JP4662804B2 - Hollow resin fine particles, method for producing hollow resin fine particles, and composite material - Google Patents

Description

The present invention relates to a hollow resin fine particle having a high porosity, high strength, excellent heat resistance and solvent resistance, a method for producing the hollow resin fine particle, and a composite material.

Hollow particles with voids inside the particles are intended for weight reduction, pore formation, heat insulation, sound insulation, low dielectric properties, impact resistance, rigidity improvement, texture improvement, anti-sinking, coating improvement, etc. Injection moldings, injection compression moldings, extrusion moldings, hollow moldings, compression moldings, sheet moldings, vacuum moldings, film moldings, rotational moldings and other molded articles, wallpaper, paints, sealants, It is used in an extremely wide range of fields such as adhesives, shoe soles, synthetic leather, tires, paper, cement, tiles, building materials, artificial wood, FRP, and porous ceramic filters.

As such hollow particles, conventionally, inorganic microballoons such as glass balloons and shirasu balloons, foamed resin fine particles mainly composed of thermoplastic polymers having gas barrier properties such as nitrile polymers and vinylidene chloride, and the like described in Patent Document 1 and the like These thermoplastic hollow resin particles are known.

However, inorganic microballoons such as glass balloons, shirasu balloons, and ceramic balloons are excellent in heat resistance and solvent resistance, but are brittle and inferior in particle strength, and are easily broken by the weak crown shear force applied during compounding in various applications. There was a problem of waking up. In addition, these inorganic balloons have a problem of poor alkali resistance.

The foamed resin fine particles mainly composed of a thermoplastic polymer are obtained by microencapsulating a volatile expansion agent that becomes gaseous at a temperature lower than the softening point temperature of the thermoplastic polymer using the thermoplastic polymer. However, such expandable resin fine particles containing a thermoplastic polymer as a main component are insufficient in heat resistance, solvent resistance and particle strength, and cannot be used for most of the various applications described above.

Furthermore, since the thermoplastic hollow resin fine particles disclosed in Patent Document 1 are not thermally expandable, the strength is superior to the foamed resin fine particles mainly composed of a thermoplastic polymer, but this is mainly due to low hollowness. This is due to the fact that when the hollowness is increased, a certain degree of strength reduction is unavoidable, and the heat resistance is insufficient, so that it may be difficult to use in the various applications described above.

On the other hand, development of hollow resin fine particles having high strength, heat resistance, and solvent resistance has been studied.
For example, Patent Document 2 and Patent Document 3 disclose that a thermally expandable microcapsule excellent in solvent resistance and heat resistance can be obtained by using a certain amount or more of a nitrile monomer as a shell of the thermally expandable microcapsule. Has been.
However, although the thermally expandable microcapsules obtained by these methods are superior in heat resistance and solvent resistance of weak crowns as compared to conventional thermally expandable capsules, they are still not at a satisfactory level. In addition, the microcapsule strength after thermal expansion has not been improved.
JP 2001-213727 A JP-A-60-21770 Japanese Patent No. 2894990

In view of the above-mentioned present situation, the present invention aims to provide hollow resin fine particles having a high porosity, high strength, excellent heat resistance and solvent resistance, a method for producing the hollow resin fine particles, and a composite material. To do.

The present invention is a hollow resin fine particle having a single-pore structure and made of an epoxy resin having a porosity of 70% or more and having a compressive strength of 5.0 MPa or more.
The present invention is described in detail below.

The hollow resin fine particles of the present invention have a single pore structure.
By having the single pore structure, the voids formed inside the hollow resin fine particles of the present invention have excellent sealing properties, and when the hollow resin fine particles of the present invention are used for various applications, a binder is formed in the voids. It is possible to prevent such a problem that components and other components enter to lower the hollow ratio.
In the present specification, the “single pore structure” refers to a structure having only one closed void, not including a plurality of voids such as a porous shape. Hereinafter, a portion made of an epoxy resin other than the voids of the hollow resin fine particles of the present invention is also referred to as a “shell portion”.

Gas is present in the voids inside the hollow resin fine particles of the present invention, and the gas is preferably air, but may be other gases.

In the hollow resin fine particles of the present invention, the lower limit of the porosity is 70%. When the porosity is less than 70%, it is not possible to sufficiently impart weight reduction, pore formation, imparting heat insulation, imparting sound insulation, cushioning, etc. to a molded body using the hollow resin fine particles of the present invention. . The upper limit of the porosity is not particularly limited, but the preferable upper limit is 99% and the more preferable upper limit is 95% because it is necessary to maintain the shape and the strength.

The hollow resin fine particles of the present invention have a lower limit of compressive strength of 5.0 MPa. If it is less than 5.0 MPa, it is added when shear molding force when the hollow resin fine particles of the present invention are kneaded with a molten resin or an inorganic material to form a composite material or when a molded body is pressure-molded using the composite material. May be destroyed by the pressure applied. A preferred lower limit is 10 MPa, and a more preferred lower limit is 50 MPa. In addition, in this specification, the said compressive strength is 10 weight% fracture | rupture pressure strength by ASTM-D3102 (glycerol use).

Further, the average particle diameter of the hollow resin fine particles of the present invention is not particularly limited, but the preferable lower limit is 100 nm, and the preferable upper limit is 500 μm. When the thickness is less than 100 nm, aggregation of the hollow resin fine particles of the present invention may occur and the handleability may be inferior. When the thickness exceeds 500 μm, the hollow resin fine particles of the present invention are stably produced by the method described below. Formation of droplets becomes difficult. A more preferable lower limit is 500 nm, and a more preferable upper limit is 100 μm.

The true specific gravity of the hollow resin fine particles of the present invention is not particularly limited, but a preferred lower limit is 0.01 g / cm ³ and a preferred upper limit is 1.0 g / cm ³ . If it is less than 0.01 g / cm ³ , the shell part of the hollow resin fine particles of the present invention may become too thin and the particle strength may be significantly reduced. If it exceeds 1.0 g / cm ³ , the shell part becomes thick. Therefore, the characteristics as hollow particles may not be exhibited. A more preferred upper limit is 0.4 g / cm ³ .

The hollow resin fine particles of the present invention are made of an epoxy resin.
The epoxy resin is not particularly limited, for example, glycidyl ether type, glycidyl ester type, glycidyl amine type, aliphatic type, alicyclic type, novolac type, aminophenol type, hydatoin type, isocyanurate type, biphenol type, Any epoxy resin such as naphthalene type and hydrogenated products or fluorinated products thereof may be used.

Such hollow resin fine particles of the present invention can be easily produced by reacting a thermosetting monomer containing an epoxy monomer having a predetermined epoxy equivalent with a hydrophilic curing agent by an interfacial polymerization method.
That is, the hollow resin fine particles of the present invention are capable of polymerizing a lipophilic reactive component composed of a thermosetting monomer containing an epoxy monomer having an epoxy equivalent of 500 or less in an amount of 60% by weight or more in a polar medium containing a hydrophilic curing agent. It can be produced by a method comprising a step of preparing a dispersion dispersed as droplets, and a step of reacting the lipophilic reaction component with the hydrophilic curing agent at the polymerizable droplet interface. Such a method for producing hollow resin fine particles of the present invention is also one aspect of the present invention.

In the method for producing hollow resin fine particles of the present invention, a lipophilic reactive component composed of a thermosetting monomer containing an epoxy monomer having an epoxy equivalent of 500 or less is 60% by weight or more is polymerized in a polar medium containing a hydrophilic curing agent. A step of preparing a dispersion liquid dispersed as a conductive droplet.

The said thermosetting monomer contains the epoxy monomer whose epoxy equivalent is 500 or less, and the minimum of the content is 60 weight%. If it is less than 60% by weight, the shell part of the hollow resin fine particles to be produced is insufficiently crosslinked, the strength, heat resistance and solvent resistance are insufficient, and the lower limit of the porosity is difficult to be 70%. It becomes. The minimum with preferable content of the said epoxy monomer whose poxy equivalent is 500 or less is 80 weight%, and a more preferable minimum is 90 weight%.

The epoxy monomer having an epoxy equivalent of 500 or less preferably contains an epoxy monomer having an epoxy equivalent of 200 or less, and the preferred lower limit of the blending amount is 10% by weight. The hollow resin fine particles of the present invention produced using such a thermosetting monomer have a high crosslink density in the shell portion, and are excellent in strength, solvent resistance, and heat resistance. The more preferable lower limit of the epoxy monomer having an epoxy equivalent of 200 or less in the epoxy monomer having an epoxy equivalent of 500 or less is 30% by weight, and the more preferable lower limit is 50% by weight.

The epoxy monomer having an epoxy equivalent of 500 or less and the epoxy monomer having an epoxy equivalent of 200 or less have lipophilic properties and react with amines, thiols, polycarboxylic acids, and acid anhydrides to give resins. Glycidyl ether type, glycidyl ester type, glycidyl amine type, aliphatic type, alicyclic type, novolac type, aminophenol type, hydatoin type, isocyanurate type, biphenol type, naphthalene type and their hydrogenated products, fluorinated products Any of these can be used.

The epoxy monomer having an epoxy equivalent of 200 or less is not particularly limited. For example, Epototo YD115, Epototo YD127, Epototo YD128 (trade name, manufactured by Toto Kasei), Epicoat 825, Epicoat 827, Epicoat 828 (trade name Japan Epoxy Resin) Bisphenol A type epoxy resin such as EPICLON 840, EPICLON 850 (trade name, manufactured by Dainippon Ink &Chemicals); Epototo YDF-170, Epototo YDF175S (trade name, manufactured by Toto Kasei), Epicoat 806, Epicoat 807 (Product) Name Bisphenol F type epoxy resin such as EPOCLON 830, EPICLON 835 (trade name manufactured by Dainippon Ink &Chemicals); Epototo YDPN-638, Epototo Y DCN-701, Epototo YDCN-702, Epototo YDCN-703, Epototo YDCN-704, Epototo YDCN-500 (trade name, manufactured by Toto Kasei), Epicoat 152, Epicoat 154 (trade name, manufactured by Japan Epoxy Resin), EPICLON N- 655, EPICLON N-740, EPICLON N-770, EPICLON N-775, EPICLON N-865 (trade name, manufactured by Dainippon Ink and Chemicals) and the like; Epototo YH-434, Epototo YH434-L (trade name Toto Kasei), Epicoat 1031S, Epicoat 1032H60, Epicoat 604, Epicoat 630 (trade name, manufactured by Japan Epoxy Resin), EPICLON 430 (trade name, manufactured by Dainippon Ink and Chemicals), TE Special multifunctional types such as RAD-X, TETRAD-C (trade name, manufactured by Mitsubishi Gas Chemical Company); biphenyl type epoxy resins such as Epicoat YX4000, Epicoat YL6121H, Epicoat YL6640, Epicoat YL6677 (trade name, manufactured by Japan Epoxy Resin); Aliphatic polyglycidyl ether type epoxy resins such as Epototo YH-300, Epototo YH301, Epototo YH-315, Epototo YH-324, Epototo YH-325 (trade name, manufactured by Toto Kasei Co., Ltd.); Epototo YDC-1312, Epototo YSLV-80XY Crystalline epoxy resins (trade name, manufactured by Toto Kasei Co., Ltd.); Naphthalene type epoxy resins, such as EPICLON HP-4032 and EPICLON EXA-4700 (trade name, manufactured by Dainippon Ink and Chemicals); Epicoat 19 P, Epicote YX310 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON HP-820 (trade name, manufactured by Dainippon Ink Chemical Co., Ltd.), etc .; EPICLON 725 (trade name, manufactured by Dainippon Ink Chemical Co., Ltd.), etc. A reactive diluent etc. are mentioned.
These epoxy monomers having an epoxy equivalent of 200 or less may be used alone or in combination of two or more.

Epoxy monomers having an epoxy equivalent of more than 200 and 500 or less include Epototo YD134, Epototo YD011 (trade name, manufactured by Toto Kasei Co., Ltd.), Epicoat 801, Epicoat 1001 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON860, EPICLON1050, EPICLON1055 Bisphenol A type epoxy resin (trade name, manufactured by Dainippon Ink and Chemicals Co., Ltd.); Bisphenol F type epoxy resin such as Epototo YDF-2001 (trade name, manufactured by Toto Kasei Co., Ltd.); EPICLON N-660, EPICLON N-665, EPICLON N Novolak type epoxy resins such as -670, EPICLON N-673, EPICLON N-680, EPICLON N-695 (trade name, manufactured by Dainippon Ink &Chemicals); Epicoat 157 70 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON 5500 (trade name, manufactured by Dainippon Ink & Chemicals, Inc.), etc .; Epototo YDB-360, Epototo YDB-400, Epototo YDB405 (trade name, manufactured by Toto Kasei Co., Ltd.), Brominated epoxy resins such as EPICLON152 and EPICLON153 (trade name manufactured by Dainippon Ink and Chemicals); Epototo YD-171 (trade name manufactured by Toto Kasei Co., Ltd.), Epicoat 871 (trade name manufactured by Japan Epoxy Resin), EPICLONTSR-960, EPICLON Flexible epoxy resins such as TSR-601 (trade name, manufactured by Dainippon Ink Chemical Co., Ltd.); Epototo ST-3000 (trade name, manufactured by Toto Kasei Co., Ltd.), Epicoat YX8000, Epicoat YX8034 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.), etc. -Contained epoxy resin; EPICLON HP-7200 (trade name, manufactured by Dainippon Ink and Chemicals, Inc.) dicyclopentadiene type epoxy resin, etc., and the like.
These epoxy monomers having an epoxy equivalent of more than 200 and 500 or less may be used alone or in combination of two or more.

Examples of the epoxy monomer having an epoxy equivalent of more than 500 include, for example, Epototo YD-012, Epototo YD-013, Epototo YD-014, Epototo YD-017, Epototo YD-019 (trade name, manufactured by Toto Kasei Co., Ltd.), Epicoat 1002 , Epicoat 1003, Epicoat 1055, Epicoat 1004, Epicoat 1007, Epicoat 1009, Epicoat 1010 (product name: Japan Epoxy Resin Co., Ltd.), EPICLON 3050, EPICLON 4050, EPICLON AM-020-P, EPICLON AM-030-P, EPICLON AM Bisphenol A such as -040-P, EPICLON 7050, EPICLON HM-091, EPICLON HM-101 (trade name, manufactured by Dainippon Ink & Chemicals, Inc.) Epoxy resin: Epototo YDF-2004 (trade name, manufactured by Toto Kasei Co., Ltd.), Epicoat 4004P, Epicoat 4007P, Epicoat 4010P, Epicoat 4110, Epicoat 4210 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.), etc .; Epototo YDB- Brominated epoxy resins such as 405 (trade name, manufactured by Toto Kasei Co., Ltd.), EPICLON 1123P-75M (trade name, manufactured by Dainippon Ink and Chemicals); Epototo YD-172 (trade name, manufactured by Toto Kasei Co., Ltd.), Epicort 872 (trade name Japan) Epoxy resin), EPICLON 1600-75X (trade name, Dainippon Ink Chemical Co., Ltd.) and other flexible epoxy resins; Epototo ST-4000D (trade name, manufactured by Toto Kasei Co., Ltd.), etc .; EPICLON 5800 (quotient Name manufactured by Dainippon Ink and Chemicals, Inc.) multifunctional epoxy resin or the like of, and the like.
These epoxy monomers having an epoxy equivalent exceeding 500 may be used alone or in combination of two or more.

As the epoxy monomer having an epoxy equivalent of 500 or less, an epoxy monomer having an epoxy equivalent of 200 or less, and an epoxy monomer having an epoxy equivalent of more than 500, bisphenol A type epoxy resin, bisphenol F type epoxy resin, flexible epoxy resin, And you may contain 1 or more types of those hydrogenated products. By containing these epoxy monomers, the epoxy resin constituting the hollow resin fine particles to be obtained has high toughness.

The hydrophilic curing agent is not particularly limited, and examples thereof include amine curing agents, thiol curing agents, polycarboxylic acids, and acid anhydrides. Of these, amine-based curing agents are preferred in terms of reaction temperature and cured properties.

The amine curing agent is not particularly limited, and examples thereof include ethylenediamine, 1,4-diaminobutane, 1,5-diaminoheptane, hexamethylenediamine, 1,7-diaminoheptane, 1,8-diaminooctane, , 9-diaminononane, 1,10-diaminodecane, tetramethylenediamine, bishexamethylenetriamine, phenylenediamine, diethylenetriamine, triethylenetetramine, diethylaminopropylamine, tetraethylenepentamine, norbornanediamine, isophoronediamine, xylylenediamine, etc. Polyamine; 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazo 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2 -Ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium Trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-undecylimidazolyl- (1' )]-Ethyl-s-triazine, 2,4-diamino-6- [2'- Imidazole such as til-4′-methylimidazolyl- (1 ′)]-ethyl-s-triazine, 2-phenylimidazole isocyanuric acid adduct, 2-methylimidazole isocyanuric acid adduct; piperazine, 2-methylpiperazine, 2, Piperazine compounds such as 5-dimethylpiperazine; amino group-containing prepolymers such as amino adducts of epoxy resins.

The amine curing agent preferably has an active hydrogen equivalent of 50 or less. By using an amine curing agent having an active hydrogen equivalent of 50 or less, the hollow resin fine particles of the present invention to be produced have a higher cross-linking density in the shell part, and are superior in strength, heat resistance and solvent resistance. Become.

The amine-based curing agent having an active hydrogen equivalent of 50 or less preferably contains an alkylene diamine having a lower limit of 4 carbon atoms and an upper limit of 10. By using such an amine-based curing agent, the hollow resin fine particles of the present invention to be produced have extremely high strength that satisfies both the crosslinking density and toughness.

The thiol-based curing agent is not particularly limited, and examples thereof include 1,2-ethyldithiol, 1,3-propanedithiol, 1,6-hexanedithiol, 1,9-nonanedithiol, 1,10-decanedithiol, and the like. Can be mentioned.

The polycarboxylic acid is not particularly limited. For example, oxalic acid, adipic acid, azelaic acid, sebacic acid, malonic acid, succinic acid, 1,4-cyclohexyldicarboxylic acid, (o-, m-, p-) benzene A polymer copolymer containing 10% by weight or more of any one selected from the group consisting of dicarboxylic acid, maleic acid, itaconic acid, acrylic acid, methylmethacrylic acid and the like is preferable.

The acid anhydride is not particularly limited, and examples thereof include tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, and succinic anhydride.

The blending amount of the hydrophilic curing agent is not particularly limited, and is appropriately determined according to the active hydrogen equivalent of the hydrophilic curing agent, the ratio of the epoxy monomer in the thermosetting monomer, the epoxy equivalent, and the like.

Moreover, in the manufacturing method of the hollow resin microparticles | fine-particles of this invention, you may mix | blend a nonpolymerizable compound with the said lipophilic reaction component. In addition to the role of forming stable polymerizable droplets in a polar medium and controlling the reaction rate between the oleophilic epoxy monomer and the hydrophilic curing agent, the non-polymerizable compound is used in the production of hollow resin fine particles. It has the role of increasing the porosity.

The non-polymerizable compound is liquid at the reaction temperature of the epoxy monomer in the thermosetting monomer and the hydrophilic curing agent and can be mixed with other lipophilic components. There is no particular limitation as long as it does not react with any of them and can be easily evaporated by heating, for example, butane, pentane, hexane, cyclohexane, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, Examples thereof include organic solvents such as methyl pentyl ketone, ethyl acetate, butyl acetate, methyl chloride, methylene chloride, chloroform and carbon tetrachloride.

Moreover, you may mix | blend a higher alkane or a long-chain hydrophobic compound having about 8 to 20 carbon atoms as the non-polymerizable compound. Such a compound has a role of effectively suppressing the coalescence of polymerizable droplets in a polar medium. In particular, since droplets having a particle size of 1 μm or less have the property of being easily united, when such droplets are stably formed, the higher alkane or the long-chain hydrophobic compound is blended. Preferably it is.

The higher alkane having about 8 to 20 carbon atoms and the long-chain hydrophobic compound are not particularly limited. For example, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, heptadecane, hexadecane, heptadecane, octadecane, nonadecane Eicosane, stearyl methacrylate and the like.

The blending amount of the non-polymerizable compound is not particularly limited, but a preferable lower limit is 70 parts by weight and a preferable upper limit is 1000 parts by weight with respect to 30 parts by weight of the lipophilic reaction component. If it is less than 70 parts by weight, the porosity of the hollow resin fine particles to be produced may be low. If it exceeds 1000 parts by weight, the shape of the particles cannot be maintained when the non-polymerizable compound is removed to obtain hollow resin fine particles. In some cases, the strength of the obtained hollow resin fine particles may be extremely inferior.

When the higher alkane having 8 to 20 carbon atoms or the long-chain hydrophobic compound is used, the blending amount with respect to the lipophilic reaction component is not particularly limited, but a preferred lower limit is 0.1% by weight. If it is less than 0.1% by weight, coalescence of polymerizable droplets may not be effectively suppressed.

The polar medium is not particularly limited as long as it does not mix with the lipophilic component and can prepare a dispersion of the lipophilic component. For example, water, glycine-HCl buffer, citric acid-sodium citrate A buffer solution, an acetic acid-sodium acetate buffer solution, a phosphate buffer solution, ethanol, methanol, isopropyl alcohol, and other ordinary polar media can be used arbitrarily.

The method for preparing a dispersion in which the lipophilic reaction component, the hydrophilic curing agent, the dispersion stabilizer, and the like are dispersed as polymerizable droplets in the polar medium is not particularly limited. For example, a homomixer, a biomixer, A conventionally well-known method using an omni mixer, an ultrasonic homogenizer, a microfluidizer, etc. is mentioned.

In preparing the dispersion, various additives may be added to the polar medium. For example, sodium lauryl sulfate, sodium higher alcohol sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, polyoxyethylene Sodium lauryl ether sulfate, sodium polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl ether sulfate triethanolamine, sodium dodecylbenzene sulfonate, sodium alkyl naphthalene sulfonate, sodium dialkyl sulfosuccinate, sodium alkyl diphenyl ether disulfonate, polyoxyethylene alkyl Anionic emulsifiers such as potassium ether phosphate, dipotassium alkenyl succinate and sodium alkane sulfonate Lenlauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene myristyl ether, polyoxyethylene alkyl ether, polyoxyethylene higher alcohol ether, polyoxyethylene alkylene alkyl ether, polyoxy Ethylene distyrenated phenyl ether, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan tristearate, sorbitan monooleate, sorbitan trioleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan laurate , Polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monopalmitate Nonionic emulsifiers such as tearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan trioleate, glycerol monostearate, glycerol monostearate, glycerol monooleate, lauryltrimethylammonium chloride, Cationic emulsifiers such as stearyltrimethylammonium chloride, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, alkylbenzylmethylammonium chloride, lauryl betaine, stearyl betaine, 2-alkyl-N-carboxymethyl-N-hydroxy Ethyl imidazolinium betaine, lauryl dimethyl Amphoteric emulsifiers such as tilamine oxide, partially saponified polyvinyl acetate, cellulose derivatives, poly (meth) acrylic acid, poly (meth) acrylic acid copolymer, polyvinylpyrrolidone, polyacrylamide, marialim, polystyrene sulfonic acid, polyvinyl alcohol, etc. And dispersion aids such as cetyl alcohol. The compounding amount in the case of adding these is not particularly limited, but the preferred lower limit for the polar medium is 0.01% by weight, and the preferred upper limit is 10% by weight.

The method for producing hollow resin fine particles of the present invention includes a step of reacting the hydrophilic reaction component with a hydrophilic curing agent at the polymerizable droplet interface.
For example, by heating the dispersion to a reaction temperature between the epoxy monomer in the lipophilic reaction component and the hydrophilic curing agent, the epoxy monomer in the lipophilic reaction component reacts with the hydrophilic curing agent. This produces an epoxy resin. At this time, since the polymerizable droplet containing the lipophilic reaction component and the polar medium containing the hydrophilic curing agent are phase-separated, the reaction occurs only near the interface between the polymerizable droplet and the polar medium, Resin fine particles having a shell portion made of the produced epoxy resin and encapsulating the unreacted lipophilic component (and the non-polymerizable compound) are formed.

In the method for producing hollow resin fine particles of the present invention, the hollow resin fine particles having a high porosity can be produced by removing unreacted lipophilic components encapsulated in the obtained resin fine particles.
The method for removing the unreacted lipophilic component encapsulated in the obtained resin fine particles is not particularly limited. For example, a method of blowing a gas such as nitrogen or air into the dispersion of the obtained resin fine particles; A method of depressurizing; for example, extracting and removing the lipophilic component in a solvent that can be mixed with the lipophilic component included therein.
Furthermore, the unreacted lipophilic component included can be removed from the resin fine particles by setting the temperature condition to be equal to or higher than the boiling point of the unreacted lipophilic component inside the resin fine particles.

According to the method for producing hollow resin fine particles of the present invention by such an interfacial polymerization method, the hollow resin fine particles of the present invention having a single pore structure and a porosity of 70% or more can be produced.
Moreover, the shell part of the hollow resin fine particles of the present invention to be produced is a thermosetting monomer containing an epoxy monomer having an epoxy equivalent of 500 or less, preferably 60% by weight or more, preferably 10% by weight or more of an epoxy monomer having an epoxy equivalent of 200 or less. Active hydrogen containing an oleophilic reaction component composed of a thermosetting monomer containing 60 wt% or more of an epoxy monomer having an epoxy equivalent of 500 or less and a hydrophilic curing agent, preferably an alkylenediamine having 4 to 10 carbon atoms Since it is formed by reacting an amine-based curing agent with an equivalent weight of 50 or less, it has a high cross-linking density, and has a high compressive strength lower limit of 5.0 MPa, heat resistance and solvent resistance. It will be excellent. Therefore, the hollow resin fine particles of the present invention obtained by the method for producing the hollow resin fine particles of the present invention are applied to a coated product containing an organic solvent or a plasticizer, a molded product by adding it to a high-temperature molten resin, or an inorganic material. It can be suitably used in applications that are difficult to use with conventional hollow particles, such as molded products that require kneading.

The use of the hollow resin fine particles of the present invention is not particularly limited. For example, it is intended to introduce a pore forming material used when producing a porous ceramic filter or a void formed by the hollow resin particles of the present invention inside. It can be used for various organic and inorganic composite materials.

The hollow resin fine particles of the present invention can be suitably used as a pore-forming material for producing a porous ceramic filter used when producing a porous ceramic filter. Since the hollow resin fine particles of the present invention have high strength, if the hollow resin fine particles of the present invention are used as a pore-forming material for producing a porous ceramic filter, the shearing force at the time of kneading with the ceramic material at the time of forming the porous ceramic filter In addition, the pore forming effect can be effectively exhibited without being crushed by the pressure at the time of extrusion molding.
Moreover, since the hollow resin fine particles of the present invention have a high porosity of 70% or more, when the hollow resin fine particles of the present invention are used as a pore-forming material for producing a porous ceramic filter, the organic components at the time of producing the porous ceramic filter are used. In the degreasing step to be removed, there is little generation of decomposition heat and organic gas, and the burden on the degreasing step can be reduced. The pore former for producing a porous ceramic filter comprising the hollow resin fine particles of the present invention is also one aspect of the present invention.

As a method for manufacturing a porous ceramic filter using the porous ceramic filter manufacturing pore former of the present invention, for example, the porous ceramic filter manufacturing porous material of the present invention and a ceramic material are combined with a predetermined binder component or the like. A step of kneading to prepare a ceramic slurry, a step of extruding the ceramic slurry by a conventionally known extrusion molding method or the like to produce a molded body having substantially the same shape as the porous ceramic filter, and a step of degreasing the produced molded body And the method which has the process of baking the molded object after degreasing is mentioned. The porous ceramic filter using the pore-forming material for producing the porous ceramic filter of the present invention is also one aspect of the present invention.

It does not specifically limit as said ceramic material, For example, a cordierite composition, a silicon carbide composition, a silicon nitride composition etc. are mentioned.

In addition, the hollow resin fine particles of the present invention can be suitably used for various organic and inorganic composite materials intended to introduce voids due to the hollow resin particles of the present invention. A composite material having a matrix resin is also one aspect of the present invention.

Such a composite material of the present invention has lightness, pore-forming properties, heat insulation properties, sound insulation properties, low dielectric properties, impact resistance, by introducing voids inside the matrix resin by the hollow resin fine particles of the present invention, It has excellent rigidity, texture, and anti-sink properties.

Such a composite material of the present invention is not particularly limited. For example, a lightweight injection molded article, a matte injection molded article, a high-strength injection molded article, a lightweight clay, a lightweight wallpaper, a lightweight shoe sole, a lightweight vehicle bottom paint, a lightweight Insulating material resin composition, lightweight rubber elastic body, lightweight tire, lightweight sealing agent, lightweight adhesive, lightweight FRP, lightweight synthetic leather, lightweight synthetic wood, lightweight architectural aggregate, lightweight ceramic composition, lightweight tile, lightweight artificial marble, Pressure-sensitive paper, pressure-sensitive adhesive, pressure-sensitive adhesive application, improvement of paintability, heat-resistant insulation, heat-insulating paint, sound-absorbing resin composition, vibration damping composition, low dielectric material, cement mortar composition, cure shrinkage reduction adhesion Various agents such as an agent, a curing shrinkage-reducing sealant, a matte sealant, and a composition for a porous ceramic filter can be used.
In particular, the composite material of the present invention can be suitably used as various paints, putty, sealing agents, and injection molded articles. Note that an injection-molded body made of the composite material of the present invention is also one aspect of the present invention.

The injection-molded article of the present invention has functions such as weight reduction, impact resistance improvement, rigidity improvement, anti-sink, matte, heat insulation, etc., and the above-mentioned composite material of the present invention is conventionally known as an injection molding method. It can manufacture by shape | molding by.

The injection-molded article of the present invention is obtained by molding the above-described hollow resin fine particles of the present invention and an injection molding material by a conventionally known injection molding method.
The injection molding material is not particularly limited as long as it is a meltable thermoplastic resin. For example, polyethylene resin, polypropylene resin, polystyrene resin, ABS resin, AS resin, acrylic resin, vinyl chloride resin, various polyamide resins , Polyoxymethylene resin, polycarbonate resin, modified polyphenylene ether resin, polyethylene terephthalate resin, polybutylene terephthalate resin, ultrahigh molecular weight polyethylene resin, polyvinyl acetate resin, polyvinylidene chloride resin, polysulfone resin, polyethersulfone resin, polyphenylene Sulfide resin, polyarylate resin, polyamideimide resin, polyetherimide resin, polyimide resin, polyetheretherketone resin, various liquid crystal resins, tetrafluoroethylene / perf Oroalkyl vinyl ether copolymer resin, polychlorotrifluoroethylene resin, polyvinylidene fluoride resin, polyvinyl fluoride resin, ethylene / tetrafluoroethylene copolymer resin, ethylene / trichlorofluoroethylene copolymer resin, and copolymers thereof Examples include coalescence.

According to the present invention, it is possible to provide hollow resin fine particles having a high porosity, high strength, and excellent heat resistance and solvent resistance.

Hereinafter, 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
(1) Preparation of hollow resin fine particles As an epoxy monomer component, Epicoat 828 (epoxy equivalents 184 to 194, manufactured by Japan Epoxy Resin) 20 parts by weight and Epicoat 630 (epoxy equivalents 90 to 105, manufactured by Japan Epoxy Resin) 10 parts by weight The total amount of a mixed solution obtained by mixing and stirring 70 parts by weight of toluene as a non-polymerizable compound, ion-exchanged water 400 containing 5 parts by weight of diethylenetriamine and 5 parts by weight of hexamethylenediamine as a curing agent component and 2 parts by weight of polyvinyl alcohol The mixture was added to parts by weight and stirred and emulsified with a homogenizer to prepare a dispersion in which polymerizable droplets having an average particle size of 50 μm were dispersed.
After using a 20 L polymerization vessel equipped with a stirrer, jacket, reflux condenser and thermometer, the inside of the polymerization vessel was depressurized and deoxygenated in the vessel, and then replaced with nitrogen to make the inside nitrogen atmosphere Then, the obtained dispersion was added, and the polymerization vessel was heated to 80 ° C. to initiate polymerization. After polymerization for 4 hours and a aging period of 1 hour thereafter, the polymerization vessel was cooled to room temperature to obtain a slurry containing resin fine particles encapsulating an epoxy monomer component and the like.
The obtained slurry was dehydrated with a centle, and then the epoxy monomer remaining inside the resin fine particles was removed by vacuum drying to obtain hollow resin particles.

(2) A hollow resin obtained with respect to 100 parts by weight of a polypropylene / ethylene block copolymer having a production density of 0.9082 g / cm ³ , an MFR of 30 g / 10 min, and a copolymer part of 12% by weight. 25 parts by weight of fine particles were sufficiently melt-kneaded and granulated in a high-speed mixer under a temperature condition of 220 ° C. to produce pellets for injection molding. Then, the produced pellet was shape | molded on the conditions of the molding pressure of 10 MPa (100 kg / cm < ² >) using the injection compression molding machine.
The cross section of the obtained molded body was observed using an electron microscope (manufactured by Hitachi High-Technologies Corporation, “S-3500N”) to observe the destruction state of the hollow resin fine particles. The results are shown in Table 1.

(3) Production of molded body for porous ceramic filter 100 parts by volume of a ceramic composition composed of 40 parts by weight of silicon carbide, 50 parts by weight of silicon nitride, and 10 parts by weight of carbon powder is used as a pore former. 30 parts by volume of the obtained hollow resin fine particles were added. And after adding 8 weight part of methylcellulose and water and kneading, it was set as the clay which can be extruded.
Next, a honeycomb structure having an outer dimension of 100 mm, a cell dimension of 2.0 mm, and a wall thickness of 0.4 mm was produced from each batch of clay by a known extrusion molding method.
The cross section of the manufactured honeycomb structure was observed using an electron microscope (manufactured by Hitachi High-Technologies Corporation, “S-3500N”) to observe the fracture state of the hollow resin fine particles. The results are shown in Table 1.

(Example 2)
The total amount of the mixed solution obtained by mixing and stirring 20 parts by weight of Epototo YH-434L (epoxy equivalent 110 to 130, manufactured by Tohto Kasei Co., Ltd.) as an epoxy monomer component and 80 parts by weight of toluene as a non-polymerizable compound is used as a curing agent component. Addition to 400 parts by weight of ion-exchanged water containing 3 parts by weight of ethylenediamine and 3 parts by weight of hexamethylenediamine and 2 parts by weight of polyvinyl alcohol, followed by stirring and emulsification with a homogenizer, dispersed droplets having an average particle size of 46 μm. A dispersion was prepared. Thereafter, the hollow resin fine particles were prepared in the same manner as in Example 1 except that the obtained dispersion was used, and the injection-molded article and in the same manner as in Example 1 except that the obtained hollow resin fine particles were used. A honeycomb structure was produced.

(Example 3)
A curing agent is prepared by mixing and stirring 10 parts by weight of Epototo YDCN-704 (epoxy equivalent 195 to 220, manufactured by Tohto Kasei Co., Ltd.) as an epoxy prepolymer component and 90 parts by weight of toluene as a non-polymerizable organic solvent. A solution having an average particle size of 64 μm is added to 400 parts by weight of ion-exchanged water containing 2 parts by weight of diethylenetriamine and 2 parts by weight of hexamethylenediamine and 2 parts by weight of polyvinyl alcohol as an amine component, and stirred and emulsified with a homogenizer. A dispersion in which droplets were dispersed was prepared. Thereafter, the hollow resin fine particles were prepared in the same manner as in Example 1 except that the obtained dispersion was used, and the injection-molded article and in the same manner as in Example 1 except that the obtained hollow resin fine particles were used. A honeycomb structure was produced.

(Comparative Example 1)
Example 1 except that instead of the hollow resin fine particles, “thermally expandable microcapsule F-85D” manufactured by Matsumoto Yushi Seiyaku Co., Ltd., which is a thermoplastic thermally expandable microcapsule, was heated at 170 ° C. for 1 minute. An injection molded body and a honeycomb structure were produced by the same method as described above.

(Comparative Example 2)
Implemented except that a glass balloon having a true density of 0.13 g / cm ³ , a volume average particle diameter of 62 μm, and a 10% by weight breaking pressure strength of 3.0 MPa (30 kg / cm ² ) was used in place of the hollow resin fine particles. An injection molded body and a honeycomb structure were produced in the same manner as in Example 1.

(Evaluation)
The hollow resin fine particles, microballoons, glass balloons, injection molded bodies, and honeycomb structures obtained in Examples 1 to 3 and Comparative Examples 1 and 2 were evaluated by the following methods. The results are shown in Table 1.

(1) Average particle diameter of hollow resin fine particles, etc. The volume average particle diameter was measured using a laser diffraction particle size distribution analyzer (“LA-910” manufactured by Horiba, Ltd.). Three places were sampled from arbitrary places of the powder, and the average value was used.

(2) Measurement of true specific gravity and porosity of hollow resin fine particles, etc. Using a densitometer (manufactured by Shimadzu Corporation, “Accumic 1330”), the true specific gravity of fine particles including voids inside the fine particles is measured, and the porosity is further determined. Calculated.

(3) Measurement of 10% by weight breaking pressure strength The 10% by weight breaking pressure strength was measured according to ASTM-D3102 (using glycerol).

(4) Molding Test The cross sections of the injection molded bodies obtained in Examples 1 to 3 and Comparative Examples 1 and 2 and the honeycomb structure were obtained using an electron microscope (manufactured by Hitachi High-Technologies Corporation, “S-3500N”). Observation was made and the fracture state of the particles was judged according to the following criteria.
○: No crushing △: Some crushing ×: Almost crushing

According to the present invention, it is possible to provide hollow resin fine particles having a high porosity, high strength, and excellent heat resistance and solvent resistance.

Claims (4)

A method for producing hollow resin fine particles comprising a single-pore structure, an epoxy resin having a porosity of 70% or more and a compressive strength of 5.0 MPa or more ,
The epoxy equivalent of the lipophilic reaction Ingredient made of a thermosetting monomer containing less than 500 epoxy monomer 60 wt% or more and a non-polymerizable compound is dispersed as the polymerizable liquid droplets in a polar medium comprising a hydrophilic curing agent Preparing a dispersion,
Possess said lipophilic reactive component in the polymerizable liquid droplets surfactant, a step of reacting the hydrophilic curing agent,
A method for producing hollow resin fine particles , comprising adding 70 to 1000 parts by weight of the non-polymerizable compound to 30 parts by weight of the lipophilic reaction component . Epoxy equivalent of 500 or less epoxy monomers, method of manufacturing the hollow resin particles of claim 1, wherein the epoxy equivalent contains 200 or less of the epoxy monomer 10 wt% or more. Hydrophilic thermosetting agent, production method of the hollow resin fine particles according to claim 2 Symbol placing active hydrogen equivalent is characterized in that it is a 50 following amine curing agent. The method for producing hollow resin fine particles according to claim 3, wherein the amine-based curing agent having an active hydrogen equivalent of 50 or less contains an alkylenediamine having 4 to 10 carbon atoms.