed polymer particle, the monomer of the forming material and the monofunctional monomer (a) are generally compounds of the same system, but they may be different.

  Examples of the case of the same system include a combination of styrene polymer particles (b) and styrene monomer (a), and examples of different cases include acrylic polymer particles (b) and styrene. The combination with a system monomer (a) is mention | raise | lifted.

The seed polymer particles (b) usually have a monodisperse or almost monodisperse particle size distribution, and the particle size is generally about 0.01 to 50 μm, preferably about 0.5 to 20 μm. It may be in the range. Such seed polymer particles (b) can be obtained by a dispersion polymerization method or an emulsion polymerization method, which are methods for producing general polymer particles. In addition, the polymer can be easily obtained by pulverization and classification. Among these, a dispersion polymerization method that can obtain a large particle size and can obtain a monodispersed particle size distribution is preferable. If necessary, the seed polymer particles (b) may be aggregates of particles having various particle sizes.
The poorly water-soluble organic solvent (c)
The poorly water-soluble organic solvent (c) dissolves or swells the polymer formed from the monomer (a) and the seed polymer particles (b). In the poorly water-soluble organic solvent (c), “to” has the same meaning as “to” of the seed polymer particles (b).

Examples of the poorly water-soluble organic solvent (c) include aromatic solvents such as toluene, xylene and benzene, esters such as ethyl acetate and butyl acetate, and aliphatic hydrocarbon solvents such as hexane and heptane. Of these, aromatic solvents such as toluene and xylene are preferred.
Oil-soluble polymerization initiator (e)
The oil-soluble polymerization initiator (e) initiates polymerization of the monomer (a) and the like absorbed inside the seed polymer particles (b). Therefore, what is necessary is just to use an oil-soluble thing as this polymeric initiator (e).

Examples of the oil-soluble polymerization initiator (e) include radical polymerization initiators such as azo compounds such as azobisisobutyronitrile, cumene hydroperoxide, t-butyl hydroperoxide, dicumyl peroxide, Those soluble in monomers such as peroxides such as di-t-butyl peroxide, benzoyl peroxide, and lauroyl peroxide. Moreover, you may use the photoinitiator which starts superposition | polymerization by light, such as an ultraviolet-ray. Such a photopolymerization initiator is not particularly limited as long as it is oil-soluble, and includes those conventionally used.
Water-soluble polymerization inhibitor In the first method for producing hollow fine particles of the present invention, it is preferable to use a water-soluble polymerization inhibitor. That is, by reducing the solubility of the monomer (a) in the dispersion, the monomer (a) is forcibly absorbed in the seed polymer particles (b) and almost exists in the dispersion medium part (continuous phase). No longer. However, there is a slight amount remaining in the dispersion medium portion, and when this is polymerized, fine polymer particles are produced. As a result, the resulting hollow polymer particles may have a non-uniform particle size distribution. Therefore, by using the water-soluble polymerization inhibitor, the polymerization of the monomer (a) in the dispersion medium part is prevented, and the particle size distribution of the resulting hollow polymer particles becomes more uniform. In addition, since this polymerization inhibitor is water-soluble, it is not absorbed in the seed polymer particles (b), and there is no possibility of inhibiting the polymerization reaction in the seed polymer particles (b).

The water-soluble polymerization inhibitor is not particularly limited as long as it is water-soluble and insoluble in the monomer (a). Examples of such water-soluble polymerization inhibitors include inorganic polymerization inhibitors and organic polymerization inhibitors. Examples of the inorganic polymerization inhibitors include alkali metal salts such as nitrous acid, thiocyanic acid and isothiocyanic acid, alkali metal salts such as alkaline earth metal salts, ammonium salts and phosphinic acid, and salts of inorganic acids such as alkaline earth metal salts. And a bromide such as sodium and potassium, a halide such as iodide such as sodium, potassium, calcium and ammonium, or a transition metal ion. Examples of the organic polymerization inhibitor include water-soluble hydroquinones, catechols, amines and nitro compounds.
Hydrophilic solvent (f)
Next, the hydrophilic solvent (f) serving as a solvent for the dispersion system will be described.

  Examples of the hydrophilic solvent (f) include lower alcohols such as methanol, ethanol and isopropanol; polyhydric alcohols such as ethylene glycol, propylene glycol, butanediol, diethylene glycol and triethylene glycol; cellosolves such as methyl cellosolve and ethyl cellosolve, acetone And hydrophilic organic solvents such as ketones such as methyl ethyl ketone; ethers such as tetrahydrofuran; esters such as methyl formate.

  Such a hydrophilic solvent (f) is appropriately determined according to the types of the monomer (a) and the seed polymer particles (b). That is, it is necessary to select one that dissolves the monomer (a) and does not dissolve the polymer and the seed polymer particles (b). Among the hydrophilic solvents (f), it is preferable to use a lower alcohol such as ethanol because the monomer (a) is excellent in solubility and can be blended with water at an arbitrary ratio.

The hydrophilic solvent (f) in the first method of the present invention includes water. For example, the above hydrophilic organic solvent can be used alone, but may be used in combination with water. Since the water mixing ratio should not greatly reduce the solubility of the monomer (a), it is usually about 20 to 50% by weight with respect to the total amount of the hydrophilic solvent (f). On the contrary, in the polymerization step of the monomer (a), it is desirable that the solubility of the monomer (a) is as low as possible. Therefore, it is preferable to add as much water as possible. In some cases, the seed particles absorb the hydrophobic monomer. The medium may be replaced with water later.
Other components used In the process for producing the hollow polymer particles of the present invention, various additives such as a colorant, various pigments and a release agent can be used.
Each process
<First aspect>
First, the monomer (a) is dissolved in the hydrophilic solvent (f) to prepare a monomer solution. The amount of the monomer (a) used varies depending on the type of the hydrophilic solvent (f) and the monomer (a), but is usually about 1 to 30% by weight with respect to the hydrophilic solvent.

  Next, seed polymer particles (b), a water-insoluble solvent (c), a dispersion stabilizer (d), a polymerization initiator (e), and, if necessary, a water-soluble polymerization inhibitor are added to this solution.

The addition amount of the seed polymer particles (b) varies depending on the particle size of the target hollow polymer particles. That is, since the hollow polymer particles are formed by increasing the seed polymer particles (b), n ³ times as many monomers are used to increase the particle diameter of the seed polymer particles (b) n times. (A) is required. Therefore, the blending ratio of the seed polymer particles (b) is generally 1: 1 to 1:10 in a weight ratio with respect to the total amount of the monomer (a) and the hardly water-soluble organic solvent (c) in the dispersion. ⁴ , preferably in the range of 1:10 to 1:10 ³ .

  Further, a dispersion of the seed polymer particles (b) (hydrophilic solvent (f), poorly water-soluble monomer (a), seed polymer particles (b), water-insoluble solvent (c), dispersion stabilizer (d) and The blending ratio with respect to the oil-soluble polymerization initiator (e) is usually about 0.01 to 50% by weight, preferably about 0.1 to 20% by weight.

  The amount of the hardly water-soluble solvent (c) used is usually about 10 to 1000% by weight, preferably about 50 to 500% by weight, based on the hardly water-soluble monomer.

  The blending ratio of the dispersion stabilizer (d) is as described above.

  The blending ratio of the polymerization initiator (e) is about 0.001 to 10% by weight, preferably about 0.01 to 5% by weight, based on the monomer (a).

  The blending ratio of the polymerization inhibitor is usually about 0.0001 to 0.1% by weight, preferably about 0.001 to 0.05% by weight, based on the dispersion system for seed polymerization described later.

  Next, the solubility of the monomer (a) and the like is reduced in this dispersion. Examples of means for reducing the solubility include a method of adding water to the dispersion and a method of reducing the temperature of the entire dispersion. In the method of adding water to the dispersion, the medium may be replaced with water completely or almost completely. When a mixture of a hydrophilic organic solvent and water is used as the hydrophilic solvent (f), the hydrophilic organic solvent may be evaporated to relatively increase the water concentration. Preferred is a method in which water is added to the dispersion and the temperature of the dispersion is further lowered in two steps.

  Thus, by reducing the solubility of the monomer (a) and the like, the components of the monomer (a), the poorly water-soluble organic solvent (b), and the oil-soluble polymerization initiator (e) 3 are converted into seed polymer particles (b ) Is forcibly absorbed in. As a result, the seed polymer particles (b) swell. At this time, since the poorly water-soluble organic solvent (c) dissolves the seed polymer particles (b), in the seed polymer particles (b), the dissolving component of the seed polymer particles (b) and the monomer (a ), A poorly water-soluble organic solvent (c), and an oil-soluble polymerization initiator (e). And in the case of a monomer (a), this absorption ratio is 50% or more with respect to the whole monomer (a), Preferably it is 90% or more. The adjustment of the absorptance can be performed by changing the degree of decrease in the solubility of the monomer (a).

  Next, the monomer (a) absorbed in the seed polymer particles (b) is seed-polymerized. In general, this polymerization may be performed in an atmosphere of an inert gas such as nitrogen gas at a temperature of about −30 ° C. to 90 ° C., and preferably about 30 to 80 ° C. This polymerization reaction occurs by the action of the polymerization initiator (e). In addition, the polymerization time varies depending on the type of the absorbed monomer (a) and the like, but generally about 0.1 to 30 hours is appropriate.

  This operation consisting of swelling and seed polymerization may be performed only once, for example, or may be performed a plurality of times until the particles grow to a predetermined particle size.

  By the above operation, the shell mainly contains the polymer or copolymer of the monomer (a), and further contains the constituent polymer or copolymer of the seed polymer particle (b), and the hollow portion, Open hollow microparticles with a part of the opening being obtained.

  Further, in the seed polymerization reaction, if a water-soluble polymerization inhibitor is used as described above, the polymerization reaction of the monomer (a) remaining in the dispersion medium portion does not occur. As a result, it is possible to prevent the formation of fine polymer particles that contribute to the unevenness of the particle size distribution. In this manner, open hollow fine particles having a single true spherical hollow portion can be produced.

In addition, the open hollow fine particles obtained in this way may be used as a dispersion (suspension), or filtered and washed with water if necessary, and then used in various forms in the form of powder. it can. Furthermore, the fine particles in the form of suspension or powder may be dried by natural evaporation, reduced pressure treatment or the like.
<Second aspect>
In the second aspect, in the dispersion preparation step, instead of adding the dispersion stabilizer (d), a poorly water-soluble monomer (a), a poorly water-soluble organic solvent (c), and an oil-soluble polymerization initiator (e) A dispersion stabilizer (d ′) capable of uniformly dispersing the seed polymer particles (b) in the dissolved hydrophilic solvent (f) is added.

  Further, after the step of reducing the concentration of the monomer (a) in the dispersion, for example, the medium is replaced with water, and the dispersion stabilizer (d) is added to the dispersion before the polymerization step of the poorly water-soluble monomer (a). To do.

The addition amount of the dispersion stabilizer in this case (d) is the total usage 0.1 to 10 g / ^{m 2} approximately per oil droplet total area of the dispersion stabilizer (d), and preferably 1 to 5 g / ^{m 2} degree What should I do. That is, when the polymer dispersion stabilizer (d ′) is used in the dispersion preparation step, at this time, the dispersion stabilizer (d) is about 0.1 to 10 g / m ² per total area of the oil droplets, preferably What is necessary is just to add so that it may become about 1-5 g / m < ² >. In addition, when the dispersion stabilizer (d) is used in the dispersion system preparation step, the amount used at this time is 0.1 to 10 g / total oil droplet total area with the addition amount in the dispersion system preparation step. m ^2, preferably about may be such that the 1 to 5 g / ^{m 2} approximately.
(II) First Open Hollow Fine Particle of the Present Invention The first open hollow fine particle of the present invention comprises a shell having an opening and a hollow portion, and the shell is a polymer or copolymer of a polyfunctional monomer and a single unit. It includes a mixture of a polymer or copolymer of a functional monomer, or a mixture of a copolymer of a polyfunctional monomer and a monofunctional monomer and a polymer or copolymer of a monofunctional monomer.

  The polymer or copolymer of the above monofunctional monomer is a constituent component of the polymer particle (b). When the amount of seed polymer particles (b) used is negligibly small relative to the amount of poorly water-soluble monomer (a) used, the shell is substantially a monofunctional monomer polymer or copolymer. Is not included.

The opening is usually single. The surface area of the opening varies depending on the type and amount of the dispersion stabilizer (d), but usually occupies about 10 ^{−3 to} 20% of the shell surface area when there is no opening. Within this range, the opening area can be arbitrarily adjusted by adjusting the amount of use according to the type of the dispersion stabilizer (d).

  The average particle diameter is generally in the range of about 0.1 to 50 μm, preferably about 1 to 10 μm. This particle size distribution is usually monodisperse and uniform.

  Moreover, the volume ratio of the hollow part when it is assumed that no opening is formed in the shell of the first open hollow fine particles of the present invention is about 5 to 80%, particularly about 10 to 50% on average. .

  In the present specification, the “volume ratio of the hollow portion” A is calculated by the following equation.

A (%) = (rh / rp) ³ × 100
(In the formula, rh is the radius of the hollow portion of the open hollow fine particles (1/2 of the inner diameter of the shell), and rp is the radius of the open hollow fine particles (1/2 of the outer diameter of the shell).)
In the present invention, the hollow of the hollow polymer particles is intended to include not only the case where nothing exists in the hollow part but also the case where the poorly water-soluble organic solvent (c) and the like are present in the hollow part. is there.
In the present invention, the average particle diameter, the shell thickness, and the volume ratio of the hollow portion are average values of particle diameters measured with an optical microscope for 200 fine particles.
(III) Production method of second open hollow fine particles of the present invention The second open hollow fine particle production method of the present invention is an aqueous dispersion stabilizer solution having a molecular weight of 20000 or less and having an ionic or nonionic surface active ability. (A) Crosslinkable monomer or crosslinkable monomer and monofunctional monomer, (B) Low compatibility with polymers or copolymers obtained by polymerizing or copolymerizing the above monomers, and poorly water-soluble And (C) a mixture containing an initiator is dispersed to perform suspension polymerization (first embodiment).

The method for producing the second open hollow fine particles of the present invention also includes the following second aspect. That is, in an aqueous solution of a dispersion stabilizer having an ionic or nonionic surface active ability with a molecular weight of 20000 or less, (A) a crosslinkable monomer or a crosslinkable monomer and a monofunctional monomer, (B ′) a poorly water-soluble solvent, (D) The compatibility with the polymer obtained by polymerizing or copolymerizing the monomer is low, and the interfacial tension (γ ^p ) (mN / m) between the auxiliary polymer and water is polymerized or copolymerized. Suspension polymerization is carried out by dispersing a mixture containing an auxiliary polymer in which the relationship between the resulting polymer and water and the interfacial tension (γ ^q ) (mN / m) is γ ^p ≧ γ ^q , and (C) an initiator. Is the way to do.
The type of dispersion stabilizer available dispersion stabilizer are as described for the first aspect of the dispersion stabilizer of the first method of the present invention (d). Moreover, the article weight, the oil droplets total area per 0.1 to 10 g / ^{m 2,} preferably about may be used so that 1 to 5 g / ^{m 2} approximately. If the dispersion stabilizer concentration is too low, it is difficult to form openings, whereas if it is too high, emulsion polymerization occurs simultaneously and by-product fine particles are likely to be produced. However, such a problem does not occur in the above range.
The monomer crosslinking monomer and monofunctional monomer are preferably hydrophobic, but this requirement is usually met.

  As the monomer, a crosslinkable monomer is used, or a crosslinkable monomer and a monofunctional monomer are used. When only a crosslinkable monomer is used as the monomer, the obtained open hollow fine particles have extremely high strength.

  When the monomer component is a mixture of a crosslinkable monomer and a monofunctional monomer, the strength of the obtained open hollow fine particles can be arbitrarily set by adjusting the mixing ratio of the two. The finer the particles, the higher the content of the crosslinkable monomer.

  When the crosslinkable monomer and the monofunctional monomer are used in combination, the ratio of the crosslinkable monomer is preferably 5% by weight or more, more preferably 10% by weight or more based on the total amount of the monofunctional monomer and the crosslinkable monomer. Preferably, 50% by weight or more is even more preferable.

  As the crosslinkable monomer, for example, the polyfunctional monomer exemplified in the first method of the present invention can be used. In particular, divinylbenzene, ethylene glycol dimethacrylate and the like are preferable, and divinylbenzene is most preferable. A crosslinkable monomer can be used individually by 1 type or in combination of 2 or more types.

  As the monofunctional monomer, for example, the monofunctional monomer exemplified in the first method of the present invention can be used. A monofunctional monomer can be used individually by 1 type or in combination of 2 or more types.

  As the monofunctional monomer to be copolymerized with the crosslinkable monomer, monovinyl aromatic monomer, acrylic monomer, vinyl ester monomer, and vinyl ether monomer are preferable, and monovinyl aromatic monomer, acrylic monomer, and vinyl ester monomer are more preferable. preferable. Particularly preferred are styrene, methyl methacrylate and butyl methacrylate.

As a suitable combination of both when using a crosslinkable monomer and a monofunctional monomer in combination, divinylbenzene as a crosslinkable monomer and styrene as a monofunctional monomer alone, acrylate ester alone, methacrylate ester alone, Examples include styrene and acrylic acid esters, styrene and methacrylic acid esters, acrylic acid esters and methacrylic acid esters, combinations with styrene and acrylic acid esters and methacrylic acid esters, and the like.
solvent
<Solvent (B) of the first aspect>
As the solvent (B), a solvent that has low compatibility with the polymer or copolymer of the monomer and is hardly water soluble is used. More particularly, the interfacial tension ^{(γ x) (mN / m} ) between the solvent and water, interfacial tension between the polymer and water obtained by monomer polymerization or copolymerization to (γ ^y) (mN / A solvent having a relationship with m) such that γ ^x ≧ γ ^y may be used. As a result, when the monomer is polymerized and adsorbed at the interface with water, the polymer or copolymer is more easily adsorbed at the interface with water than the solvent, and as a result, fine particles having hollow portions are obtained. It is done.

  As such a solvent, for example, an aliphatic solvent having 8 to 18 carbon atoms, particularly 12 to 18 carbon atoms, particularly an aliphatic hydrocarbon solvent can be used.

Examples of combinations of a polymer or copolymer and a solvent that satisfy the above-described relationship of γ ^x ≧ γ ^y include, for example, a combination of polydivinylbenzene and hexadecane, a combination of polydivinylbenzene and dodecane, and a polydivinylbenzene and hexadecane. And a combination of polydivinylbenzene and dodecane.

  In the present specification, the compatibility between the solvent and the polymer or copolymer is measured by the following method. That is, an initiator (2% by weight with respect to the monomer component) is added to a monomer solution containing the raw material monomer and solvent in an appropriate weight ratio, and the polymerization reaction of the monomer component is performed in a nitrogen gas atmosphere at 30 ° C. Wake up. This reaction is carried out in a quartz glass cell having an optical path length of 1 cm, and the light transmittance is measured over time when irradiated with light having a wavelength of 550 nm. As the concentration of the solvent is increased, the transmittance, which was about 100% at the beginning, rapidly decreases to near 0% as the polymerization time elapses due to phase separation of the polymer. In this case, when the compatibility between the solvent and the polymer is low, it decreases to near 0%, but when the compatibility between the solvent and the polymer is high, the transmittance hardly decreases. Further, the lower the compatibility between the solvent and the polymer, the shorter the time from the start of polymerization until the decrease in transmittance occurs.

  As a solvent having low compatibility with the polymer, when the transmittance is measured by the above method, the polymerization rate of the monomer is about 1 to 10%, preferably about 1 to 5%, and the transmittance is lowered. Is mentioned.

  In the present specification, the interfacial tension is a value measured by Dunui's platinum ring method as defined in ASTM-971-50.

Although the usage-amount of a solvent can be selected from a wide range, generally about 0.05-4 weight part is preferable with respect to 1 weight part of monomers, and about 0.1-1 weight part is more preferable. If the amount of the solvent is too large, the shell layer is dented and the hollow portion is reduced or disappears, but such a problem does not occur within the above range.
<Solvent (B ′) of Second Embodiment>
In the second aspect, since an auxiliary polymer is used, any solvent that is poorly water-soluble can be used without limitation. As the solvent (B ′), for example, an aliphatic or aromatic hydrocarbon solvent having 6 to 18 carbon atoms, preferably an aliphatic or aromatic saturated hydrocarbon solvent can be used.

Examples of combinations of the polymer or copolymer and the solvent (B ′) include, for example, a combination of polydivinylbenzene and toluene, a combination of polydivinylbenzene and xylene, a combination of polydivinylbenzene and hexadecane, and polydivinylbenzene. And a combination of dodecane and the like.
Initiator The initiator used in the present invention is for initiating polymerization of the monomer in the droplet, and an oil-soluble polymerization initiator can be widely used. For example, azo compounds such as azobisisobutyronitrile which is a radical polymerization initiator, cumene hydroperoxide, t-butyl hydroperoxide, dicumyl peroxide, di-t-butyl peroxide, benzoyl peroxide, lauroyl peroxide, etc. Those soluble in monomers such as peroxides. Moreover, you may use the photoinitiator which starts superposition | polymerization by light, such as an ultraviolet-ray. Such a photopolymerization initiator is not particularly limited as long as it is oil-soluble, and those conventionally used can be used.

The amount of the initiator used is preferably about 0.005 to 0.1 parts by weight, particularly about 0.01 to 0.05 parts by weight, with respect to 1 part by weight of the monomer.
Auxiliary polymer As the auxiliary polymer, the compatibility with the polymer obtained by polymerizing or copolymerizing the monomer is low, and the interfacial tension (γ ^p ) (mN / m) between the auxiliary polymer and water and the monomer are polymerized or A polymer in which the relationship between the interfacial tension (γ ^q ) (mN / m) between the polymer obtained by copolymerization and water is γ ^p ≧ γ ^q can be used.

The compatibility of the auxiliary polymer with the polymer is measured by replacing the solvent with the auxiliary polymer in a method for measuring the compatibility between the solvent and water. The interfacial tension between the auxiliary polymer and water and the interfacial tension between the polymer and water are values measured by the method of ASTM-971-50.
Suspension polymerization
<First aspect>
A mixture containing the monomer, the solvent (B) and the initiator in the above proportions is dispersed in the aqueous solution of the specific dispersion stabilizer described above. This mixture is preferably a homogeneous solution in which the monomer and initiator are dissolved in a solvent.

  This mixture is preferably used in an amount of about 1 to 200 parts by weight, particularly about 10 to 100 parts by weight per 100 parts by weight of the dispersion stabilizer aqueous solution, but is not particularly limited to this range. .

  As the dispersion method, various known methods such as a dispersion method using mechanical shearing force such as a homogenizer or a membrane emulsification method can be employed. Although the temperature condition in the case of dispersion | distribution will not be limited if it is below the temperature which influences decomposition | disassembly of the initiator to be used, Usually, about 0-30 degreeC is preferable.

  In the above dispersion method, the size of droplets formed by dispersing a mixture of a monomer, a solvent and an initiator is not monodispersed, but generally droplets having various different particle sizes are mixed. Therefore, the finally obtained magnetic hollow fine particles are also an aggregate of fine particles having different particle sizes.

  On the other hand, by selecting a dispersion method, it is possible to make the size of the droplets uniform and obtain monodispersed droplets. As a method for obtaining such monodispersed droplets, for example, a method of producing monodispersed droplets by a membrane emulsification method using porous glass (SPG), a seed swelling method (JP-A-8-20604), or the like. Can be mentioned.

  When such monodispersed droplets having a uniform particle size are prepared, the finally obtained open hollow fine particles are also monodispersed with a uniform particle size.

  In any case, the average particle size of the droplets may be appropriately determined according to the desired average particle size of the open hollow fine particles, but is generally about 0.1 to 50 μm, particularly about 1 to 20 μm. Is preferred. By appropriately setting the viscosity of the mixture, the amount of the dispersion stabilizer used, the viscosity of the dispersion stabilizer aqueous solution, and the dispersion method / dispersion condition within the above ranges, the droplet average particle diameter in this range can be obtained.

  In order to subject the aqueous solution of the dispersion stabilizer in which the mixture thus obtained is dispersed to suspension polymerization, the aqueous solution may be heated while stirring.

  The heating temperature is not particularly limited as long as it is a temperature at which the monomer can be polymerized by the initiator in the droplets of the above mixture, but is generally about 30 to 90 ° C, particularly about 40 to 70 ° C. .

  Suspension polymerization is performed until the desired fine particles are obtained. The time required for suspension polymerization varies depending on the type of monomer and initiator used, but is generally about 3 to 30 hours.

  The suspension polymerization is preferably performed in an inert gas atmosphere such as nitrogen gas or argon gas.

By performing suspension polymerization in this way, the monomer is polymerized in droplets of a mixture of monomer, solvent and initiator. In the polymer or copolymer obtained by polymerization, phase separation is promoted by the presence of the solvent, and as a result, a shell having a single layer structure composed of the polymer or copolymer is formed. In addition, one opening is usually formed in the shell.
<Second aspect>
The second aspect is the same as the first aspect except that a mixture containing the monomer, the solvent (B ′), the auxiliary polymer and the initiator in the above proportions is dispersed in the aqueous solution of the specific dispersion stabilizer described above. Let
(IV) Open hollow fine particles The second open hollow fine particles of the present invention obtained as described above comprise a shell having an opening and a hollow portion, and the shell is a polymer or copolymer of a crosslinkable monomer, or It is a fine particle composed of a copolymer of a crosslinkable monomer and a monofunctional monomer. This fine particle usually has one opening. Further, the shape of the opening is not constant.

The opening area is usually about 10 ^{−3 to} 20% of the shell surface area when it is assumed that there is no opening. By adjusting the amount of the dispersion stabilizer used, the opening area can be appropriately adjusted within this range.

  The polymer or copolymer constituting the shell is as described in the item of the method of the present invention.

  The average thickness of the shell of the open hollow fine particles of the present invention is usually about 0.01 to 4 μm, particularly about 0.05 to 1 μm.

  Moreover, the volume ratio of the hollow part when it is assumed that the opening part is not formed in the shell of the open hollow fine particle of the present invention is about 5 to 80%, especially about 10 to 50% on average.

  Moreover, the average particle diameter of the open hollow fine particles obtained by the method of the present invention is usually about 0.1 to 50 μm, particularly about 1 to 20 μm. In the production method described above, by adjusting the particle size of the droplets of the mixture composed of the monomer, the solvent and the initiator dispersed in the dispersion stabilizer aqueous solution, the hollow hollow microparticles having the particle size according to the purpose can be obtained. That's fine.

The hollow portion of the second open hollow fine particle includes both a case where nothing exists in the hollow portion and a case where a solvent is present.
EXAMPLES Next, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.
Example 1
First, seed polymer particles were prepared. That is, first, a mixed solution of 20 ml of styrene, 36 ml of ion-exchanged water, 144 ml of ethanol, 284 ml of azobisisobutyronitrile and 2 g of polyacrylic acid was put into a three-necked separable flask equipped with a refluxer, and 100 rpm under a nitrogen gas stream. The mixture was reacted at 70 ° C. for 12 hours with stirring for dispersion polymerization to obtain seed polymer particles. When the seed polymer particles were observed with an optical microscope, they were monodisperse particles having a particle size (diameter) of about 1.7 μm.

  0.03 g of the obtained seed polymer particles are dispersed in a solution of 7 g of ethanol, 3 g of ion-exchanged water, 0.3 g of divinylbenzene, 0.3 g of xylene, 0.1 g of SDS and 0.006 g of benzoyl peroxide to give an emulsion (dispersion). Was prepared.

  To this emulsion, 40 g of water was dropped at a rate of 2.66 ml / h to absorb divinylbenzene, xylene and benzoyl peroxide in the seed particles. When the emulsion was observed with an optical microscope in this state, the particles were spherical and swelled to a particle size of about 4 μm.

This emulsion was centrifuged to replace the medium with water, and 0.1 g of SDS was added (at this time, the SDS concentration in the aqueous medium was 43.3 mM; 1.9 g / m ² per oil droplet surface area), and then stirred in a seal. Then, the reaction was carried out at 70 ° C. for 24 hours to carry out seed polymerization.

  The polymer obtained by the seed polymerization reaction was filtered and then dried to obtain fine particles.

  The average particle diameter of the fine particles was 3.6 μm.

  When the fine particles were observed using an optical microscope, a scanning microscope, a transmission microscope, and a confocal laser microscope, an opening was recognized in about 31% of the hollow fine particles. The surface area of the opening was about 0.5%, assuming no opening in the shell.

  The thickness of the shell was 0.8 μm, and the volume ratio of the hollow portion was about 15%.

When the particle size distribution of the open hollow particles was measured with an optical microscope, it showed a substantially monodispersed particle size distribution.
Example 2
In Example 1, the amount of SDS used was 0.12 g (SDS concentration with respect to the total volume was about 52 mmol / L; 2.3 g / m ² per oil droplet surface area). Fine particles were obtained.

About 100% of the obtained fine particles had an opening, and the ratio of the surface area of the opening was about 0.7% on the assumption that no opening was formed in the shell. The average particle diameter, shell thickness, and volume ratio of the hollow part were the same as those of the fine particles obtained in Example 1.
Example 3
In Example 1, the amount of SDS used was 0.16 g (SDS concentration with respect to the total volume was about 70 mmol / L; 3.0 g / m ² per oil droplet surface area). Fine particles were obtained.

About 100% of the obtained fine particles have an opening, and the ratio of the surface area of the opening was about 4% on the assumption that no opening was formed in the shell. The average particle diameter, shell thickness, and volume ratio of the hollow part were the same as those of the fine particles obtained in Example 1.
Example 4
In Example 1, the amount of SDS used was 0.06 g (the concentration of SDS relative to the total volume was about 26 mmol / L; 1.1 g / m ² per oil droplet surface area). Fine particles were obtained.

About 0% of the obtained fine particles had an opening, and the ratio of the surface area of the opening was about 0% when it was assumed that no opening was formed in the shell. The average particle diameter, shell thickness, and volume ratio of the hollow part were the same as those of the fine particles obtained in Example 1.
Example 5
In Example 1, when the dispersion stabilizer in the swelling stage was used in the same manner for 5 mg of polyvinyl alcohol, the amount of SDS used after medium replacement was 0.1 g (the concentration of SDS relative to the total volume was about 39 mmol / L; oil Fine particles were obtained in the same manner as in Example 1 except that the amount was 1.9 g / m ² per droplet surface area.

About 5% of the obtained fine particles had an opening, and the ratio of the surface area of the opening was about 0.15% on the assumption that no opening was formed in the shell. The average particle diameter, shell thickness, and volume ratio of the hollow part were the same as those of the fine particles obtained in Example 1.
Example 6
In Example 5, the amount of SDS used was 0.12 g (the concentration of SDS with respect to the total capacity of 70 g of ethanol and 70 g of ion-exchanged water was about 52 mmol / L; 2.3 g / m ² per oil droplet surface area). In the same manner as in Example 1, fine particles were obtained.

About 75% of the obtained fine particles had openings, and the ratio of the surface area of the openings was about 0.8% when it was assumed that no openings were formed in the shell. The average particle diameter, shell thickness, and volume ratio of the hollow part were the same as those of the fine particles obtained in Example 1.
Example 7
In Example 5, the amount of SDS used was 0.14 g (the concentration of SDS with respect to the total capacity of 70 g of ethanol and 70 g of ion-exchanged water was about 60 mmol / L; 2.6 g / m ² per oil droplet surface area). In the same manner as in Example 1, fine particles were obtained.

About 100% of the obtained fine particles had an opening, and the ratio of the surface area of the opening was about 1.8% when it was assumed that no opening was formed in the shell. The average particle diameter, shell thickness, and volume ratio of the hollow part were the same as those of the fine particles obtained in Example 1.
Example 8
In Example 1, 0.16 g of Emulgen 150, which is a nonionic surfactant, was used instead of SDS (the concentration of SDS with respect to the total volume was about 7 mmol / L; 3.0 g / m ² per oil droplet surface area) Except that, fine particles were obtained in the same manner as in Example 1.

About 100% of the obtained fine particles had an opening, and the ratio of the surface area of the opening was about 0.5% on the assumption that no opening was formed in the shell. The average particle diameter, shell thickness, and volume ratio of the hollow part were the same as those of the fine particles obtained in Example 1.
Comparative Example 1
In Example 1, fine particles were obtained in the same manner as in Example 1 except that 0.005 g of polyvinyl alcohol (polymerization degree 1700, saponification degree 88%) was used instead of SDS as the dispersion stabilizer.

  The obtained fine particles were hollow fine particles having no openings. The average particle size was 3.6 μm, the shell thickness was 0.8 μm, and the volume ratio of the hollow portion was 15%.

  A scanning electron micrograph of the fine particles obtained in Example 1 is shown in FIG. It can be seen that in the almost monodispersed hollow fine particles, irregular openings are formed in part.

  Moreover, the relationship between SDS density | concentration and opening part formation rate in the microparticles | fine-particles obtained by Examples 5-7 and the comparative example 1 is shown with a graph in FIG. As apparent from FIG. 2, the opening formation rate increased as the SDS concentration increased in the range of 20 to 58 mmol / L, and openings were formed in almost all fine particles in the range of 58 to 68 mmol / L.

  In the SDS range, the opening area increased as the SDS concentration increased.

2 is a scanning electron micrograph (drawing substitute photograph) of fine particles obtained in Example 1. FIG. It is a graph which shows the relationship between SDS density | concentration which is a dispersion stabilizer, and an opening part formation rate.

Claims (21)

Preparing a dispersion by the following Solvent (f) to the following the (a) ~ (e) are dispersed,
Constituting the dispersion (a) ~ (e) sac Chimo Nomar (a), organic solvent (c), the species by reducing the solubility of及BiShigeru initiator (e) polymer particles ( b) the model Nomar (a), organic solvent (c), a step of absorbing及BiShigeru initiator and (e),
Method for producing a hollow open particulates and a step of selective polymerization of the seed polymer particles (b) Medium demo Nomar (a).
(A) Many having two or more polymerizable reactive groups selected from the group consisting of divinylbenzene, divinylbiphenyl, divinylnaphthalene, diallylphthalate, triallyl cyanurate, ethylene glycol dimethacrylate, and tetraethylene glycol dimethacrylate A functional monomer or a mixture of the polyfunctional monomer and a monofunctional monomer having one polymerizable reactive group .
(B) mode Nomar (a) in dissolved or absorb this swelling seed polymer particles.
A polymer and seed polymeric particle (b) the solution or organic solvent Ru swell it formed from (c) Mo Nomar (a), the organic solvent is toluene, xylene, benzene, ethyl acetate, A solvent that is butyl acetate, hexane or heptane .
(D) A dispersion stabilizer having an ionic or nonionic surface active ability with a molecular weight of 20000 or less.
(E) a monomer-soluble polymerization initiator, which is azobisisobutyronitrile, cumene hydroperoxide, t-butyl hydroperoxide, dicumyl peroxide, di-t-butyl peroxide, peroxide A polymerization initiator which is benzoyl or lauroyl peroxide .
(F) dissolving the above liver Nomar (a), and a I溶 medium such dissolved polymer and seed polymer particles (b) formed from monomers (a), the solvent is methanol, ethanol , Isopropanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, triethylene glycol, methyl cellosolve, ethyl cellosolve, acetone, methyl ethyl ketone, tetrahydrofuran or methyl formate . The process according to claim 1, wherein the monomer (a) is divinylbenzene. The process according to claim 1 or 2, wherein the organic solvent (c) is toluene, xylene or benzene. The method according to any one of claims 1 to 3, wherein the polymerization initiator (e) is benzoyl peroxide or lauroyl peroxide. The method according to claim 1, wherein the solvent (f) is methanol, ethanol or isopropanol. The method according to any one of claims 1 to 5, wherein the dispersion stabilizer (d) comprises an anionic surfactant. The method according to claim 1, the concentration of the dispersion stabilizer (d), the unit oil total area per 0.1 to 10 g / m ² for Solvent (f). Below in the following Solvent (f) (a), ( b), (c), a step of preparing a dispersion by dispersing (d ') and (e),
Constituting the dispersion (a), (b), (c), (d ') and (e) sac Chimo Nomar (a), organic solvent (c),及BiShigeru initiator (e seed polymer particles (b) in the mode Nomar by reducing the solubility of) (a), organic solvent (c), a step of absorbing及BiShigeru initiator and (e),
The following step (d) adding a dispersion stabilizer;
Method for producing a hollow open particulates and a step of selective polymerization of the seed polymer particles (b) Medium demo Nomar (a).
(A) Many having two or more polymerizable reactive groups selected from the group consisting of divinylbenzene, divinylbiphenyl, divinylnaphthalene, diallylphthalate, triallyl cyanurate, ethylene glycol dimethacrylate, and tetraethylene glycol dimethacrylate A functional monomer or a mixture of the polyfunctional monomer and a monofunctional monomer having one polymerizable reactive group .
(B) mode Nomar (a) in dissolved or absorb this swelling seed polymer particles.
A polymer and seed polymeric particle (b) the solution or organic solvent Ru swell it formed from (c) Mo Nomar (a), the organic solvent is toluene, xylene, benzene, ethyl acetate, A solvent that is butyl acetate, hexane or heptane .
(D) A dispersion stabilizer having an ionic or nonionic surface active ability with a molecular weight of 20000 or less.
(D ′) A dispersion stabilizer.
(E) a monomer-soluble polymerization initiator, which is azobisisobutyronitrile, cumene hydroperoxide, t-butyl hydroperoxide, dicumyl peroxide, di-t-butyl peroxide, peroxide A polymerization initiator which is benzoyl or lauroyl peroxide .
(F) dissolving the above liver Nomar (a), and a I溶 medium such dissolved polymer and seed polymer particles (b) formed from monomers (a), the solvent is methanol, ethanol , Isopropanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, triethylene glycol, methyl cellosolve, ethyl cellosolve, acetone, methyl ethyl ketone, tetrahydrofuran or methyl formate . The method according to claim 8, wherein the monomer (a) is divinylbenzene. The process according to claim 8 or 9, wherein the organic solvent (c) is toluene, xylene or benzene. The method according to any one of claims 8 to 10, wherein the polymerization initiator (e) is benzoyl peroxide or lauroyl peroxide. The method according to any one of claims 8 to 11, wherein the dispersion stabilizer (d) comprises an anionic surfactant. The method of any of claims 8 to 12 concentrations of the dispersion stabilizer (d), the unit oil total area per 0.1 to 10 g / m ² for Solvent (f). In an aqueous solution of a dispersion stabilizer having an ionic or nonionic surface active ability with a molecular weight of 20000 or less, (A) a crosslinkable monomer, or a crosslinkable monomer and a monofunctional monomer, (B) having 8 to 18 carbon atoms A method for producing open hollow fine particles, in which a mixture containing an aliphatic solvent and (C) an initiator is dispersed and suspension polymerization is performed. The method according to claim 14, wherein the dispersion stabilizer comprises an anionic surfactant. The method according to claim 14 or 15, wherein the concentration of the dispersion stabilizer is 0.1 to 10 g / m ² per unit oil droplet total area. As the solvent, the interfacial tension (γ ^x ) (mN / m) between the solvent and water and the interfacial tension (γ ^y ) (mN / m) between the polymer obtained by polymerizing or copolymerizing the monomers and water. The method according to any one of claims 14 to 16, wherein a solvent having a relationship of γ ^x ≧ γ ^y is used. In an aqueous solution of a dispersion stabilizer having an ionic or nonionic surface active ability with a molecular weight of 20000 or less, (A) a crosslinkable monomer or a crosslinkable monomer and a monofunctional monomer, (B ′) having 6 to 18 carbon atoms 2% by weight of an initiator based on the monomer component is added to a solution containing an aliphatic or aromatic hydrocarbon solvent, (D) the monomer (A), and the auxiliary polymer, and at 30 ° C. in a nitrogen gas atmosphere Then, when the polymerization reaction of the monomer component is caused, this reaction is performed in a quartz glass cell having an optical path length of 1 cm, and the light transmittance when the light of wavelength 550 nm is irradiated is measured over time, the polymerization of the monomer is performed. It is an auxiliary polymer that causes a decrease in transmittance at a rate of 1 to 10% , and is obtained by polymerizing or copolymerizing monomers with an interfacial tension (γ ^p ) (mN / m) between the auxiliary polymer and water. interfacial tension between the polymer and water ^{(γ q) (mN / m} ) and the related There γ ^p ≧ γ ^q a is an auxiliary polymer, and (C) dispersing the mixture containing the initiator, the manufacturing method of opening hollow particulates for performing suspension polymerization. The method of claim 18, wherein the dispersion stabilizer comprises an anionic surfactant. The method according to claim 18 or 19, wherein the concentration of the dispersion stabilizer is 0.1 to 10 g / m ² per unit oil droplet total area. As the solvent, the interfacial tension (γ ^x ) (mN / m) between the solvent and water and the interfacial tension (γ ^y ) (mN / m) between the polymer obtained by polymerizing or copolymerizing the monomers and water. 21) The method according to any one of claims 18 to 20, wherein a solvent having a relationship of γ ^x ≧ γ ^y is used.

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