WO2015087987A1

WO2015087987A1 - Particle production method, particles, and dispersion

Info

Publication number: WO2015087987A1
Application number: PCT/JP2014/082902
Authority: WO
Inventors: 金子　尚史; 貴司芥川; 修一篠原; 太田　浩二; 理根布谷; 健一郎榎; 大輝松田; 泰治山下; 要吉井
Original assignee: 三洋化成工業株式会社
Priority date: 2013-12-11
Filing date: 2014-12-11
Publication date: 2015-06-18
Also published as: JP6513028B2; JPWO2015087987A1

Abstract

The purpose of the present invention is to provide a micronized-particle production method whereby a solid is quickly crushed and disintegrated using a small amount of power. The particle (P) production method of the present invention is a production method for particles (P) that contain a substance (A), the method including a step for the volumetric expansion of a mixture (X) that has as constituent parts a compressible fluid (F) and a solid source material (B) that contains the substance (A). The production method is characterized in that, immediately prior to volumetric expansion, the substance (A) is not melted and/or dissolved into the mixture (X).

Description

Method for producing particle, particle and dispersion

The present invention relates to a method for producing particles, particles and a dispersion. Specifically, the present invention relates to a method for producing particles in which a volume expansion of a compressive fluid is generated inside a solid, and the solid is pulverized and crushed, the particles obtained by the method, and a dispersion containing the particles.

In the manufacturing process of paints, inks, electronic circuits, abrasives, cosmetics, foods, pharmaceuticals, and other various processes, there are steps to refine solid materials such as solid particles. It took a long time and a lot of power.
In addition, as a method for improving the above-described method, a method of forming fine particles using a compressive fluid such as supercritical carbon dioxide has been proposed (Patent Document 1). However, in the method described in Patent Document 1, Therefore, it is indispensable that the substance to be formed into fine particles is dissolved in carbon dioxide in a supercritical state. Moreover, the substance insoluble in supercritical carbon dioxide cannot be made into fine particles by the method of Patent Document 1. Further, as an improved version of Patent Document 1, a method has been proposed in which supercritical carbon dioxide is mixed after the dispersoid is dissolved in a solvent, and particles are obtained by volume expansion from a temperature equal to or higher than the melting point of the dispersoid ( Patent Document 2) has a problem that the stability of particles over time is insufficient.

Japanese Patent No. 3754372 JP 2011-115780 A

The problem to be solved by the present invention is to provide a method for producing fine particles by pulverizing and crushing a solid quickly and with less power.

According to the present invention, the particles (P) containing the substance (A) including the step of volume-expanding the mixture (X) containing the solid raw material (B) containing the substance (A) and the compressive fluid (F) as constituent components. There is provided a method for producing particles (P), characterized in that the substance (A) is not melted and / or not dissolved in the mixture (X) immediately before volume expansion, Is resolved.

According to the present invention, a solid raw material and a compressive fluid are mixed, the compressive fluid is infiltrated into the solid, and the solid is pulverized and crushed by volume expansion. Particles can be obtained.

It is a flowchart of the experimental apparatus used for preparation of the dispersion liquid by the mixing method by line blend in this invention.

The present invention is described in detail below.
The present invention includes particles (P) containing a substance (A), including a step of volume-expanding a mixture (X) containing a solid raw material (B) containing the substance (A) and a compressive fluid (F) as constituent components. In which the substance (A) is not melted and / or not dissolved in the mixture (X) immediately before volume expansion.
Since the substance (A) is not melted and / or not dissolved in the mixture (X) immediately before volume expansion, the solid raw material (B) is suitably pulverized and crushed.

Examples of the substance (A) used in the present invention include inorganic substances, organic substances, inorganic pigments, organic pigments, dyes, metals, metal oxides, metal salts, ceramics, pharmaceuticals, polymerization initiators, catalysts, ultraviolet absorbers, semiconductors, and Examples thereof include solid carbon materials. When the mixture (X) with the compressive fluid is formed, it is not limited to these as long as it does not dissolve in the medium containing the compressive fluid and is in a solid state even after the pressure reduction.

The solid raw material (B) means a solid material having any shape including the substance (A). Although there is no restriction | limiting in particular as a shape, For example, granular shape, porous shape, plate shape, or fiber shape is mentioned.

The inorganic substance is not particularly limited as long as it is an inorganic substance containing a metallic element and / or a nonmetallic element. As metal elements, Mg, Al, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, In , Sn, Hf, Ta, W, Re, Os, Ir, Pt, Au and the like, and inorganic substances containing at least one of these metal elements.

Nonmetallic elements include H, B, C, N, O, F, Si, P, S, Cl, Ge, As, Se, Br, Sb, Te, I, etc., and these nonmetallic elements are at least Those inorganic substances containing one kind are listed.

As inorganic substances containing these metal elements and / or non-metal elements, ceramics, semiconductors, inorganic pigments, solid carbon materials, oxides, sulfides, phosphides, carbides, nitrides, arsenides, halides, hydroxides, oxo Examples include acids, sulfates, nitrates, carbonates, acetates, silicates, cyanates, cyanates, thiocyanates, phosphates, titanates, metal complexes, minerals, and the like.

Ceramics include silicon carbide, silicon nitride, alumina, zirconia, and barium titanate. Semiconductors include silicon, germanium, gallium arsenide, aluminum gallium arsenide, indium gallium arsenide, zinc selenide, indium gallium phosphide, and manganese. Inorganic pigments such as zinc ferrite, barium ferrite, yttrium iron garnet, etc. include carbon black, titanium oxide, zinc white, zinc oxide, tripone, iron oxide, aluminum oxide, silicon dioxide, kaolinite, montmorillonite, talc, barium sulfate, carbonic acid Calcium, Silica, Alumina, Cadmium Red, Bengal, Molybdenum Red, Chrome Vermilion, Molybdate Orange, Yellow Lead, Chrome Yellow, Cadmium Yellow, Yellow Iron Oxide, Titanium Yellow, Acid Chromium, pyridian, cobalt green, titanium cobalt green, cobalt chrome green, ultramarine blue, ultramarine blue, bitumen, cobalt blue, cerulean blue, manganese violet, cobalt violet, mica, etc., solid carbon materials include graphite, activated carbon, hard carbon , Soft carbon, carbon fiber, fullerene, carbon nanotube, graphene, graphite, diamond, carbon black, acetylene black, mesoporous carbon, etc., oxides include aluminum oxide, zinc oxide, calcium oxide, silicon oxide, titanium oxide, iron oxide Magnesium oxide, indium tin oxide, etc., sulfides, iron sulfide, copper sulfide, etc., phosphides, cobalt phosphide, tungsten phosphide, etc., carbides, carbonized Nungsten, calcium carbide, etc., nitrides such as silicon nitride and boron nitride, arsenides such as gallium arsenide and nickel arsenide, halides such as aluminum chloride and zirconia chloride, and hydroxides such as hydroxide Aluminum, calcium hydroxide, etc., as sulfate, zinc sulfate, potassium aluminum sulfate dodecahydrate, etc., as nitrate, potassium nitrate, calcium nitrate, etc., as carbonate, barium carbonate, lithium carbonate, etc., as acetate Potassium acetate, sodium acetate, silicate, aluminosilicate, etc., cyanate, sodium cyanate, potassium cyanate, etc., cyanate, potassium cyanide, etc., thiocyanate, thiocyanate Examples of phosphates such as sodium and potassium thiocyanate include calcium phosphate. Potassium phosphate, titanate as barium titanate, strontium titanate etc., metal complex as ammine complex, cyano complex, hydroxy complex, halogeno complex etc., minerals include wollastonite, hydroxyapatite , Montmorillonite, mica, zeolite, kaolinite, hydrotalcite and the like.
In addition, silica balloon, porous silica, neodymium fine particles, and the like are also included.

Organic materials include colorants (organic pigments, dyes), natural products, fluorescent materials, phosphorescent materials, waxes, crystalline resins, amorphous resins, fillers, antistatic agents, charge control agents, UV absorbers, oxidation agents Examples include, but are not limited to, inhibitors, antiblocking agents, heat stabilizers, flame retardants, recontamination inhibitors, and synthetic wood. Examples of the amorphous resin include vinyl resin, epoxy resin, polyester resin, polyamide resin, polyimide resin, silicon resin, phenol resin, melamine resin, urea resin, aniline resin, ionomer resin, polycarbonate resin, acrylic resin, and the like. Also, two or more of the above resins may be used in combination. As the natural product, cellulose and the like are preferable. Of these, organic pigments, vinyl resins, polyester resins, polyurethane resins, epoxy resins, and combinations thereof are more preferable from the viewpoint that particles can be easily refined.

Hereinafter, organic pigments, dyes, vinyl resins, polyester resins, polyurethane resins and epoxy resins, which are preferable as organic substances, will be described in detail.

Organic pigments and dyes include monoazo, disazo, metal complex azo, anthraquinone, indigo, phthalocyanine, pyrazolone, stilbene, thiazole, quinoline, diphenylmethane, triphenylmethane, acridine, xanthene, azine, thiazine, oxazine, polymethine, indophenol As an organic pigment such as perylene, anthraquinone, azo lake, insoluble azo, condensed azo, azomethine, quinophthalone, benzimidazolone, phthalocyanine, perylene, dioxazine, indigo, quinacridone, Examples thereof include isoindolinone series, benzimidazolone series, diketopyrrolopyrrole series, metal complexes, and the like, and mixtures thereof.
Specific examples include Carbon Black, Sudan Black SM, First Yellow-G, Benzidine Yellow, Pigment Yellow, Indian First Orange, Pigment Red, Irgasin Red, Paranitroaniline Red, Toluidine Red, Carmine FB, Pigment Orange R, Lake Red 2G, rhodamine FB, rhodamine B lake, methyl violet B lake, phthalocyanine blue, pigment blue, brilliant green, phthalocyanine green, oil yellow GG, Kayaset YG, olasol brown B, and oil pink OP.
The vinyl resin is a polymer obtained by homopolymerizing or copolymerizing vinyl monomers. Examples of the vinyl monomer include the following (1) to (10).
(1) Vinyl hydrocarbon:
(1-1) Aliphatic vinyl hydrocarbon:
Alkenes such as ethylene, propylene, butene, isobutylene, pentene, heptene, diisobutylene, octene, dodecene, octadecene, other α-olefins, etc .; alkadienes such as butadiene, isoprene, 1,4-pentadiene, 1,6 -Hexadiene, 1,7-octadiene.
(1-2) Alicyclic vinyl hydrocarbon:
Mono- or di-cycloalkenes and alkadienes such as cyclohexene, (di) cyclopentadiene, vinylcyclohexene, ethylidenebicycloheptene and the like; terpenes such as pinene, limonene and indene.
(1-3) Aromatic vinyl hydrocarbon:
Styrene and its hydrocarbyl (alkyl, cycloalkyl, aralkyl and / or alkenyl) substitutes such as α-methylstyrene, vinyltoluene, 2,4-dimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, phenylstyrene, cyclohexyl Styrene, benzylstyrene, crotylbenzene, divinylbenzene, divinyltoluene, divinylxylene, trivinylbenzene, and the like; and vinylnaphthalene.

(2) Carboxyl group-containing vinyl monomer and metal salt thereof:
Unsaturated monocarboxylic acid, unsaturated dicarboxylic acid having 3 to 30 carbon atoms and anhydride and monoalkyl (carbon number 1 to 24) ester thereof such as (meth) acrylic acid, (anhydrous) maleic acid, monoalkyl maleate Carboxyl group-containing vinyl monomers such as esters, fumaric acid, fumaric acid monoalkyl esters, crotonic acid, itaconic acid, itaconic acid monoalkyl esters, itaconic acid glycol monoether, citraconic acid, citraconic acid monoalkyl esters, cinnamic acid; Metal salt.

(3) Sulfone group-containing vinyl monomer, vinyl sulfate monoester product and salts thereof:
Alkene sulfonic acids having 2 to 14 carbon atoms such as vinyl sulfonic acid, (meth) allyl sulfonic acid, methyl vinyl sulfonic acid, styrene sulfonic acid; and alkyl derivatives thereof having 2 to 24 carbon atoms such as α-methyl styrene sulfonic acid Sulfo (hydroxy) alkyl- (meth) acrylate or (meth) acrylamide, such as sulfopropyl (meth) acrylate, 2-hydroxy-3- (meth) acryloxypropylsulfonic acid, 2- (meth) acryloylamino-2 , 2-dimethylethanesulfonic acid, 2- (meth) acryloyloxyethanesulfonic acid, 3- (meth) acryloyloxy-2-hydroxypropanesulfonic acid, 2- (meth) acrylamido-2-methylpropanesulfonic acid, 3- (Meth) acrylamide-2-hi Roxypropanesulfonic acid, alkyl (C3-18) allylsulfosuccinic acid, poly (n = 2-30) oxyalkylene (ethylene, propylene, butylene: single, random, block may be) mono (meth) acrylate sulfate [Poly (n = 5 to 15) oxypropylene monomethacrylate sulfate, etc.], polyoxyethylene polycyclic phenyl ether sulfate, and sulfate or sulfone represented by the following general formulas (1-1) to (1-3) Acid group-containing monomers; and salts thereof.

(Wherein R represents an alkyl group having 1 to 15 carbon atoms, A represents an alkylene group having 2 to 4 carbon atoms, and when n is plural, they may be the same or different, and when they are different, they may be random or block). Ar represents a benzene ring, n represents an integer of 1 to 50, and R ′ represents an alkyl group having 1 to 15 carbon atoms which may be substituted with a fluorine atom.)

(4) Phosphoric acid group-containing vinyl monomer and salt thereof:
(Meth) acryloyloxyalkyl (C1 to C24) phosphoric acid monoesters such as 2-hydroxyethyl (meth) acryloyl phosphate, phenyl-2-acryloyloxyethyl phosphate, (meth) acryloyloxyalkyl (1 to 24 carbon atoms) Phosphonic acids, such as 2-acryloyloxyethylphosphonic acid; and their salts. C1 to C24 mean 1 to 24 carbon atoms.

Examples of the salts (organic acid salts) of (2) to (4) above include metal salts, ammonium salts, and amine salts (including quaternary ammonium salts). Examples of the metal forming the metal salt include Al, Ti, Cr, Mn, Fe, Zn, Ba, Zr, Ca, Mg, Na, and K.
Alkali metal salts and amine salts are preferred, and sodium salts and tertiary monoamine salts having 3 to 20 carbon atoms are more preferred.

(5) Hydroxyl group-containing vinyl monomer:
Hydroxystyrene, N-methylol (meth) acrylamide, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, (meth) allyl alcohol, crotyl alcohol, isocrotyl alcohol, 1- Buten-3-ol, 2-buten-1-ol, 2-butene-1,4-diol, propargyl alcohol, 2-hydroxyethylpropenyl ether, sucrose allyl ether, and the like.

(6) Nitrogen-containing vinyl monomer:
(6-1) Amino group-containing vinyl monomer: aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, t-butylaminoethyl methacrylate, N-aminoethyl (meth) acrylamide, (Meth) allylamine, morpholinoethyl (meth) acrylate, 4-vinylpyridine, 2-vinylpyridine, crotylamine, N, N-dimethylaminostyrene, methyl α-acetaminoacrylate, vinylimidazole, N-vinylpyrrole, N-vinylthio Pyrrolidone, N-arylphenylenediamine, aminocarbazole, aminothiazole, aminoindole, aminopyrrole, aminoimidazole, aminomercaptothiazole, salts thereof and the like.
(6-2) Amide group-containing vinyl monomers: (meth) acrylamide, N-methyl (meth) acrylamide, N-butylacrylamide, diacetone acrylamide, N-methylol (meth) acrylamide, N, N′-methylene-bis ( (Meth) acrylamide, cinnamic amide, N, N-dimethylacrylamide, N, N-dibenzylacrylamide, methacrylformamide, N-methyl N-vinylacetamide, N-vinylpyrrolidone, etc. (6-3) Nitrile group-containing vinyl monomers: (Meth) acrylonitrile, cyanostyrene, cyanoacrylate and the like.
(6-4) Quaternary ammonium cationic group-containing vinyl monomers: tertiary amines such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide, diallylamine and the like Quaternized products of group-containing vinyl monomers (quaternized with a quaternizing agent such as methyl chloride, dimethyl sulfate, benzyl chloride, dimethyl carbonate).
(6-5) Nitro group-containing vinyl monomer: nitrostyrene and the like.

(7) Epoxy group-containing vinyl monomer:
Glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, p-vinylphenylphenyl oxide and the like.

(8) Halogen element-containing vinyl monomer:
Vinyl chloride, vinyl bromide, vinylidene chloride, allyl chloride, chlorostyrene, bromostyrene, dichlorostyrene, chloromethylstyrene, tetrafluorostyrene, chloroprene and the like.

(9) Vinyl esters, vinyl (thio) ethers, vinyl ketones, vinyl sulfones:
(9-1) Vinyl esters such as vinyl acetate, vinyl butyrate, vinyl propionate, vinyl butyrate, diallyl phthalate, diallyl adipate, isopropenyl acetate, vinyl methacrylate, methyl 4-vinylbenzoate, cyclohexyl methacrylate, benzyl methacrylate, phenyl (Meth) acrylate, vinyl methoxyacetate, vinyl benzoate, ethyl α-ethoxy acrylate, alkyl (meth) acrylate having an alkyl group having 1 to 50 carbon atoms [methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) Acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, hexadecyl (meth) acrylate, heptade (Meth) acrylate, eicosyl (meth) acrylate, etc.], dialkyl fumarate (two alkyl groups are linear, branched or alicyclic groups having 2 to 8 carbon atoms), dialkyl maleate Ate (two alkyl groups are straight-chain, branched-chain or alicyclic groups having 2 to 8 carbon atoms), poly (meth) allyloxyalkanes [diallyloxyethane, triaryloxyethane , Tetraallyloxyethane, tetraallyloxypropane, tetraallyloxybutane, tetrametaallyloxyethane, etc.] vinyl monomers having a polyalkylene glycol chain [polyethylene glycol (molecular weight 300) mono (meth) acrylate, polypropylene glycol ( Molecular weight 500) monoacrylate, methyl alcohol ethylene oxide (ethylene oxide) 10 mol adducts (meth) acrylates, lauryl alcohol EO 30 mol adducts (meth) acrylates, etc.], poly (meth) acrylates [poly (meth) acrylates of polyhydric alcohols: ethylene glycol Di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, polyethylene glycol di (meth) acrylate, etc.].
(9-2) Vinyl (thio) ether, such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, vinyl butyl ether, vinyl 2-ethylhexyl ether, vinyl phenyl ether, vinyl 2-methoxyethyl ether, methoxybutadiene, vinyl 2- Butoxyethyl ether, 3,4-dihydro1,2-pyran, 2-butoxy-2′-vinyloxydiethyl ether, vinyl 2-ethylmercaptoethyl ether, acetoxystyrene, phenoxystyrene, and the like.
(9-3) Vinyl ketones such as vinyl methyl ketone, vinyl ethyl ketone, vinyl phenyl ketone (9-4) Vinyl sulfones such as divinyl sulfide, p-vinyl diphenyl sulfide, vinyl ethyl sulfide, vinyl ethyl sulfone, divinyl sulfone, divinyl sulfone Faux side etc.

(10) Other vinyl monomers:
(10-1) Isocyanatoethyl (meth) acrylate, m-isopropenyl-α, α-dimethylbenzyl isocyanate and the like.

(10-2) Monomer having a dimethylsiloxane group: methacryl-modified silicone is preferable, and examples thereof include those having a structure represented by the following formula.
(CH ₃ ) ₃ SiO ((CH ₃ ) ₂ SiO) _a Si (CH ₃ ) ₂ R (where a is an average value of 15 to 45, and R is an organically modified group containing a methacryl group)
An example of R includes C ₃ H ₆ OCOC (CH ₃ ) ═CH ₂ .

(10-3) Monomers containing fluorine: Perfluoroolefins such as tetrafluoroethylene (TFE), hexafluoropropylene (HFP), chlorotrifluoroethylene (CTFE); perfluoro (alkyl vinyl ether) (PFAVE), perfluoro (1,3-dioxole), perfluoro (2,2-dimethyl-1,3-dioxole) (PFDD), perfluoro- (2-methylene-4-methyl-1,3-dioxolane) (MMD), perfluoro Perfluorovinyl ethers such as fluorobutenyl vinyl ether (PFBVE); vinylidene fluoride (VdF), trifluoroethylene, 1,2-difluoroethylene, vinyl fluoride, trifluoropropylene, 3,3,3-trifluoro-2- Trifluoromethyl prope , 3,3,3-trifluoropropene, perfluoro (butyl) ethylene (PFBE) and other hydrogen atom-containing fluoroolefins; 1,1-dihydroperfluorooctyl acrylate (DPFOA), 1,1-dihydroperfluorooctyl methacrylate (DPFOMA), 2- (perfluorooctyl) ethyl acrylate (PFOEA), 2- (perfluorooctyl) ethyl methacrylate (PFOEMA), 2- (perfluorohexyl) ethyl methacrylate (PFHEMA), 2- (perfluorobutyl) Polyfluoroalkyl (meth) acrylates such as ethyl methacrylate (PFBEMA); α-fluorostyrene, β-fluorostyrene, α, β-difluorostyrene, β, β-difluorostyrene, α, β, β-trifluoro Styrene, α-trifluoromethylstyrene, 2,4,6-tri (trifluoromethyl) styrene, 2,3,4,5,6-pentafluorostyrene, 2,3,4,5,6-pentafluoro- Examples thereof include fluorostyrene such as α-methylstyrene and 2,3,4,5,6-pentafluoro-β-methylstyrene.

When a vinyl resin containing a salt of an organic acid is used as the vinyl monomer, this resin may be, for example, Al, Ti, Cr, among the salts of the monomers (2) to (4) as at least a part of the vinyl monomer. It can be obtained by using one or more metal salts selected from Mn, Fe, Zn, Ba, and Zr. The amount of these organic acid salts used in all monomers used for the polymerization is preferably 5 to 60% by weight. The lower limit is more preferably 10% by weight, and the upper limit is more preferably 50% by weight.

Examples of the copolymer of vinyl monomers include polymers obtained by copolymerizing any of the above monomers (1) to (10) in a binary or higher number at an arbitrary ratio. (Meth) acrylic acid ester- (meth) acrylic acid copolymer, styrene-butadiene- (meth) acrylic acid copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-acrylonitrile- ( (Meth) acrylic acid copolymer, styrene- (meth) acrylic acid copolymer, styrene- (meth) acrylic acid-divinylbenzene copolymer, styrene-styrenesulfonic acid- (meth) acrylic acid ester copolymer, and Examples thereof include salts of these copolymers.

Examples of polyester resins include polycondensates of polyols with polycarboxylic acids or acid anhydrides or lower alkyl esters thereof, and metal salts of these polycondensates. The polyol is a diol (11) and a polyol (12) having a valence of 3 to 8 or higher, and the polycarboxylic acid or its acid anhydride or its lower alkyl ester is a dicarboxylic acid (13) or 3 to 6 Examples thereof include polycarboxylic acids (14) having a valence of 1 or higher and acid anhydrides or lower alkyl esters thereof.
The ratio of the polyol and the polycarboxylic acid is preferably 2/1 to 1/5, more preferably 1.5 / 1 to the equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. 1/4, particularly preferably from 1 / 1.3 to 1/3.
In order to keep the carboxyl group content within the above preferred range, the polyester having an excess of hydroxyl groups may be treated with polycarboxylic acid.

Examples of the diol (11) include alkylene glycols having 2 to 36 carbon atoms (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, octanediol, Decanediol, dodecanediol, tetradecandiol, neopentyl glycol, 2,2-diethyl-1,3-propanediol, etc.); alkylene ether glycols having 4 to 36 carbon atoms (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol) Polypropylene glycol, polytetramethylene ether glycol, etc.); alicyclic diols having 4 to 36 carbon atoms (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); Alkylene oxide or alicyclic diol alkylene oxide (hereinafter abbreviated as AO) [EO, propylene oxide (hereinafter abbreviated as PO), butylene oxide (hereinafter abbreviated as BO), etc.) adduct (addition mole number 1 to 120) ); AO (EO, PO, BO, etc.) adducts of bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.) (addition moles 2-30); polylactone diol (poly ε-caprolactone diol, etc.); and polybutadiene Diol etc. are mentioned.

As the diol (11), in addition to the diol having no functional group other than the above hydroxyl group, a diol (11a) having another functional group may be used. Examples of the diol (11a) include a diol having a carboxyl group, a diol having a sulfonic acid group or a sulfamic acid group, and salts thereof.
Diols having a carboxyl group include dialkylol alkanoic acids [from C6-24, such as 2,2-dimethylolpropionic acid (DMPA), 2,2-dimethylolbutanoic acid, 2,2-dimethylolheptanoic acid. 2,2-dimethyloloctanoic acid, etc.].
Examples of the diol having a sulfonic acid group or a sulfamic acid group include a sulfamic acid diol [N, N-bis (2-hydroxyalkyl) sulfamic acid (alkyl group is C1-6) or an AO adduct thereof (EO is EO or PO as AO). Etc., AO addition mole number 1 to 6): for example, N, N-bis (2-hydroxyethyl) sulfamic acid and N, N-bis (2-hydroxyethyl) sulfamic acid PO2 molar adduct, etc.]; bis (2 -Hydroxyethyl) phosphate and the like.
Examples of the salt of the diol having a functional group other than the hydroxyl group include salts of the functional group with the tertiary amine having 3 to 30 carbon atoms (such as triethylamine) and / or alkali metal (such as sodium). It is done.
Among these, preferred are alkylene glycols having 2 to 12 carbon atoms, diols having a carboxyl group, AO adducts of bisphenols, and combinations thereof.

Examples of the polyol (12) having a valence of 3 to 8 or higher include polyhydric aliphatic alcohols having a valence of 3 to 8 or more having 3 to 36 carbon atoms (alkane polyol and its intramolecular or intermolecular). Dehydrates such as glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, sorbitan, and polyglycerin; sugars and derivatives thereof such as sucrose and methylglucoside); AO adducts of polyhydric fatty alcohols (addition) AO adducts of trisphenols (trisphenol PA, etc.) (addition moles 2-30); AO adducts of novolak resins (phenol novolac, cresol novolac, etc.) (addition moles 2-30) ); Acrylic polyol [hydroxyethyl (meth) acrylate and other vinyl Copolymerization products of Rumonoma]; and the like.
Among these, preferred are trivalent to octavalent or higher valent polyhydric aliphatic alcohols and novolak resin AO adducts, and more preferred are novolak resin AO adducts.

Examples of the dicarboxylic acid (13) include alkane dicarboxylic acids having 4 to 36 carbon atoms (succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedicarboxylic acid, octadecanedicarboxylic acid, decylsuccinic acid, etc.) and alkenyl succinic acids (dodecenyl succinic acid, Pentadecenyl succinic acid, octadecenyl succinic acid, etc.); alicyclic dicarboxylic acid having 6 to 40 carbon atoms (dimer acid (dimerized linoleic acid) etc.), alkenedicarboxylic acid having 4 to 36 carbon atoms (maleic acid) Acid, fumaric acid, citraconic acid, etc.); aromatic dicarboxylic acids having 8 to 36 carbon atoms (phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, etc.). Of these, alkene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms are preferable.
Examples of the polycarboxylic acid (14) having a valence of 3 to 6 or higher include aromatic polycarboxylic acids having 9 to 20 carbon atoms (trimellitic acid, pyromellitic acid, etc.).
Examples of the dicarboxylic acid (13) or the polycarboxylic acid (14) having a valence of 3 to 6 or higher include the above acid anhydrides or lower alkyl esters having 1 to 4 carbon atoms (methyl ester, ethyl ester). , Isopropyl ester, etc.) may be used.

When a polyester resin containing a structural unit of an organic acid salt is used, this resin is synthesized, for example, by synthesizing a polyester having an COOH residue (acid value is preferably 1 to 100, more preferably 5 to 50), The at least one COOH group can be obtained by converting it into a salt of at least one metal selected from Al, Ti, Cr, Mn, Fe, Zn, Ba, and Zr.
As a method for forming a metal salt, for example, it is obtained by reacting a polyester having a COOH group with a hydroxide of the corresponding metal.

Examples of the polyurethane resin include polyisocyanate (15) and active hydrogen-containing compound {water, polyol [including diol (11) (including diol (11a) having a functional group other than hydroxyl group)], and trivalent to octavalent or higher Polyol (12)], polycarboxylic acid [dicarboxylic acid (13), and polycarboxylic acid (14) having a valence of 3 to 6 or more], and obtained by polycondensation of polyol and polycarboxylic acid. Polyester polyols, ring-opening polymers of lactones having 6 to 12 carbon atoms, polyadditions of polyamine (16), polythiol (17), and combinations thereof}, and polyisocyanate (15) and an active hydrogen-containing compound. A terminal isocyanate group prepolymer obtained by reaction, and an equivalent amount of primary and isocyanate groups of the prepolymer; Or a secondary monoamine (18) is obtained by reacting, and amino group-containing polyurethane resins.
The content of the carboxyl group in the polyurethane resin is preferably 0.1 to 10% by weight based on the weight of the polyurethane resin.

Examples of the polyisocyanate (15) include aromatic polyisocyanates having 6 to 20 carbon atoms (excluding carbon in the NCO group, the same shall apply hereinafter), aliphatic polyisocyanates having 2 to 18 carbon atoms, and alicyclic rings having 4 to 15 carbon atoms. Formula polyisocyanates, araliphatic polyisocyanates having 8 to 15 carbon atoms and modified products of these polyisocyanates (urethane groups, carbodiimide groups, allophanate groups, urea groups, burette groups, uretdione groups, uretoimine groups, isocyanurate groups, Oxazolidone group-containing modified products) and mixtures of two or more thereof.

Specific examples of the aromatic polyisocyanate having 6 to 20 carbon atoms include 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate (TDI), crude TDI, 2, 4′- or 4,4′-diphenylmethane diisocyanate (MDI), crude MDI [crude diaminophenylmethane [condensation product of formaldehyde and aromatic amine (aniline) or a mixture thereof; diaminodiphenylmethane and a small amount (for example, 5 to 20 wt.] %)) With a trifunctional or higher polyamine]]: phosgenate: polyallyl polyisocyanate (PAPI)], 1,5-naphthylene diisocyanate, 4,4 ′, 4 ″ -triphenylmethane triisocyanate, m-or and p-isocyanatophenylsulfonyl isocyanate.
Specific examples of the aliphatic polyisocyanate having 2 to 18 carbon atoms include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4 Trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethylcaproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6- Aliphatic polyisocyanates such as diisocyanatohexanoate are listed.
Specific examples of the alicyclic polyisocyanate having 4 to 15 carbon atoms include isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated). TDI), bis (2-isocyanatoethyl) -4-cyclohexene-1,2-dicarboxylate, 2,5- and / or 2,6-norbornane diisocyanate.
Specific examples of the araliphatic polyisocyanate having 8 to 15 carbon atoms include m- or p-xylylene diisocyanate (XDI), α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI) and the like. Can be mentioned.
Examples of the modified polyisocyanate include urethane group, carbodiimide group, allophanate group, urea group, burette group, uretdione group, uretoimine group, isocyanurate group, and oxazolidone group-containing modified product.
Specifically, modified MDI (urethane-modified MDI, carbodiimide-modified MDI, trihydrocarbyl phosphate-modified MDI, etc.), modified polyisocyanates such as urethane-modified TDI, and mixtures of two or more thereof (for example, modified MDI and urethane-modified TDI). (Combined use with an isocyanate-containing prepolymer)] is included.
Among these, preferred are aromatic polyisocyanates having 6 to 15 carbon atoms, aliphatic polyisocyanates having 4 to 12 carbon atoms, and alicyclic polyisocyanates having 4 to 15 carbon atoms, and particularly preferred are TDI, MDI, HDI, hydrogenated MDI, and IPDI.

Examples of polyamine (16) include
Aliphatic polyamines (C2 to C18): [1] Aliphatic polyamines {C2 to C6 alkylenediamine (ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, etc.), polyalkylene (C2 to C6) polyamine [Diethylenetriamine, iminobispropylamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, etc.]}; [2] These alkyls (C1 to C4) or hydroxyalkyls (C2 to C4) Substituted compounds [dialkyl (C1-C3) aminopropylamine, trimethylhexamethylenediamine, aminoethylethanolamine, 2,5-dimethyl-2,5-hexamethylenediamine, methyliminobispro [3] Alicyclic or heterocyclic-containing aliphatic polyamine [3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5,5] undecane, etc.]; 4] Aromatic ring-containing aliphatic amines (C8 to C15) (xylylenediamine, tetrachloro-p-xylylenediamine, etc.)
Alicyclic polyamines (C4 to C15): 1,3-diaminocyclohexane, isophoronediamine, mensendiamine, 4,4′-methylenedicyclohexanediamine (hydrogenated methylenedianiline), etc.
Heterocyclic polyamines (C4 to C15): piperazine, N-aminoethylpiperazine, 1,4-diaminoethylpiperazine, 1,4bis (2-amino-2-methylpropyl) piperazine, etc.
Aromatic polyamines (C6 to C20): [1] unsubstituted aromatic polyamine 1,2-, 1,3- or 1,4-phenylenediamine, 2,4'- or 4,4'-diphenylmethanediamine, crude Diphenylmethanediamine (polyphenylpolymethylenepolyamine), diaminodiphenylsulfone, benzidine, thiodianiline, bis (3,4-diaminophenyl) sulfone, 2,6-diaminopyridine, m-aminobenzylamine, triphenylmethane-4,4 ' , 4 ″ -triamine, naphthylenediamine, etc.]; [2] Aromatic polyamines having a nucleus-substituted alkyl group (C1-C4 alkyl group such as methyl, ethyl, n- or i-propyl, butyl, etc.), for example 2,4 -Or 2,6-tolylenediamine, crude tolylenediamine, diethyltolylenediamine 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-bis (o-toluidine), dianisidine, diaminoditolyl sulfone, 1,3-dimethyl-2,4-diaminobenzene, , 3-Dimethyl-2,6-diaminobenzene, 1,4-diisopropyl-2,5-diaminobenzene, 2,4-diaminomesitylene, 1-methyl-3,5-diethyl-2,4-diaminobenzene, 2 , 3-Dimethyl-1,4-diaminonaphthalene, 2,6-dimethyl-1,5-diaminonaphthalene, 3,3 ′, 5,5′-tetramethylbenzidine, 3,3 ′, 5,5′-tetra Methyl-4,4'-diaminodiphenylmethane, 3,5-diethyl-3'-methyl-2 ', 4-diaminodiphenylmethane, 3,3'-diethyl-2,2'-diaminodiph Nylmethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 3,3 ', 5,5'-tetraethyl-4,4'-diaminobenzophenone, 3,3', 5,5'-tetraethyl-4 , 4'-diaminodiphenyl ether, 3,3 ', 5,5'-tetraisopropyl-4,4'-diaminodiphenylsulfone, and the like, and mixtures of these isomers in various proportions; [3] Nuclear-substituted electron withdrawing groups Aromatic polyamines [Methylenebis-o-chloroaniline, 4-chloro-o-phenylenediamine, 2-chloro-, etc.] (halogens such as Cl, Br, I, F, etc .; alkoxy groups such as methoxy and ethoxy; nitro groups, etc.) 1,4-phenylenediamine, 3-amino-4-chloroaniline, 4-bromo-1,3-phenylenediamine, 2,5-dichloro-1,4-pheny Diamine, 5-nitro-1,3-phenylenediamine, 3-dimethoxy-4-aminoaniline; 4,4'-diamino-3,3'-dimethyl-5,5'-dibromo-diphenylmethane, 3,3'- Dichlorobenzidine, 3,3′-dimethoxybenzidine, bis (4-amino-3-chlorophenyl) oxide, bis (4-amino-2-chlorophenyl) propane, bis (4-amino-2-chlorophenyl) sulfone, bis (4 -Amino-3-methoxyphenyl) decane, bis (4-aminophenyl) sulfide, bis (4-aminophenyl) tellide, bis (4-aminophenyl) selenide, bis (4-amino-3-methoxyphenyl) disulfide, 4,4'-methylenebis (2-iodoaniline), 4,4'-methylenebis (2-bromoanily) ), 4,4′-methylenebis (2-fluoroaniline), 4-aminophenyl-2-chloroaniline, etc.]; [4] Aromatic polyamines having secondary amino groups [aromatics of [1] to [3] above A part or all of —NH ₂ of the group polyamine is replaced by —NH—R ′ (R ′ is an alkyl group such as a lower alkyl group such as methyl, ethyl, etc.)] [4,4′-di (methyl Amino) diphenylmethane, 1-methyl-2-methylamino-4-aminobenzene, etc.], polyamide polyamine: dicarboxylic acid (dimer acid, etc.) and excess (more than 2 moles per mole of acid) polyamines (the above alkylenediamine, Low molecular weight polyamide polyamines obtained by condensation with polyalkylene polyamines, etc., polyether polyamines: polyether polyols (polyalkylene glycols) Hydrides of cyanoethylation products of Lumpur, etc.).

Examples of the polythiol (17) include alkanedithiols having 2 to 36 carbon atoms (ethylene dithiol, 1,4-butanedithiol, 1,6-hexanedithiol, etc.).

Examples of the primary and / or secondary monoamine (18) include alkylamines having 2 to 24 carbon atoms (ethylamine, n-butylamine, isobutylamine, etc.) and the like.

Examples of the epoxy resin include a ring-opening polymer of polyepoxide (19), polyepoxide (19) and active hydrogen group-containing compound (T) {water, polyol [the diol (11) and a polyol having a valence of 3 or more (12). ], Dicarboxylic acid (13), polyaddition product of polycarboxylic acid (14), polyamine (16), polythiol (17) etc. having a valence of 3 or more, or polyepoxide (19) and dicarboxylic acid (13) Or the hardened | cured material with the acid anhydride of polycarboxylic acid (14) of the valence more than trivalence etc. are mentioned.

The polyepoxide (19) used in the present invention is not particularly limited as long as it has two or more epoxy groups in the molecule. A preferable polyepoxide (19) is one having 2 to 6 epoxy groups in the molecule from the viewpoint of mechanical properties of the cured product. The epoxy equivalent of the polyepoxide (19) (molecular weight per epoxy group) is usually from 65 to 1,000, and preferably from 90 to 500. When the epoxy equivalent exceeds 1000, the cross-linked structure becomes loose and the physical properties such as water resistance, chemical resistance and mechanical strength of the cured product are deteriorated. On the other hand, it is difficult to synthesize an epoxy equivalent of less than 65. is there.

Examples of the polyepoxide (19) include aromatic polyepoxy compounds, heterocyclic polyepoxy compounds, alicyclic polyepoxy compounds, and aliphatic polyepoxy compounds. Examples of aromatic polyepoxy compounds include glycidyl ethers and glycidyl ethers of polyhydric phenols, glycidyl aromatic polyamines, and glycidylated products of aminophenols. Examples of glycidyl ethers of polyphenols include bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, bisphenol B diglycidyl ether, bisphenol AD diglycidyl ether, bisphenol S diglycidyl ether, halogenated bisphenol A diglycidyl, and tetrachlorobisphenol A. Diglycidyl ether, catechin diglycidyl ether, resorcinol diglycidyl ether, hydroquinone diglycidyl ether, pyrogallol triglycidyl ether, 1,5-dihydroxynaphthalene diglycidyl ether, dihydroxybiphenyl diglycidyl ether, octachloro-4,4'-dihydroxybiphenyl di Glycidyl ether, tetramethylbiphenyl diglycidyl ester Ter, dihydroxynaphthylcresol triglycidyl ether, tris (hydroxyphenyl) methane triglycidyl ether, dinaphthyltriol triglycidyl ether, tetrakis (4-hydroxyphenyl) ethanetetraglycidyl ether, p-glycidylphenyldimethyltolylbisphenol A glycidyl ether, trismethyl -Tret-butyl-butylhydroxymethane triglycidyl ether, 9,9'-bis (4-hydroxyphenyl) furorange glycidyl ether, 4,4'-oxybis (1,4-phenylethyl) tetracresol glycidyl ether, 4 , 4′-oxybis (1,4-phenylethyl) phenylglycidyl ether, bis (dihydroxynaphthalene) tetraglycidyl ether, Glycidyl ether form of enol or cresol novolac resin, glycidyl ether form of limonene phenol novolak resin, diglycidyl ether form obtained from the reaction of 2 mol of bisphenol A and 3 mol of epichlorohydrin, phenol and glyoxal, glutaraldehyde, or formaldehyde Examples thereof include polyglycidyl ethers of polyphenols obtained by a condensation reaction and polyglycidyl ethers of polyphenols obtained by a condensation reaction of resorcin and acetone. Examples of the glycidyl ester of polyhydric phenol include diglycidyl phthalate, diglycidyl isophthalate, and diglycidyl terephthalate. Examples of the glycidyl aromatic polyamine include N, N-diglycidylaniline, N, N, N ′, N′-tetraglycidylxylylenediamine, N, N, N ′, N′-tetraglycidyldiphenylmethanediamine and the like. Further, in the present invention, as the aromatic system, triglycidyl ether of p-aminophenol, tolylene diisocyanate or diglycidyl urethane compound obtained by addition reaction of diphenylmethane diisocyanate and glycidol, obtained by reacting a polyol with the above two reactants. The glycidyl group-containing polyurethane (pre) polymer and an alkylene oxide (ethylene oxide or propylene oxide) adduct of bisphenol A are also included. Heterocyclic polyepoxy compounds include trisglycidyl melamine; alicyclic polyepoxy compounds include vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, bis (2,3-epoxycyclopentyl). Ether, ethylene glycol bisepoxy dicyclopentyl ether, 3,4-epoxy-6-methylcyclohexylmethyl-3 ′, 4′-epoxy-6′-methylcyclohexanecarboxylate, bis (3,4-epoxy-6-methylcyclohexyl) Methyl) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) butylamine, dimer acid diglycidyl ester and the like. The alicyclic polyepoxy compound also includes a nuclear hydrogenated product of the aromatic polyepoxide compound. Examples of the aliphatic polyepoxy compound include polyglycidyl ethers of polyhydric aliphatic alcohols, polyglycidyl esters of polyhydric fatty acids, and glycidyl aliphatic amines. Polyglycidyl ethers of polyhydric aliphatic alcohols include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol Examples include diglycidyl ether, polytetramethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane polyglycidyl ether, glycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, sorbitol polyglycidyl ether and polyglycerol polyglycidyl ether. It is done. Examples of polyglycidyl ester of polyvalent fatty acid include diglycidyl oxalate, diglycidyl malate, diglycidyl succinate, diglycidyl glutarate, diglycidyl adipate, diglycidyl pimelate and the like. Examples of the glycidyl aliphatic amine include N, N, N ′, N′-tetraglycidylhexamethylenediamine. In the present invention, the aliphatic polyepoxy compound includes a (co) polymer of diglycidyl ether and glycidyl (meth) acrylate. Of these, preferred are aliphatic polyepoxy compounds and aromatic polyepoxy compounds. Two or more of the polyepoxides of the present invention may be used in combination.

In the present invention, the organic substance preferably has a melting point. The organic material preferably has a glass transition point.

In the present invention, “not melted” means less than the melting point or less than the glass transition temperature of the solid material (B) containing the substance (A), and the solid material (B) remains solid in the mixture (X). Means that Even when particles are obtained by volume expansion of the mixture (X) at a melting point or higher than the glass transition temperature, the obtained particles have insufficient stability.

In the present invention, “not dissolved” means that the solid raw material (B) containing the substance (A) is not dissolved in the compressive fluid (F) and is maintained in a solid state, or in the mixture (X). When the medium (M) is included, it means that the solid raw material (B) is not dissolved in the medium (M) and is maintained in a solid state.

The solid raw material (B) containing the substance (A) is not dissolved and / or does not melt in the mixture (X) immediately before the volume expansion, so that the compressive fluid can penetrate into the solid raw material. By generating volume expansion inside the solid raw material, the solid raw material (B) is pulverized and crushed to produce particles (P) composed of the solid raw material (B) containing the substance (A).

In the present invention, the mixture (X) is composed of the solid raw material (B) and the compressive fluid (F), and the medium (M) if the solid raw material (B) exists as a solid in the mixture (X). It is possible to add the particle forming aid (D).

The medium (M) and the particle forming aid (D) are preferably liquid in the mixture (X). By liquid is meant dissolved or melted.
Whether the solid raw material is maintained in a solid state in the mixture and whether the particle forming aid is in a liquid state are visually confirmed from an observation window provided in the pressure vessel.

In addition, the additives [dispersants, leveling agents, plasticizers, antistatic agents, charge control agents, UV absorbers, antiblocking agents, heat stabilizers, flame retardants, fillers, washings as long as the performance of the present invention is not impaired. Agent, foaming agent, wetting agent, moisturizing agent, emulsifier, solubilizer, dispersant, pearlizing agent, styling agent, bactericidal agent, antibacterial agent, preservative, scrub agent, viscosity modifier, gelling agent, defoaming agent Agent, antistatic agent, plasticizer, mold release agent, ultraviolet absorber, light stabilizer and infrared absorber, polymerization inhibitor, initiator (thermal polymerization initiator, photopolymerization initiator, etc.), acid generator (thermal acid) Generators, photoacid generators, etc.), base generators (thermal base generators, photobase generators, etc.)] may be used.
These additives may be either liquid or solid in the mixture (X), but are more preferably liquid.

In the present invention, the compressive fluid (F) may be carbon dioxide, methane, ethylene, alternative chlorofluorocarbon, etc., but is preferably carbon dioxide from the viewpoint of safety and ease of handling, and more preferably supercritical. Carbon dioxide, subcritical carbon dioxide, or liquid carbon dioxide.

In the present invention, liquid carbon dioxide refers to a triple point of carbon dioxide (temperature = −57 ° C., pressure 0.5 MPa) and a critical point of carbon dioxide (temperature = −57 ° C.) on a phase diagram represented by a temperature axis and a pressure axis of carbon dioxide. Supercritical carbon dioxide, which represents carbon dioxide, which is the temperature / pressure condition of the portion surrounded by the gas-liquid boundary line passing through (temperature = 31 ° C., pressure = 7.4 MPa), the isotherm of the critical temperature, and the solid-liquid boundary line Represents carbon dioxide which is a temperature / pressure condition above the critical temperature (however, the pressure represents the total pressure in the case of a mixed gas of two or more components).

In the present invention, the solid raw material (B) preferably has pores of a size that allows the compressive fluid to penetrate inside. The size of the pores may be any size as long as the compressible fluid (F) can permeate, but in order to efficiently receive pulverization and crushing forces due to expansion during decompression, the pore size present on the surface of the solid raw material (B). Is preferably 10 μm or less, more preferably 1 μm or less, still more preferably 100 nm or less, and particularly preferably 10 nm or less.

The pore diameter is measured with a scanning electron microscope.

In order to receive a large amount of pulverization and crushing force due to volume expansion of the compressive fluid (F), the solid raw material (B) is preferably a material having voids therein, and more preferably a porous material. The porosity is preferably 1% or more, more preferably 3% or more, and particularly preferably 10% or more. The porosity can be measured using a PorMaster 60-GT manufactured by Quantachrome.

The pressure at the time of mixing the compressive fluid (F) is preferably 2 MPa or more, more preferably 3 MPa or more, and further preferably 4 MPa or more. The higher the pressure, the more easily the compressive fluid (F) penetrates into the solid raw material (B) and is pulverized.

In the present invention, the mixture (X) is composed of the solid raw material (B) containing the substance (A) and the compressive fluid (F), and may contain a medium (M) and a particle forming aid (D) as necessary. However, at this time, the proportion of the compressive fluid (F) is 1 to 99% by weight, preferably 5 to 90% by weight, more preferably 10 to 80% by weight, particularly preferably based on the weight of the mixture (X). Is 15 to 70% by weight.
If the solid raw material exists as a solid in the mixture, various additives may be used in combination to prepare other physical property values (viscosity, diffusion coefficient, dielectric constant, solubility, interfacial tension), for example. Moreover, although it is desirable that the purity of carbon dioxide is high, a part of the gas may be mixed.

Examples of gases include inert gases such as nitrogen, helium, argon, and air. The weight fraction of carbon dioxide in the total of carbon dioxide and gas is preferably 70% by weight or more, more preferably 80% by weight or more, and particularly preferably 90% by weight or more.

The volume ratio of the solid raw material (B) and the compressive fluid (F) in the mixture (X) may be any ratio as long as the mixture (X) is at the target temperature and pressure.
The volume ratio of the compressive fluid (F) to the mixture (X) is preferably 0.2 to 0.9, more preferably 0.3 to 0.8, as the compressive fluid (F) / the mixture (X). Hereinafter, it is particularly preferably 0.4 or more and 0.7 or less.

However, from the viewpoint of handling, the mixture (X) preferably has fluidity, and therefore, the solid raw material (B), the compressible fluid (F), and the medium (M) are preferably adjusted to flow ratios. The fluidity can be observed using a pressure vessel with a window.

The amount of the medium (M) is preferably 1 to 100 parts by weight, more preferably 2 to 90 parts by weight, more preferably 3 to 80 parts by weight with respect to 1 part by weight of the solid raw material (B). Particularly preferred is 4 to 70 parts by weight. Within this range, a liquid in which particles are dispersed can be obtained with a viscosity that allows easy handling.

The mixture of the solid raw material (B), the compressive fluid (F), and if necessary, the medium (M) and the granulating aid (D) needs to be instantaneously decompressed and expanded at atmospheric pressure. Preferably there is. Further, from the viewpoint of particle size distribution, at 25 ° C., it is preferably 1000 Pa · s or less, more preferably 100 Pa · s or less, and particularly preferably 10 Pa · s or less.

The time required for mixing the solid raw material (B), the compressive fluid (F) and the medium (M) in the mixture (X) is such that the compressive fluid (F) sufficiently penetrates into the pores of the solid raw material (B). There is no problem if it is longer than the time during which no pressure drop occurs. Further, even if the time is shorter than that, the reproducibility of the degree of permeation decreases, and as a result, coarse powder is generated and the particle distribution of the particles (P) deteriorates, but pulverization and pulverization can be performed. If there is no problem with the presence of the coarse powder, there is no problem even if it is less than the time during which the pressure drop does not occur over time.

Moreover, the pressure at the time of mixing a mixture with compressive fluid (F) [especially supercritical carbon dioxide, subcritical carbon dioxide, or liquid carbon dioxide] disperses solid raw material (B) well in a compressive fluid. Therefore, it is preferably 2 MPa or more, more preferably 4 MPa or more, further preferably 6 MPa or more, and particularly preferably 8 MPa or more. From the viewpoint of equipment cost and operation cost, it is preferably 40 MPa or less. The pressure is more preferably 4 to 35 MPa, still more preferably 8 to 30 MPa, and particularly preferably 8.5 to 25 MPa.

Compressing the compressible fluid to a predetermined pressure or atmospheric pressure to cause rapid expansion of the fluid, thereby refining the solid raw material (B) into which the fluid has permeated. The pressure after expansion under reduced pressure is not particularly limited as long as it does not cause vaporization of the solid raw material (B) and solidification of the compressible fluid, but the pressure difference during expansion under reduced pressure of the compressive fluid is 2 to 100 MPa. The pressure difference is more preferably 5 to 30 MPa, particularly preferably 7 to 25 MPa.

Preparation of the mixture (X) can be performed by a batch mixing method, a continuous mixing method, or the like. The batch type mixing method includes a method in a pressure vessel, and the continuous mixing method includes a line blend (in-line mixing) method. It is preferable from the viewpoints of improvement in quality, constant quality, and reduction in manufacturing space.

A specific example of the apparatus used for the batch type mixing method is a mixer such as a pressure vessel. In the case of the batch type mixing method, as a preparation procedure of the mixture, a solid raw material is charged into the pressure vessel and heated as necessary. A compressive fluid is introduced into the kettle by a pressurizing means such as a pump provided in the pressure kettle until a desired pressure is reached. Thereafter, mixing is performed by stirring or the like for a predetermined time, and particles are produced by ejecting the mixture from a high pressure state to a predetermined pressure or the atmosphere at once. There are no limitations on the length and pipe diameter of the mixer portion of the apparatus and the number of mixing apparatuses (elements), but it must be able to withstand the working pressure.
As described above, it is preferable to provide a nozzle for taking out the mixture at the outlet of the apparatus used for the batch type mixing method. There is no particular limitation as long as it can withstand the working pressure, and it is preferable to be able to eject the mixture from a high pressure state to a predetermined pressure or the atmosphere.

In the case of the line blend method, the mixture (X) and the compressible fluid (F), in which the solid raw material and the medium (M) are mixed as necessary, are transported through the line by using a pump, and from the nozzle for taking out the mixture Particles are produced by ejecting the mixture from a high pressure state to a predetermined pressure or atmosphere. There are no limitations on the length and pipe diameter of the mixer portion of the apparatus and the number of mixing apparatuses (elements), but it must be able to withstand the working pressure.
The residence time in the apparatus is not particularly limited as long as the mixing is sufficiently performed, but is preferably 0.1 to 1800 seconds.

Specific examples of equipment used in the line blend system include static inline mixers such as static mixers, inline mixers, lamond super mixers, and sulzer mixers, and agitation type inline mixers such as vibrator mixers and turbo mixers. It is done. There is no limitation on the length and pipe diameter of the mixer portion of the apparatus and the number of mixing apparatuses (elements), but it must be able to withstand the target pressure.

It is preferable to equip the outlet of the apparatus used for the line blending method with a nozzle for removing the slurry similar to the pressure vessel.

An apparatus used for such a line blending method will be described with reference to the drawings.
FIG. 1 is a flowchart of an experimental apparatus used for producing a dispersion in the mixing method by line blending in the present invention.

As a method for mixing the mixture (X) and carbon dioxide in a liquid or supercritical state as a compressive fluid, first, the compressive fluid is subjected to line blending from the carbon dioxide cylinder B1 through the carbon dioxide pump P2 (static mixer). M1), the pressure and temperature at which carbon dioxide becomes liquid or supercritical is adjusted, and then the mixture (X) is introduced from the dissolution tank T1 into liquid or supercritical carbon dioxide through the solution pump P1. The method is preferred.
The temperature at which line blending is performed is the same as in the case of mixing using the above-described pressure vessel. The residence time in the apparatus is not particularly limited as long as the mixing is sufficiently performed, but is preferably 0.1 to 1800 seconds.
Next, by opening the valve V1 leading to the pressure receiving tank T2, the mixture (X) after line blending is decompressed and expanded to atmospheric pressure, and the compressive fluid is vaporized and removed, whereby the particles are dispersed in the dispersion medium. A dispersion is obtained.

In the above-described two methods, when the mixture (X) is volume-expanded, it is preferable to reduce the pressure to a target pressure at once in order to efficiently obtain pulverization and crushing power. Therefore, when the mixture (X) is prepared and the compressive fluid (F) is removed to obtain the dispersion liquid (L), an exhaust pressure valve capable of reducing the mixture to the target pressure at once is required. In addition, when the mixture (X) is prepared in a pressure vessel or in a line and then the mixture (X) is transferred to another receiving container prepared at a target pressure, the nozzle having a diameter that can transfer the mixture (X) And a regulator that keeps the receiving vessel at the same pressure. However, in the latter case, a regulator is not required if the pressure in the receiving container is atmospheric pressure.

In the case of using the particle forming aid (D), additive, and medium (M), these may be mixed at the same time when the solid raw material (B) and the compressive fluid (F) are mixed. B) or a compressive fluid (F) may be mixed. Furthermore, after mixing the solid material and the compressive fluid, pressure may be introduced and mixed in the process up to volume expansion.

The produced particles (P) have a median diameter of 0.01 μm or more and less than 100 μm, more preferably 0.01 μm or more and less than 10 μm, more preferably 0.01 μm or more and less than 6 μm, and particularly preferably 0.01 μm or more and less than 1 μm. Is less than. The median diameter is a dynamic light scattering particle size distribution measuring device (for example, LB-550: manufactured by Horiba, Ltd.), a laser particle size distribution measuring device (for example, LA-920: manufactured by Horiba, Ltd.), and Multisizer III (Beckman Coulter, Inc.). Etc.). In addition, when it is difficult to measure with these measuring instruments, measurement is performed with SEM, TEM, or the like.

The particles (P) in the dispersion (L) obtained by the present invention have good stability during storage. Good stability means that there is no change in the median diameter of the particles during storage and there is no increase in the amount of coarse particles.

The rate of change of the median diameter during storage of the particles (P) in the dispersion (L) obtained by the present invention is preferably 100% or less, more preferably 50%, still more preferably 25%, particularly preferably. Is 10%. When the rate of change exceeds 100%, problems such as unstable production in various applications tend to occur. For example, when the change rate of the median diameter of the pigment particles is 100% or more, the stability in the coating becomes poor, and problems such as loss of flatness of the coating film due to the aggregated pigment particles are likely to occur.

The amount of increase in the amount of coarse particles of the dispersion of the present invention is preferably 0.5% by volume or less, more preferably 0.1% by volume or less as long as the absolute value of the amount of coarse particles preferably does not exceed 1% by volume. More preferably, it is 0.01 volume% or less. The smaller the increase, the more stable the dispersion during storage. When the increase exceeds 0.5% by volume, the stability in the paint becomes poor and the flatness of the coating film is lost due to the agglomerated pigment particles. It becomes easy to generate problems such as.
Coarse particles refer to particles having a median diameter x 3 times or more.

As the stability of the particles during storage, the dispersion was allowed to stand at 10 ° C. for 24 hours, and the median diameter and the amount of coarse particles before and after standing were measured by the above-mentioned methods, and the median diameter change rate and coarse particles were measured. The amount of increase is calculated.

The change rate of the median diameter is obtained by the following calculation.
Formula 1 B / A × 100-100 = Change rate of median diameter (%)
Measured value A: median diameter of dispersion liquid left to stand at 10 ° C. for 24 hours Measured value B: median diameter in dispersion liquid within one hour after production

The amount of increase in the amount of coarse particles is determined by the following calculation.
Formula 2 CD = Increase amount of coarse particles (%)
Measured value C: Coarse particle amount (%) in the dispersion liquid allowed to stand at 10 ° C. for 24 hours
Measured value D: Coarse particle amount (%) in the dispersion within one hour after production

Examples of the medium (M) include water, a solvent (S), an ionic liquid, a monomer, and a polymer. The medium (M) is selected from the group consisting of water, a solvent (S), a monomer, and a polymer. It is preferable to include the above.

Solvent (S) includes mineral oil (mineral spirit, etc.) ketone solvent (acetone, methyl ethyl ketone, etc.), ether solvent (tetrahydrofuran, diethyl ether, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, cyclic ether, etc.), ester solvent (Acetic acid ester, pyruvic acid ester, 2-hydroxyisobutyric acid ester, lactic acid ester, etc.), amide solvent (dimethylformamide, etc.), alcohol solvent (methanol, ethanol, isopropanol, fluorine-containing alcohol, etc.), aromatic hydrocarbon solvent (toluene) And xylene), and aliphatic hydrocarbon solvents (octane, decane, etc.).

Examples of the ionic liquid include imidazolium (eg, ethylmethylimidazolium), pyridine, alicyclic amine, and aliphatic amine as cation types. Anions include bromide ions, triflates, borons such as halogens and tetraphenylborates, carboxylic acids such as fatty acids, sulfonic acids such as dodecylbenzenesulfonic acid and toluenesulfonic acid, and phosphorus systems such as hexafluorophosphate. It is done. These cations and anions can be selected and used.

As the monomer, the above-described vinyl monomer capable of radical polymerization and monomers capable of ionic polymerization, condensation polymerization, ring-opening polymerization, and addition polymerization are used. As the monomer, a monofunctional polymerizable monomer or a polyfunctional polymerizable monomer can be used, and two or more kinds may be used in combination.
Monomers include styrene, methyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, butadiene, urethane acrylate, polyfunctional (meth) acrylate, silicone (meth) acrylate, dipenta And erythritol pentaacrylate.

The monomer dissolves the compressive fluid (F), particularly carbon dioxide, preferably at least 20% by weight based on the weight of the monomer at 25 ° C. and 10 MPa, more preferably 50 to 200% by weight, still more preferably 80%. ~ 150% by weight.

The solubility parameter (SP value) of the monomer is preferably 7 to 18, more preferably 8 to 16, and particularly preferably 9 to 14. The SP value is expressed by the square root of the ratio between the cohesive energy density and the molecular volume as shown below.
SP = (ΔE / V) ^1/2
Here, ΔE represents the cohesive energy density. V represents the molecular volume, and its value is determined by Robert, EF. Based on calculations by Robert F. Fedors et al., For example, described in Polymer Engineering and Science, Vol. 14, pages 147-154.

In this production method, when the medium is formed into particles in the monomer, the content of the polymerizable monomer reactant in the dispersion is small and the particles are polymerizable monomers even if the polymerization inhibitor is not substantially contained. It is possible to produce a dispersion finely dispersed therein.

“Substantially free” means that the content of the polymerization inhibitor is 1000 ppm or less based on the weight of the mixture (X) in the step of purchasing commercially available monomers and producing particles in this production method. It is preferably 500 ppm, more preferably 300 ppm, particularly preferably 0 ppm.

The reactant content (monomer conversion rate) of the polymerizable monomer in the step of producing particles using the polymerizable monomer as a medium means the polymerization amount (polymerization rate) of the monomer. From the viewpoint of the physical properties of the resin finally obtained by polymerizing the monomer, the monomer conversion in the dispersion is preferably less than 5% by weight, more preferably less than 2% by weight, still more preferably 1% by weight. %. In the case of 5% by weight or more, physical properties such as resin strength and heat resistant storage stability are lowered. For this reason, conventional sand grinders using physical shearing cannot be realized with the above-mentioned polymerization inhibitor amount, and the method of dispersing using the volume expansion of the compressible fluid is optimal.

The monomer conversion rate is a value determined by the following calculation method using ¹ H-NMR method.

Details of the ¹ H-NMR method will be specifically described below.

<Measurement conditions>
Measuring device: AVANCE300 (manufactured by Nippon Bruker Co., Ltd.)
Frequency: 300MHz
Deuterated solvent: Deuterated dimethyl sulfoxide The deuterated solvent here is deuterated dimethyl sulfoxide, deuterated chloroform, deuterated toluene, deuterated dimethylformamide, etc. It can be selected as appropriate.
<Calculation method of monomer conversion>
Here, styrene will be described as an example of the polymerizable monomer.
When styrene before dispersing measuring ¹ H-NMR, signals derived from the vinyl group (r1) is observed near 6.7 ppm, aromatic-derived signal (s1) is observed near 7.3 ~ 7.4 ppm . Similarly, when the dispersion-treated sample is subjected to ¹ H-NMR measurement and a vinyl group-derived signal (r2) and an aromatic-derived signal (s2) are observed, the monomer conversion is calculated by the following equation [1].
Monomer conversion (%) = {1− (r2 / s2) / (r1 / s1)} × 100 [1]
However,
r1: Integral value of a signal derived from a vinyl group near 6.7 ppm before dispersion processing s1: Integral value of a signal derived from an aromatic group near 7.3 to 7.4 ppm before dispersion processing r2: 6. Integral value of a signal derived from a vinyl group around 7 ppm s2: An integral value of a signal derived from an aromatic group around 7.3 to 7.4 ppm after dispersion processing.

As the polymer, since the polymer alone does not have fluidity, it is preferable to use it in a state of being dissolved in a solvent and having fluidity. Examples of the polymer include polyether, polyester resin, polyurethane resin, polyolefin resin (polyethylene, polypropylene, etc.), polyvinyl resin, and the like. Polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polystyrene, styrene / acrylonitrile copolymer, ABS resin, polyethylene, ethylene / vinyl acetate copolymer, polypropylene, polyacetal, polymethyl methacrylate, methacryl / styrene copolymer, polyurethane Examples of the resin include cellulose acetate, polycarbonate, polyester resin, fluorine resin, polyamide resin, phenol resin, urea resin, melamine resin, and epoxy resin.

As the particle formation aid (D), it is desirable to adsorb to the solid raw material in the mixture. Therefore, it is desirable that the particle formation aid (D) has an adsorption group.

Examples of adsorbing groups include acidic groups such as carboxylic acid groups and sulfonic acid groups, basic groups such as amino groups and imidazole groups, hydrophilic groups such as hydroxyl groups and ether groups, and hydrophobic groups such as alkyl groups and phenyl groups. And a halogen group. Particularly preferred are acidic groups and basic groups.

When the particle forming aid has an adsorbing group, the particle forming aid molecule may have an adsorbing group on either the side chain and / or the terminal.

Further, the particle forming aid may have the following groups in addition to the adsorbing group. Examples thereof include a fluorescent site, an enzyme affinity site, a sugar chain site, a polymerizable functional group, a chain transfer group, and the like.
The number of adsorbing groups and groups other than adsorbing groups may be one or more, and different types of adsorbing groups may be used in combination.

The composition of the particle forming aid (D) is preferably a polymerized polymer having an acidic or basic functional group as an adsorbing group or a salt of a polymer compound. Examples thereof include vinyl copolymers having acidic groups and / or basic groups, polyesters, and polyolefins, and alkylammonium salts of polymer compounds having acidic groups. By having a functional group, it becomes easier to adsorb on the surface of the solid raw material (B), and particle formation of the solid raw material (B) in the medium (M) can be promoted.

Further, the particle formation aid (D) preferably has a peak molecular weight in the range of 1,000 to 1,000,000 in the molecular weight distribution, more preferably 1,050 to 100,000. More preferably, it is 1,100 or more and 30,000 or less, and particularly preferably 1,200 or more and 10,000 or less. By having the peak molecular weight in this range, the particle forming aid (D) is more easily dissolved in the medium (M) and can be efficiently adsorbed on the surface of the solid raw material (B). In addition to the above peak molecular weight, the particle formation aid (D) may have a peak molecular weight in the range of less than 1,000 (preferably 200 to 990).
In the present invention, the peak molecular weight of the particle forming aid (D) can be measured under the following conditions using gel permeation chromatography (GPC).
Apparatus (example): “HLC-8120” [manufactured by Tosoh Corporation]
Column (example): 2 “TSK GEL GMH6” [manufactured by Tosoh Corporation]
Measurement temperature: 40 ° C
Sample solution: 0.25 wt% THF solution (filtered insolubles with a glass filter)
Solution injection volume: 100 μl
Detector: Refractive index detector Reference material: Standard polystyrene (TSK standard POLYSTYREN E) 12 points (Molecular weight: 500, 1,050, 2,800, 5,970, 9,100, 18,100, 37,900,96, 400, 190,000, 355,000, 1,090,000, 2,890,000) [manufactured by Tosoh Corporation]

Examples of the skeleton of the particle forming aid (D) include polyether, polyester resin, polycarbonate resin, polyurethane resin, epoxy resin, vinyl polymer, and silicon resin. Moreover, those block resins may be used.

Examples of the particle forming aid (D) include the following.
SN Sparse 70 (manufactured by San Nopco), Solsperse 32500, Solsperse 37500, Solsperse 38500, Solsperse 55000, Solsperse 76500, polyvinyl alcohol, styrene-maleic acid copolymer manufactured by Lubrizol, DISPERBYK-106 manufactured by BYK Japan 108, 145, BYK-9076, 9077, and ANTI-TERRA-U100, Ajinomoto Fine Techno Co., Ltd., Azisper PB822, sodium dodecylbenzenesulfonate, Cymac US-120 manufactured by Toagosei Co., Ltd., and Nippon Lubrizol Co., Ltd. SOLPERSE 21000, 24000, 28000, 32000, 33000, 36000, 41000, 54000, 56000, and 7100 Etc. The.

The particles (P) can be produced by the production method of the present invention. Such particles are the particles (P) of the present invention.

A dispersion containing particles (P) and particles can be produced by the production method of the present invention. Such a dispersion is a dispersion of the present invention. When the dispersion medium is a liquid, the dispersion of the present invention is a dispersion in which particles (P) are dispersed in the dispersion medium.

When the particles (P) of the present invention are particles (P) in which the solid raw material (B) is made of a solid carbon material, the particles (P) of the present invention and the dispersion as the dispersion of the present invention are electrically conductive compositions. It can be used as a resin composition or the like.

When the particles (P) of the present invention are particles (P) in which the solid raw material (B) is made of mineral or clay, the dispersion liquid as the particles (P) of the present invention and the dispersion of the present invention is a resin composition or the like. Can be used as Examples of the use of the resin composition include a coating film forming composition and a rubber composition. Examples of uses of the rubber composition include building materials and automobile parts. Applications of the coating film forming composition include paints and surface coating agents.

Examples of the use of the conductive composition include electrical and electronic parts, OA equipment parts, semiconductor-related members, transport containers, automobile exterior parts, and the like. Applications of electrical and electronic parts include use for conductive coating agents and battery electrodes. Examples of the use of the transport container include a transport tray such as an IC chip.

When the particle (P) of the present invention is a conductive composition in which the solid raw material (B) includes a solid carbon material, the long diameter of the solid carbon material is preferably 300 nm or less, and further from an industrial and conductive viewpoint. The thickness is preferably 1 to 300 nm, particularly preferably 2 to 250 nm, and most preferably 3 to 200 nm. The aspect ratio (length / major axis ratio) of the solid carbon material is preferably 10 or more, more preferably from 10 to 10,000, particularly preferably from the viewpoints of conductivity, moldability, coating property, and dust generation. 30 to 8000.

When the particles (P) of the present invention are the solid raw material (B) is a conductive composition, the molded product, the coating film, etc. obtained from the dispersion as the dispersion of the present invention containing the conductive composition The conductive composition has a volume resistivity of 10 ¹² Ω · cm or less, or a surface resistance of 10 ¹² Ω / sq or less.

When the molded article made of the conductive composition is a transport container, the volume resistivity value is preferably 10 ² to 10 ¹² Ω · cm, more preferably 10 ⁴ to 10 ¹⁰ Ω · cm. When the volume specific resistance value is within this range, electric charges are difficult to be charged, dust and dust are less likely to adhere to the transport container, and precision equipment around the molded product is not damaged.

In the case of a conductive film made of the conductive composition, the surface resistance value is preferably 10 ² to 10 ¹² Ω / sq, more preferably 10 ⁴ to 10 ¹⁰ Ω / sq. When the surface resistance value is within this range, the charge is difficult to be charged, and the same effect as the volume specific resistance value is obtained.

When the particles (P) of the present invention are particles (P) composed of a solid raw material (B) containing a non-metallic inorganic material composed of a metal oxide, the dispersion as the dispersion of the present invention is an abrasive or an ultraviolet absorbing material. It can be used for solar cells, transparent electrodes, cosmetics, magnetic recording media, and the like.

Examples of the metal oxide include oxides of the above metal elements, or oxides composed of two or more of these may be used.

When the particles (P) of the present invention contain a non-metallic inorganic material made of titanium oxide, the dispersion as the dispersion of the present invention can be used for ultraviolet absorbers, cosmetics and the like.

When the particles (P) of the present invention contain barium ferrite, the dispersion as the dispersion of the present invention can be used for a magnetic recording medium or the like.

Hereinafter, the present invention will be further described with reference to examples, but the present invention is not limited thereto. In the following description, “parts” indicates parts by weight.

Various measurements in the following production examples, comparative production examples, examples and comparative examples were performed under the following conditions.

The weight average molecular weight (Mw) was measured by gel permeation chromatography (GPC).
The measurement conditions for GPC are shown below.
Device: HLC-8120 manufactured by Tosoh Corporation
Column: TSK GEL GMH6 2 [manufactured by Tosoh Corporation]
Measurement temperature: 40 ° C
Sample solution: 0.25 wt% THF solution Solution injection amount: 100 μL
Detection device: Refractive index detector Reference material: 12 standard polystyrene (TSK standard POLYSYRENE) manufactured by Tosoh Corporation (molecular weight: 500, 1,050, 2,800, 9,100, 18,100, 37,900, 96, 400, 190,000, 355,000, 1,090,000, 2,890,000)

Glass transition temperature and melting point were measured by DSC.
DSC measurement condition differential scanning calorimeter {for example, DSC210, manufactured by Seiko Denshi Kogyo Co., Ltd.], the sample to be measured was heated to 200 ° C., cooled to 0 ° C. at a cooling rate of 10 ° C./min, The temperature was increased at a rate of 20 ° C./min, and the endothermic change was measured.

The measurement of the median diameter and the particle size distribution were performed with LA-920 (laser type particle size distribution measuring device: manufactured by Horiba Seisakusho) or LB-550 (dynamic light scattering type particle size distribution measuring device: manufactured by Horiba Seisakusho).
The change rate of the median diameter was obtained by the following calculation.
Formula 1 B / A × 100-100 = Change rate of median diameter (%)
Measured value A: median diameter of dispersion liquid left to stand at 10 ° C. for 24 hours Measured value B: median diameter in dispersion liquid within one hour after production

The amount of increase in the amount of coarse particles was determined by the following calculation.
Formula 2 CD = Increase amount of coarse particles (%)
Measured value C: Coarse particle amount (%) in the dispersion liquid allowed to stand at 10 ° C. for 24 hours
Measured value D: Coarse particle amount (%) in the dispersion within one hour after production
In addition, the particle | grains more than (median diameter x3) micrometer were made into the coarse particle.

<Example 1>
In a pressure-resistant reaction vessel equipped with a stirrer and a thermometer, 15 parts of graphene (melting point: 3000 ° C.) was charged to 40% of the reaction vessel volume, heated while being sealed and stirred, and the system temperature was raised to 40 ° C. did. After heating, carbon dioxide is supplied to 5 MPa and stirred for 10 minutes, and then the nozzle attached to the lower part of the container is fully opened and opened to the atmosphere (0.1 MPa) to vaporize and remove carbon dioxide. Particles (P-1) were obtained. The median diameter of the particles (P-1) by LA-920 was 0.12 μm. The amount of coarse particles was 0%. The graphene before pulverization had a pore diameter of 2 nm and a porosity of 10%.

<Example 2>
In a pressure-resistant reaction vessel equipped with a stir bar and a thermometer, 8 parts of silica (RY200, manufactured by Nippon Aerosil Co., Ltd., melting point 1650 ° C.) and 40 parts of mineral oil (mineral spirit, manufactured by Idemitsu Kosan) were added to 40% of the volume of the reaction vessel. Until the temperature inside the system was increased to 40 ° C. After heating, carbon dioxide is supplied to 5 MPa and stirred for 10 minutes, and then the nozzle attached to the lower part of the container is fully opened and opened to the atmosphere (0.1 MPa) to vaporize and remove carbon dioxide, and particles A dispersion liquid (L-1) in which (P-2) was dispersed was obtained. The median diameter of the particles (P-2) by LB-550 was 0.06 μm. The amount of coarse particles was 0%. The porosity of the silica before pulverization was 35%.

<Example 3>
In a pressure-resistant reaction vessel equipped with a stir bar and a thermometer, 4.0 parts of azo lake pigment [Pigment Red (CI Pigment Red 57: 1)], a granulating aid (SOLPERSE 71000: acid value 0, amine value 78). Comb polymer, which has a peak at a molecular weight of 3,800, made by Nippon Lubrizol) 45 parts of acetone solution of 1.0 part was charged to 40% of the volume of the reaction vessel, sealed and heated with stirring, The temperature in the system was raised to 85 ° C. After heating, carbon dioxide is supplied to 10 MPa and stirred for 10 minutes, and then the nozzle attached to the lower part of the container is fully opened and opened to the atmosphere (0.1 MPa) to vaporize and remove carbon dioxide, and particles A dispersion (L-2) of (P-3) was obtained. The median diameter of the particles (P-3) by LA-920 was 0.23 μm, and the amount of coarse particles was 0%.

<Example 4>
In a pressure-resistant reaction vessel equipped with a stir bar and a thermometer, phthalocyanine pigment (cyanine blue (CI Pigment Blue 15: 3)) 8.85 parts, granulating aid (DISPERBYK-106: acid value 132, amine) A salt of a polymer compound having a value of 74. 40 parts of an acetone solution of 1.2 parts having a peak at molecular weights of 1,200 and 460 (manufactured by Big Chemie Japan) is charged to 40% of the volume of the reaction vessel, sealed and stirred. Then, the temperature was raised to 85 ° C. in the system. After heating, carbon dioxide is supplied to 10 MPa and stirred for 10 minutes, and then the nozzle attached to the lower part of the container is fully opened and opened to the atmosphere (0.1 MPa) to vaporize and remove carbon dioxide, and particles A dispersion (L-3) of (P-4) was obtained. The median diameter of the particles (P-4) by LA-920 was 0.36 μm, and the amount of coarse particles was 0%.

<Example 5>
In a pressure-resistant reaction vessel equipped with a stir bar and a thermometer, 4.0 parts of carbon black pigment, a particle-forming aid (BYK-9076: salt of a polymer copolymer having an acid value of 38 and an amine value of 44, a molecular weight of 3, The methyl ethyl ketone solution (55 parts) having a peak at 000 (made by Big Chemie Japan) (2.0 parts) was charged to 30% of the volume of the reaction vessel, sealed and heated with stirring, and the system temperature was raised to 90 ° C. . After heating, carbon dioxide is supplied to 10 MPa and stirred for 10 minutes, and then the nozzle attached to the lower part of the container is fully opened and opened to the atmosphere (0.1 MPa) to vaporize and remove carbon dioxide, and particles A dispersion (L-4) of (P-5) was obtained. The median diameter of the particles (P-5) by LA-920 was 0.43 μm, and the amount of coarse particles was 0%.

<Example 6>
In a pressure-resistant reaction vessel equipped with a stir bar and a thermometer, benzimidazolone pigment [Pigment Yellow (CI Pigment Yellow 180)] 7.0 parts, a particleizing aid (SOLPERSE 54000: acid value 35, amine value 0) 45 parts of a tetrahydrofuran solution of 1.0 part of a linear polymer having a peak at a molecular weight of 2,900 (manufactured by Nihon Lubrizol) is charged to 60% of the volume of the reaction vessel, sealed and heated with stirring. The temperature inside the system was raised to 50 ° C. After raising the temperature and supplying carbon dioxide to 10 MPa and stirring for 15 minutes, the nozzle attached to the lower part of the container is fully opened and opened to the atmosphere (0.1 MPa) to vaporize and remove carbon dioxide, and particles A dispersion (L-5) of (P-6) was obtained. The median diameter of the particles (P-6) by LA-920 was 0.31 μm, and the amount of coarse particles was 0%.

<Example 7>
In a pressure-resistant reaction vessel equipped with a stirrer and a thermometer, 4.0 parts of quinacridone pigment [Pigment Red (CI Pigment Red 122)], a granulating aid (DISPERBYK-145: acid value 76, amine value 71) A salt of a polymer compound. 45 parts of an ethyl acetate solution of 1.0 part having a peak at a molecular weight of 1,700 (manufactured by Big Chemie Japan) is charged to 40% of the volume of the reaction vessel, sealed and heated with stirring. The temperature inside the system was raised to 80 ° C. After heating, carbon dioxide is supplied to 10 MPa and stirred for 20 minutes, and then the nozzle attached to the lower part of the container is fully opened and opened to the atmosphere (0.1 MPa) to vaporize and remove the carbon dioxide, thereby A dispersion (L-6) of (P-7) was obtained. The median diameter of the particles (P-7) by LA-920 was 0.46 μm, and the amount of coarse particles was 0%.

<Example 8>
In the experimental apparatus using the line blending method shown in FIG. 1 (as a line blending apparatus (M1), a static mixer (manufactured by Noritake Company Limited; inner diameter 3.4 mm, number of elements 27) was used) 11.5 parts of acetone (DISPERBYK-106) 411.5 parts of acetone solution and 88.5 parts of phthalocyanine pigment [phthalocyanine blue (CI Pigment Blue 15: 3)] were charged, sealed and heated with stirring. The system temperature was raised to 85 ° C. to prepare a slurry. Carbon dioxide was introduced from the cylinder B1 and the pump P2 at a flow rate of 0.2 L / h, and the valve V1 was adjusted to 10 MPa. Next, the slurry is introduced from the tank T1 and the pump P1 at a flow rate of 0.5 L / h, and while maintaining 10 MPa, the mixed liquid line-blended with M1 is released from the nozzle into T2 (0.1 MPa). Then, carbon dioxide was vaporized and removed to obtain a dispersion liquid (L-7) of particles (P-8). Got. The median diameter of the particles (P-8) by LA-920 was 0.21 μm, and the amount of coarse particles was 0% by volume.

<Example 9>
Instead of the acetone solution of the particle forming aid (DISPERBYK-106), 411.5 parts of an acetone solution of 20 parts of the particle forming aid (SOLPERSE 71000) were added to a phthalocyanine pigment [phthalocyanine blue (CI Pigment Blue 15: 3). )] In the same manner as in Example 8 except that 80 parts of an azo lake pigment [Pigment Red (CI Pigment Red 57: 1)] is charged. -8) was obtained. The median diameter of the particles (P-9) by LA-920 was 0.20 μm, and the amount of coarse particles was 0% by volume.

The evaluation results of Examples 1 to 9 are shown in Table 1.

<Production Example 1> [Preparation of mixture of pigments (C-1)]
In a beaker, Pigment Red 57: 1 [SYMULER Brilliant Carmine 6B, manufactured by DIC Corporation] 110 parts, styrene monomer [Showa Chemical Co., Ltd., containing tert-Butylcatecohol 30 ppm as a stabilizer], and AZPAR as a particleizing aid 11 parts of PB822 [manufactured by Ajinomoto Fine Techno Co., Ltd.] were added, and the mixture was stirred at 2,000 rpm with a TK homomixer at 5 ° C. to prepare a mixed solution (C-1).

<Production Example 2> [Preparation of mixture of pigments (C-2)]
In a beaker, Pigment Red 57: 1 [SYMULER Brilliant Carmine 6B, manufactured by DIC Corporation] 110 parts, butyl acrylate [manufactured by Showa Chemical Co., Ltd., containing 100 ppm of hydroquinone monomethyl ether as a stabilizer], and as a particle forming aid 11 parts of Ajisper PB822 [manufactured by Ajinomoto Fine Techno Co., Ltd.] was added and stirred at 2,000 rpm with a TK homomixer at 5 ° C. to prepare a mixed liquid (C-2).

<Production Example 3> [Preparation of mixture of pigments (C-3)]
In a beaker, Pigment Yellow 180 [FAST Yellow HG, manufactured by Clariant Co., Ltd.] 110 parts, 2-hydroxyethyl methacrylate [manufactured by Nippon Shokubai Co., Ltd., containing 50 ppm of hydroquinone as a stabilizer], 385 parts, and Azisper as a particleizing aid 11 parts of PB822 [manufactured by Ajinomoto Fine Techno Co., Ltd.] were added, and the mixture was stirred at 2,000 rpm with a TK homomixer at 5 ° C. to prepare a mixed solution (C-3).

<Production Example 4> [Preparation of mixture of pigments (C-4)]
In a beaker, pigment blue 15: 3 [cyanine blue 4920, manufactured by Dainichi Seika Kogyo Co., Ltd.] 110 parts, styrene monomer [manufactured by Showa Chemical Co., Ltd., containing tert-Butylcatecohol 30 ppm as a stabilizer], and particle formation aid Was added 11 parts of Addisper PB822 [manufactured by Ajinomoto Fine Techno Co., Ltd.] and stirred at 2,000 rpm with a TK homomixer at 5 ° C. to prepare a mixed liquid (C-4).

<Production Example 5> [Preparation of mixed liquid of anti-blocking filler (C-5)]
In a beaker, 110 parts of silica [Nipsil-NA, manufactured by Tosoh Silica Co., Ltd.] and 440 parts of a styrene monomer [manufactured by Showa Chemical Co., Ltd., containing 30 ppm of tert-Butylcatecohol as a stabilizer] were placed at 5 ° C. with a TK homomixer. The mixture was stirred at 2,000 rpm to prepare a mixed solution (C-5).

<Production Example 6> [Preparation of mixture of pigments (C-6)]
In a beaker, 110 parts of titanium oxide [CR-EL, manufactured by Ishihara Sangyo Co., Ltd.] and 440 parts of styrene monomer (manufactured by Showa Chemical Co., Ltd., containing tert-Butylcatecohol 30 ppm as a stabilizer) are placed at 5 ° C. with a TK homomixer. The mixture was stirred at 2,000 rpm to prepare a mixed solution (C-6).

<Production Example 7> [Preparation of anti-blocking filler mixed solution (C-7)]
In a beaker, 110 parts of silica [Nipsil-NA, manufactured by Tosoh Silica Co., Ltd.], styrene monomer [manufactured by Showa Chemical Co., Ltd., containing tert-Butylcatecohol 30 ppm as a stabilizer], and butyl acrylate [manufactured by Showa Chemical Co., Ltd.] 88 parts hydroquinone monomethyl ether as a stabilizer] was added, and the mixture was stirred at 2,000 rpm with a TK homomixer at 5 ° C. to prepare a mixed solution (C-7).

<Production Example 8> [Preparation of solid carbon mixed solution (C-8)]
In a beaker, SAF carbon black [Vulcan 10H, manufactured by Cabot Japan Co., Ltd.] 200 parts, butadiene [made by Mitsui Chemicals Co., Ltd.] 80 parts, styrene monomer [produced by Showa Chemical Co., Ltd., containing tert-Butylcatecohol 30 ppm as a stabilizer], In addition, 11 parts of Azisper PB822 [manufactured by Ajinomoto Fine Techno Co., Ltd.] was added as a particle forming aid, and the mixture was stirred at 2,000 rpm with a TK homomixer at 5 ° C. to prepare a mixed solution (C-8).

<Production Example 9> [Preparation of reinforcing filler mixed solution (C-9)]
In a beaker, 110 parts of wollastonite [manufactured by Sakai Kogyo Co., Ltd.], 385 parts of styrene monomer (manufactured by Showa Chemical Co., Ltd., containing 30 ppm of tert-Butylcatecohol as a stabilizer), and Azisper PB822 [Ajinomoto Fine Techno Co., Ltd.] as a dispersant. [Production] 11 parts were added, and the mixture was stirred at 2,000 rpm with a TK homomixer at 5 ° C to prepare a mixed solution (C-9).

<Production Example 10> [Preparation of gas barrier filler mixed solution (C-10)]
In a beaker, 110 parts of montmorillonite [Kunipia HY, manufactured by Kunimine Kogyo Co., Ltd.] and 385 parts of DA600 [manufactured by Sanyo Kasei Kogyo Co., Ltd.] are placed and stirred at 2,000 rpm with a TK homomixer at 5 ° C. As a result, a mixed solution (C-10) was produced.

<Production Example 11> [Preparation of Lightweight Filler Mixed Solution (C-11)]
In a beaker, 110 parts of a silica balloon [manufactured by Nippon Steel Co., Ltd.], 385 parts of a styrene monomer [manufactured by Showa Chemical Co., Ltd., containing tert-Butylcatecohol 30 ppm as a stabilizer], and Cymac US-120 [Toagosei Co., Ltd.] as a particleizing aid 11 parts] was added, and stirred at 2,000 rpm with a TK homomixer at 5 ° C. to prepare a mixed solution (C-11).

<Production Example 12> [Preparation of mixed liquid of conductive filler (C-12)]
In a beaker, 110 parts of acetylene black [manufactured by Denka Co., Ltd.], styrene monomer (manufactured by Showa Chemical Co., Ltd., containing tert-Butylcatecohol 30 ppm as a stabilizer) 385 parts, and Azisper PB822 [Ajinomoto Fine Techno Co., Ltd.] as a particleizing aid [Production] 11 parts were added, and the mixture was stirred at 2,000 rpm with a TK homomixer at 5 ° C to prepare a mixed solution (C-12).

<Production Example 13> [Preparation of mixed liquid of magnetism-imparting filler (C-13)]
In a beaker, 110 parts of neodymium fine particles [manufactured by Daido Electronics Co., Ltd.], 385 parts of styrene monomer [manufactured by Showa Chemical Co., Ltd., containing 30 ppm of tert-butylcatecohol as a stabilizer], and sodium dodecylbenzenesulfonate [Kao] 11 parts] was added, and the mixture was stirred at 2,000 rpm with a TK homomixer at 5 ° C. to prepare a mixed solution (C-13).

<Production Example 14> [Preparation of liquid mixture (C-14) of thermally conductive filler]
In a beaker, 110 parts of boron nitride [HP-P1, manufactured by Mizushima Alloy Iron Co., Ltd.], 385 parts of a styrene monomer [manufactured by Showa Chemical Co., Ltd., containing 30 ppm of tert-butylcatecohol as a stabilizer], and dodecylbenzene as a particleizing aid 11 parts of sodium sulfonate [manufactured by Kao Corporation] was added and stirred at 2,000 rpm with a TK homomixer at 5 ° C. to prepare a mixed solution (C-14).

<Production Example 15> [Preparation of mixed liquid of piezoelectric filler (C-15)]
In a beaker, barium titanate [BT-HP9DX, manufactured by Kyoritsu Material Co., Ltd.] 110 parts, styrene monomer (produced by Showa Chemical Co., Ltd., containing tert-Butylcatecohol 30 ppm as stabilizer), 385 parts, and dodecylbenzene as a particleizing aid 11 parts of sodium sulfonate [manufactured by Kao Corporation] was added and stirred at 2,000 rpm with a TK homomixer at 5 ° C. to prepare a mixed solution (C-15).

<Production Example 16> [Preparation of mixture of vibration-damping filler (C-16)]
In a beaker, 110 parts of ultrafine mica [A-11, manufactured by Yamaguchi Mica Co., Ltd.], 385 parts of polyfunctional acrylate [DA-600, manufactured by Sanyo Chemical Industries, Ltd.], and Azisper PB822 [Ajinomoto Fine Co., Ltd.] [Techno Co., Ltd.] 11 parts were added, and the mixture was stirred at 2,000 rpm with a TK homomixer at 5 ° C. to prepare a mixed solution (C-16).

<Production Example 17> [Preparation of mixed liquid of sound insulating filler (C-17)]
In a beaker, 110 parts of iron fine particles [manufactured by JFE Co., Ltd.], 385 parts of polyfunctional acrylate [DA-600, manufactured by Sanyo Kasei Kogyo Co., Ltd.], and Azisper PB822 [manufactured by Ajinomoto Fine Techno Co., Ltd.] 11 The mixture was stirred at 2,000 rpm with a TK homomixer at 5 ° C. to prepare a mixed solution (C-17).

<Production Example 18> [Preparation of mixture of slidable filler (C-18)]
In a beaker, 110 parts of graphite [manufactured by SCL, SEC Carbon Co., Ltd.], 385 parts of polyfunctional acrylate [DA-600, manufactured by Sanyo Chemical Industries, Ltd.], and Azisper PB822 [manufactured by Ajinomoto Fine Techno Co., Ltd.] as a particleizing aid 11 parts were added, and the mixture was stirred at 2,000 rpm with a TK homomixer at 5 ° C. to prepare a mixed solution (C-18).

<Production Example 19> [Preparation of mixture of heat insulating filler (C-19)]
In a beaker, 110 parts of silica balloon [manufactured by Nippon Steel Co., Ltd.], urethane acrylate [UA-1100H, manufactured by Shin-Nakamura Chemical Co., Ltd., containing 385 parts of 4-methoxyphenol as a stabilizer], and as a particleizing aid 11 parts of Cymac US-120 [manufactured by Toagosei Co., Ltd.] was added, and the mixture was stirred at 2,000 rpm with a TK homomixer at 5 ° C. to prepare a mixed solution (C-19).

<Production Example 20> [Preparation of mixed liquid of electromagnetic field absorbing filler (C-20)]
In a beaker, 100 parts of Mn—Zn soft ferrite [BSF-547, manufactured by Toda Kogyo Co., Ltd.] and 20 parts of polyfunctional acrylate [DA-600, manufactured by Sanyo Chemical Industries Co., Ltd.] are placed, and TK type at 5 ° C. The mixture was stirred at 2,000 rpm with a homomixer to prepare a mixed solution (C-20).

<Production Example 21> [Preparation of light scattering filler mixture (C-21)]
In a beaker, 110 parts of titanium oxide [R-62N, manufactured by Sakai Chemical Industry Co., Ltd.], urethane acrylate [UA-1100H, manufactured by Shin Nakamura Chemical Co., Ltd., 385 parts of 4-methoxyphenol as a stabilizer], and 11 parts of Cymac US-120 [manufactured by Toa Gosei Co., Ltd.] was added as a particleizing aid, and the mixture was stirred at 2,000 rpm with a TK homomixer at 5 ° C. to prepare a mixed solution (C-21).

<Production Example 22> [Preparation of flame retardant filler mixed solution (C-22)]
In a beaker, hydrotalcite [DHT-4A, manufactured by Kyowa Chemical Industry Co., Ltd.] 110 parts, urethane acrylate [UA-1100H, manufactured by Shin-Nakamura Chemical Co., Ltd., 385 parts of 4-methoxyphenol as a stabilizer], Then, 11 parts of Cymac US-120 (manufactured by Toa Gosei Co., Ltd.) was added as a dispersant, and the mixture was stirred at 2,000 rpm with a TK homomixer at 5 ° C. to prepare a mixed solution (C-22).

<Production Example 23> [Preparation of liquid mixture (C-23) of highly refractive filler]
In a beaker, 110 parts of fine particle titanium oxide [MT-100HD, manufactured by Teika Co., Ltd.], 55 parts of silicone methacrylate [X-22-2475, manufactured by Shin-Etsu Silicone Co., Ltd.], polyfunctional acrylate [DA-600, Sanyo Chemical Industries Ltd. 55 parts by company] was added, and the mixture was stirred at 2,000 rpm with a TK homomixer at 5 ° C. to prepare a mixed solution (C-23).

<Production Example 24> [Preparation of mixture of heat-radiating filler (C-24)]
In a beaker, 110 parts of magnesium oxide [MT-100HD, manufactured by Teika Co., Ltd.], 55 parts of silicone methacrylate [X-22-2475, manufactured by Shin-Etsu Silicone Co., Ltd.], polyfunctional acrylate [DA-600, Sanyo Chemical Industries, Ltd. [Product]] 55 parts were added, and the mixture was stirred at 2,000 rpm with a TK homomixer at 5 ° C. to prepare a mixed solution (C-24).

<Production Example 25> [Preparation of mixed solution of radiation absorbing filler (C-25)]
In a beaker, 110 parts of zinc oxide [LPZINC, manufactured by Sakai Chemical Industry Co., Ltd.], 380 parts of a polyfunctional acrylate [DA-600, manufactured by Sanyo Chemical Industries Co., Ltd.], and Ajisper PB822 [Ajinomoto Fine Techno Co., Ltd.] 11 parts by company] was added, and the mixture was stirred at 2,000 rpm with a TK homomixer at 5 ° C. to prepare a mixed solution (C-25).

<Production Example 26> [Preparation of UV-absorbing filler mixed solution (C-26)]
In a beaker, fine particle titanium oxide [MT-100HD, manufactured by Teika Co., Ltd.] 110 parts, silicone methacrylate [X-22-2475, manufactured by Shin-Etsu Silicone Co., Ltd.] 190 parts, polyfunctional acrylate [DA-600, Sanyo Chemical Industries Ltd. 190 parts by company] was added, and the mixture was stirred at 2,000 rpm with a TK homomixer at 5 ° C. to prepare a mixed liquid (C-26).

<Production Example 27> [Preparation of liquid mixture of hygroscopic filler (C-27)]
In a beaker, 110 parts of finely powdered calcium oxide [manufactured by Yoshizawa Lime Industry Co., Ltd.], 380 parts of polyfunctional acrylate [DA-600, manufactured by Sanyo Chemical Industries Co., Ltd.], and Ajisper PB822 [Ajinomoto Fine Techno Co., Ltd.] [Production] 11 parts were added and stirred at 2,000 rpm with a TK homomixer at 5 ° C. to prepare a mixed solution (C-27).

<Production Example 28> [Preparation of deodorized filler mixed solution (C-28)]
In a beaker, 110 parts of zeolite [manufactured by ATR Co., Ltd.], 380 parts of polyfunctional acrylate [DA-600, manufactured by Sanyo Kasei Kogyo Co., Ltd.], and 11 parts of Azisper PB822 [manufactured by Ajinomoto Fine Techno Co., Ltd.] The mixture was stirred at 2,000 rpm with a TK homomixer at 5 ° C. to prepare a mixed solution (C-28).

<Production Example 29> [Preparation of mixed liquid of oil-absorbing filler (C-29)]
110 parts of diatomaceous calcium carbonate [manufactured by Yoshizawa Lime Industry Co., Ltd.], 380 parts of polyfunctional acrylate [DA-600, manufactured by Sanyo Kasei Kogyo Co., Ltd.] in a beaker, and Ajisper PB822 [Ajinomoto Fine Techno Co., Ltd.] 11 parts by company] was added and stirred at 2,000 rpm with a TK homomixer at 5 ° C. to prepare a mixed solution (C-29).

<Production Example 30> [Preparation of water-absorbent filler mixture (C-30)]
In a beaker, 110 parts of silica [SFP-d100, manufactured by Denki Kagaku Kogyo Co., Ltd.], 380 parts of polyfunctional acrylate [DA-600, manufactured by Sanyo Kasei Kogyo Co., Ltd.], and Azisper PB822 [Ajinomoto Fine Techno Co., Ltd.] 11 parts] was added and stirred at 2,000 rpm with a TK homomixer at 5 ° C. to prepare a mixed solution (C-30).

<Example 10>
In a pressure-resistant reaction vessel equipped with a stir bar and a thermometer, 30.0 parts of the mixed solution (C-1) obtained in Production Example 1 was charged, sealed and heated with stirring, and the system temperature was raised to 60 ° C. Warm up. After raising the temperature, carbon dioxide was supplied to 10 MPa and stirred for 10 minutes, and then the nozzle attached to the lower part of the container was fully opened to open it in the atmosphere (0.1 MPa), thereby making the dispersoid finer and Vaporization and removal were performed to obtain a dispersion (L-9) in which particles (P-10) were dispersed. The concentration of particles (P-10) in (L-9) was 20% by weight.

<Example 11>
In an experimental apparatus using the line blending method shown in FIG. 1 (a static mixer (manufactured by Noritake Company Limited; inner diameter 3.4 mm, number of elements 27) was used as the line blending apparatus (M1)) A mixture of 124 parts of the mixed solution (C-1) obtained in 1 was charged, sealed and heated with stirring, and the temperature was raised to 60 ° C. in the system to prepare a uniform solution. Carbon dioxide was introduced from the cylinder B1 and the pump P2 at a flow rate of 0.2 L / h, and the valve V1 was adjusted to 10 MPa. Next, the mixed liquid (C-1) was introduced from the tank T1 and the pump P1 at a flow rate of 0.5 L / h, and the mixed liquid line-blended with M1 was transferred from the nozzle into T2 (0.1 MPa) while maintaining 10 MPa. ), The dispersoid was refined, and carbon dioxide was vaporized and removed to obtain a dispersion liquid (L-10) in which particles (P-11) were dispersed.

<Examples 12 to 40>
Particles (P-12) to (P-40) were obtained in the same manner as in Example 10 except that the mixed liquid (C-1) in Example 10 was changed to mixed liquids (C-2) to (C-30). Dispersed dispersions (L-11) to (L-39) were obtained.

The evaluation results of Examples 10 to 40 are shown in Tables 2 to 4.

<Production Example 31>
In a pressure-resistant reaction vessel equipped with a stir bar and a thermometer, 200 parts of acetone and 2.5 parts of di-t-butylperoxyhexahydroterephthalate were charged, and after nitrogen substitution, the temperature was raised to 170 ° C. and dissolved sufficiently. A mixed solution of 5.0 parts of 2- (perfluorohexyl) acrylate (Cheminox FAAC-6, manufactured by Unimatex), 45 parts of methacrylic acid, 50 parts of methyl methacrylate, and 100 parts of acetone is added dropwise at 170 ° C. for 3 hours. The resulting mixture was then polymerized and held at this temperature for 30 minutes. Next, the solvent was removed to obtain [Amorphous Resin 1]. [Amorphous resin 1] had a weight average molecular weight of 27,000 and a glass transition temperature of 92 ° C.

<Production Example 32>
In a pressure-resistant reaction vessel equipped with a stir bar and a thermometer, 200 parts of methyl ethyl ketone and 0.5 part of di-t-butylperoxyhexahydroterephthalate are added, and after nitrogen substitution, the temperature is raised to 170 ° C. and sufficiently dissolved. 4.5 parts 2- (perfluorohexyl) acrylate (Cheminox FAAC-6, manufactured by Unimatex), 20 parts methyl methacrylate, 75 parts styrene, 2-acrylamido-2-methylpropanesulfonic acid (ATBS, Toagosei Co., Ltd.) And a mixed solution of 100 parts of methyl ethyl ketone was polymerized dropwise at 170 ° C. for 3 hours, and further kept at this temperature for 30 minutes. Next, the solvent was removed to obtain [Amorphous Resin 2]. [Amorphous resin 2] had a weight average molecular weight of 85,000 and a glass transition temperature of 98 ° C.

<Example 41>
Into a pressure resistant reaction vessel equipped with a stir bar and a thermometer, 24.0 parts of [Amorphous Resin 1] obtained in Production Example 31 and 226 parts of n-decane were charged to 40% of the volume of the pressure resistant reaction vessel, The mixture was sealed and heated with stirring, and the temperature was raised to 80 ° C. in the system. After raising the temperature, carbon dioxide was supplied to 8 MPa, and the mixture was stirred for 10 minutes. Then, the nozzle attached to the bottom of the container was fully opened to open the particles (P-41) made of [Amorphous Resin 1]. A dispersion liquid (L-40) dispersed in decane was obtained. The median diameter of the particles (P-41) was 0.24 μm. Note that LB-550 was used for measurement of the median diameter.

<Example 42>
Into a pressure resistant reaction vessel equipped with a stir bar and a thermometer, 24.0 parts of [Amorphous Resin 2] obtained in Production Example 32 and 226 parts of n-decane were charged to 40% of the volume of the pressure resistant reaction vessel, The mixture was sealed and heated with stirring, and the temperature in the system was raised to 80 ° C. After raising the temperature, carbon dioxide was supplied to 8 MPa, and the mixture was stirred for 10 minutes. The nozzle attached to the bottom of the container was fully opened to open the particles (P-42) consisting of [amorphous resin 2]. A dispersion liquid (L-41) dispersed in decane was obtained. The median diameter of the particles (P-42) was 0.09 μm. Note that LB-550 was used for measurement of the median diameter.

Table 5 shows the evaluation results of Examples 41 to 42.

Example 43 Battery Electrode A pressure-resistant reaction vessel equipped with a stir bar and a thermometer was charged with 5.0 parts of graphite and 95 parts of methyl ethyl ketone to 40% of the volume of the pressure-resistant reaction vessel, sealed and heated with stirring. The temperature inside the system was raised to 80 ° C. After raising the temperature, carbon dioxide was supplied to 8 MPa, and the mixture was stirred for 10 minutes. Then, the nozzle attached to the bottom of the container was fully opened and opened, and a dispersion (L-42) in which particles containing graphite (P-43) were dispersed in methyl ethyl ketone. ) The median diameter of the particles (P-43) was 0.02 μm. Note that LB-550 was used for measurement of the median diameter. The dispersion was applied to a polyethylene terephthalate (PET) sheet, methyl ethyl ketone was removed at room temperature, and TEM observation was performed. The average major axis of the particles (P-43) was 0.02 μm. The negative electrode obtained from this dispersion had a current capacity of 310 mAh / g in the following evaluation.

Example 44 Battery Electrode The same procedure as in Example 43 was performed except that 5.0 parts of graphite was changed to 5.0 parts of carbon nanotubes in Example 43, and particles containing carbon nanotubes (P-44) were converted to methyl ethyl ketone. A dispersed dispersion (L-43) was obtained. The median diameter of the particles (P-44) was 0.15 μm. Note that LB-550 was used for measurement of the median diameter. When the dispersion (L-44) was applied to a PET sheet, methyl ethyl ketone was removed at room temperature and TEM observation was performed, the average major axis of the particles (P-43) was 0.15 μm. The current capacity in the following evaluation of the positive electrode obtained from this dispersion was 350 mAh / g.

The evaluation results of Examples 43 to 44 are shown in Table 6.

<Example 45> Conductive composition In a pressure-resistant reaction vessel equipped with a stir bar and a thermometer, 5.0 parts of carbon nanotubes and 95 parts of polypropylene were charged to 40% of the volume of the pressure-resistant reaction vessel, sealed and stirred. Then, the temperature was raised to 180 ° C. in the system. After the temperature rise, carbon dioxide was supplied and stirred at 10 MPa for 10 minutes, and then the nozzle attached to the lower part of the container was fully opened and opened, and a dispersion liquid in which particles containing carbon nanotubes (P-45) were dispersed in polypropylene (L- 44) was obtained. The median diameter of the particles (P-45) was 0.15 μm. Note that LB-550 was used for measurement of the median diameter.
When the obtained conductive composition was observed with a TEM, the average major axis of particles (P-45) in the coating film was 0.15 μm and the average aspect ratio was 40. The conductive composition was molded with an injection molding machine [PS40E5ASE, manufactured by Nissei Plastic Industry Co., Ltd.] at a mold temperature of 50 ° C., and each test piece was prepared. In the following evaluation, the conductivity of the molded product was 1 × 10 ^7. The Ω · cm, the moldability was ○, and the dust generation property of the molded product was ○.

<Example 46> Conductive composition A pressure-resistant reaction vessel equipped with a stirrer and a thermometer was charged with 5.0 parts of carbon nanotubes and 95 parts of dipentaerythritol pentaacrylate to 40% of the volume of the pressure-resistant reaction vessel, and sealed. Then, the mixture was heated with stirring, and the system temperature was raised to 70 ° C. After raising the temperature, carbon dioxide was supplied to 15 MPa and stirred for 10 minutes, and then the nozzle attached to the lower part of the container was fully opened and opened to obtain a pre-dispersion. 3 parts of a photopolymerization initiator ((bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide)) was added to the resulting pre-dispersed liquid, and particles containing carbon nanotubes (P-46) were dipentaerythritol pentane. A dispersion liquid (L-45) dispersed in acrylate was obtained, and the median diameter of the particles (P-46) was 0.15 μm, and LB-550 was used for measurement of the median diameter.
The resulting dispersion (L-45) was applied to a PET sheet and exposed to UV light. When the obtained resin coating was observed by TEM, the average major axis of particles (P-46) in the coating was 0.15 μm and the average aspect ratio was 40. Each test piece was prepared using a bar coater. In the following evaluation, the conductivity of the coating film was 3 × 10 ⁶ Ω / sq, the coating property was ◯, and the dust generation property of the coating film was ◯.

Table 7 shows the evaluation results of Examples 45 to 46.

<Example 47> UV shielding agent In a pressure-resistant reaction vessel equipped with a stirrer and a thermometer, 5.0 parts of titanium oxide and 95 parts of methyl ethyl ketone were charged to 40% of the volume of the pressure-resistant reaction vessel, and sealed and stirred. The system was heated and the system temperature was raised to 80 ° C. After raising the temperature, carbon dioxide was supplied to 8 MPa, and the mixture was stirred for 10 minutes. Then, the nozzle attached to the bottom of the container was fully opened and opened to disperse the dispersion containing titanium oxide particles (P-47) in methyl ethyl ketone ( L-46) was obtained. The median diameter of the particles (P-47) after 1 hour of production was 0.08 μm. Note that LB-550 was used for measurement of the median diameter.

The evaluation results of Example 47 are shown in Table 8.

<Examples 48 to 51> Rubber composition The composition, the kneading time in the first stage of kneading, and the temperature (° C.) of the rubber composition when the vulcanization accelerator is added during the kneading are shown in Table 9. And a rubber composition of Examples 48 to 51 was prepared.
In the step of mixing the rubber components and carbon black of Examples 48 and 50, 23.5 parts of styrene monomer, 50 parts of carbon black and 23.5 parts of acetone were sealed in a pressure-resistant reaction vessel equipped with a stirring bar and a thermometer. After heating with stirring and raising the temperature in the system to 120 ° C., mixing carbon dioxide and setting the pressure in the system to 12 MPa, the nozzle attached to the bottom of the container is fully opened and opened, so that carbon black A liquid in which particles (P-48) containing particles and particles (P-50) were dispersed was obtained. 76.5 parts of butadiene was mixed with the obtained liquid to obtain dispersion (L-47) and dispersion (L-49). The median diameter was 1.0 μm for particles (P-48) and 0.9 μm for particles (P-50). A pre-rubber composition in which particles (P-48) or particles (P-50) are dispersed by conducting a living anionic polymerization reaction using an organolithium compound as a polymerization initiator in dispersion (L-47) and dispersion (L-49), respectively. I got a thing. Note that LB-550 was used for measurement of the median diameter.
In the stage of mixing the rubber components and carbon black of Examples 49 and 51, 23.5 parts of styrene monomer and 50 parts of carbon black were sealed and heated in a pressure-resistant reaction vessel equipped with a stirring bar and a thermometer. Then, the temperature inside the system was raised to 80 ° C., carbon dioxide was mixed and the pressure inside the system was adjusted to 8 MPa, and then the nozzle attached to the lower part of the container was fully opened to open the particles containing carbon black (P− 49) or a liquid in which particles (P-51) are dispersed. 76.5 parts of butadiene was mixed with the obtained liquid to obtain dispersion (L-48) and dispersion (L-50). The median diameter was 1.1 μm for particles (P-49) and 0.9 μm for particles (P-51). A pre-rubber in which particles (P-49) or particles (P-51) are dispersed by conducting a living anion polymerization reaction using an organolithium compound as a polymerization initiator in dispersion (L-48) and dispersion (L-50), respectively. A composition was obtained.
The pre-rubber compositions obtained in Examples 48 to 51 were kneaded with other compounding agents according to the description in the table to obtain rubber compositions.

The evaluation results of Examples 48 to 51 are shown in Table 9.

The components * 1 to 7 in Table 9 are as follows.
* 1: Cabot Japan Co., Ltd., trade name “N134”
* 2: Cabot Japan Co., Ltd., trade name “N234”
* 3: Ouchi Shinsei Chemical Industry Co., Ltd., trade name “NOCRACK 6C”
* 4: Ouchi Shinsei Chemical Co., Ltd., trade name “Noxeller MP”
* 5: Ouchi Shinsei Chemical Co., Ltd., trade name “NOCRACK 224”
* 6: Sanshin Chemical Industry Co., Ltd., trade name “Sunseller DM”
* 7: Sanshin Chemical Industry Co., Ltd., trade name “Sunseller NS”

<Examples 52 to 55> Seismic isolation rubber The composition, the kneading time in the first stage of kneading, and the temperature (° C.) of the rubber composition when the vulcanization accelerator is added during kneading are shown in Table 10. The rubber compositions of Examples 52 to 55 were prepared by kneading with a Banbury mixer.
In the stage of mixing the rubber component and carbon black of Examples 52 and 54, 23.5 parts of styrene monomer, 50 parts of carbon black, and 23.5 parts of acetone were sealed in a pressure-resistant reaction vessel equipped with a stirring bar and a thermometer. The mixture is heated with stirring, the temperature inside the system is raised to 120 ° C., carbon dioxide is introduced and the pressure in the system is set to 12 MPa, and then the nozzle attached to the lower part of the container is fully opened and opened, so that carbon black A liquid in which particles (P-52) containing particles and particles (P-54) were dispersed was obtained. 76.5 parts of butadiene was mixed with the obtained liquid to obtain dispersion (L-51) and dispersion (L-53). The median diameter was 1.1 μm for particles (P-52) and 0.9 μm for particles (P-54). Pre-rubber in which particles (P-52) or particles (P-54) are dispersed by conducting living anion polymerization reaction using an organolithium compound as a polymerization initiator in dispersion (L-51) and dispersion (L-53) A composition was obtained. Note that LB-550 was used for measurement of the median diameter.
In the stage of mixing the rubber components and carbon black of Examples 53 and 55, 23.5 parts of styrene monomer and 50 parts of carbon black were sealed and heated in a pressure-resistant reaction vessel equipped with a stirring bar and a thermometer. Then, the temperature inside the system was raised to 80 ° C., carbon dioxide was mixed and the pressure inside the system was adjusted to 8 MPa, and then the nozzle attached to the lower part of the container was fully opened to open the particles containing carbon black (P− 53) or a liquid in which particles (P-55) were dispersed, respectively. 76.5 parts of butadiene was mixed with the obtained liquid to obtain dispersion (L-52) and dispersion (L-54). The median diameter was 1.0 μm for particles (P-53) and 1.0 μm for particles (P-55). The resulting dispersion (L-52) and dispersion (L-54) were each subjected to a living anion polymerization reaction using an organolithium compound as a polymerization initiator, to obtain particles (P-53) or particles (P-55). A dispersed pre-rubber composition was obtained.
In Examples 52 to 55, a rubber component, carbon black, and other compounding agents were added, and a vulcanization accelerator and the like were added and kneaded when the rubber composition reached the temperature shown in Table 10. Using a kneader, the rubber composition and iron powder as a powder (particle size = 40 μm, amorphous reduced iron powder) were kneaded to prepare a plug composition.
Finally, the obtained plug composition was pressure-molded at a temperature of 100 ° C. and a pressure of 1.3 ton / cm ² to produce a cylindrical seismic isolation structure plug having a diameter of 45 mm.
And the attenuation | damping performance was evaluated with the following method about the obtained cylindrical plug for base isolation structures.

The evaluation results of Examples 52 to 55 are shown in Table 10.

The components * 1 to 8 in Table 10 are as follows.
* 1: Cabot Japan Co., Ltd., trade name “N134”
* 2: Cabot Japan Co., Ltd., trade name “N234”
* 3: Ouchi Shinsei Chemical Industry Co., Ltd., trade name “NOCRACK 6C”
* 4: Ouchi Shinsei Chemical Co., Ltd., trade name “Noxeller MP”
* 5: Ouchi Shinsei Chemical Co., Ltd., trade name “NOCRACK 224”
* 6: Sanshin Chemical Industry Co., Ltd., trade name “Sunseller DM”
* 7: Sanshin Chemical Industry Co., Ltd., trade name “Sunseller NS”
* 8: Powder Tech Co., Ltd., particle size = 40μm, amorphous reduced iron

<Example 56>
A pressure-resistant reaction vessel equipped with a stir bar and a thermometer was charged with 10 parts of montmorillonite and 90 parts of dipentaerythritol tetraacrylate to 40% of the volume of the pressure-resistant reaction vessel, sealed and heated with stirring, and an internal temperature of 80 The temperature was raised to ° C. After heating, carbon dioxide was supplied to 15 MPa and stirred for 10 minutes, and then the nozzle attached to the bottom of the container was fully opened and opened to disperse particles containing montmorillonite (P-56) dispersed in dipentaerythritol tetraacrylate. A liquid (L-55) was obtained. The median diameter of the particles (P-56) was 0.11 μm.
1.6 parts of α-hydroxyalkylphenone photopolymerization initiator (manufactured by BASF, “Irgacure 184”) was added to the obtained dispersion (L-55), and a PC plate (polycarbonate plate: size 7 × 15 ( cm), thickness 2 mm) or easy-adhesive PET film (Toyobo Co., Ltd., “A4300”, size 10 × 10 (cm), thickness 125 μm). 24, the film thickness after drying was applied to 10 μm, dried at 60 ° C. for 3 minutes, and then from a height of 18 cm to 5.1 m / min using a high pressure mercury lamp 80W and one lamp. 2 passes of UV irradiation (accumulated irradiation amount: 500 mJ / cm ² ) at a conveyor speed to form a cured coating film, and the following evaluation was performed.

The evaluation results of Example 56 are shown in Table 11.

<Example 57> Magnetic tape In a pressure-resistant reaction vessel equipped with a stirrer and a thermometer, 100 parts of barium ferrite, 14 parts of SO ₃ Na group-containing polyurethane resin, 150 parts of cyclohexanone, and 150 parts of methyl ethyl ketone were 40 times the volume of the pressure-resistant reaction vessel. %, The mixture was sealed and heated with stirring, and the system temperature was raised to 60 ° C. After heating, carbon dioxide was supplied to 15 MPa, and the mixture was stirred for 10 minutes. The nozzle attached to the bottom of the container was fully opened and opened, and particles containing barium ferrite (P-57) were cyclohexanone of SO ₃ Na group-containing polyurethane resin. A magnetic layer coating liquid (L-56) was obtained as a dispersion dispersed in a methyl ethyl ketone solution. The median diameter of the dispersed barium ferrite was 0.03 μm. Note that LB-550 was used for measurement of the median diameter.
For the nonmagnetic layer coating solution, 100 parts of α-iron oxide, 25 parts of carbon black, 18 parts of SO ₃ Na group-containing polyurethane resin, 300 parts of cyclohexanone, 300 parts of methyl ethyl ketone are placed in a pressure-resistant reaction vessel equipped with a stirrer and a thermometer. Was charged to 40% of the pressure-resistant reaction vessel, sealed and heated with stirring, and the system temperature was raised to 60 ° C. After heating, carbon dioxide was supplied to 15 MPa and stirred for 10 minutes, and then the nozzle attached to the lower part of the container was fully opened and opened.
The backcoat layer coating solution was prepared in a pressure-resistant reaction vessel equipped with a stir bar and a thermometer, 80 parts α-iron oxide, 20 parts carbon black, 6 parts SO ₃ Na group-containing polyurethane resin, 13 parts vinyl chloride polymer, cyclohexanone. 150 parts and 150 parts of methyl ethyl ketone were charged to 40% of the pressure-resistant reaction vessel, sealed and heated with stirring, and the system temperature was raised to 60 ° C. After heating, carbon dioxide was supplied to 15 MPa and stirred for 10 minutes, and then the nozzle attached to the lower part of the container was fully opened and opened.
Thereafter, a support made of polyethylene naphthalate having a thickness of 5 μm (center line surface roughness (Ra value) when measured with an optical three-dimensional roughness meter using a 20 × objective lens): 1.5 nm, Young in the width direction The magnetic layer is coated with a non-magnetic layer coating solution so that the thickness after drying is 100 nm and dried, and then the thickness after drying is 70 nm. A coating solution (L-56) was applied. While the magnetic layer coating solution (L-56) was in an undried state, a magnetic field having a magnetic field strength of 0.6 T was applied in a direction perpendicular to the coated surface to perform vertical alignment treatment and then dried. Thereafter, the backcoat layer coating solution was applied to the opposite surface of the support so that the thickness after drying was 0.4 μm and dried.
Thereafter, a surface smoothing treatment was performed with a calendar composed only of a metal roll at a speed of 100 m / min, a linear pressure of 300 kg / cm, and a temperature of 100 ° C., and then a heat treatment was performed for 36 hours in a Dry environment at 70 ° C. After the heat treatment, it was slit to 1/2 inch width to obtain a magnetic tape.

Table 12 shows the evaluation results of Example 57.

<Example 58> CNT x ionic liquid In a pressure-resistant reaction vessel equipped with a stir bar and a thermometer, 5.0 parts of carbon nanotubes and 95 parts of ethylmethylimidazolium-dodecylbenzenesulfonate (EMS-DBS) were subjected to pressure-resistant reaction. The mixture was charged to 40% of the volume of the container, sealed and heated with stirring, and the system temperature was raised to 80 ° C. After heating, carbon dioxide was supplied and the pressure was adjusted to 8 MPa, and the mixture was stirred for 10 minutes. Then, the nozzle attached to the bottom of the container was fully opened and opened, and a dispersion liquid in which particles (P-58) containing carbon nanotubes were dispersed in EMS-DBS ( L-57) was obtained. The median diameter of the particles (P-58) was 0.15 μm. Note that LB-550 was used for measurement of the median diameter. When the dispersion was applied to a polyethylene terephthalate (PET) sheet, EMS-DBS was removed at room temperature and TEM observation was performed, the average major axis of the particles (P-58) was 0.15 μm.

The evaluation results of Example 58 are shown in Table 13.

<Example 59>
In a pressure-resistant reaction vessel equipped with a stirrer and a thermometer, 5.0 parts of porous silica was charged into the pressure-resistant reaction vessel, sealed and heated with stirring, and the system temperature was raised to 80 ° C. After raising the temperature, carbon dioxide was supplied to 8 MPa, and the mixture was stirred for 10 minutes. Then, the nozzle attached to the lower part of the container was fully opened and opened to obtain particles (P-59) containing porous silica. The median diameter of the particles (P-59) was 0.82 μm. The median diameter of the particles (P-59) after standing at 10 ° C. for 24 hours was 0.82 μm, and the increase in coarse particles was 0.0% by volume. Note that LB-550 was used for measurement of the median diameter.

<Example 60>
In a pressure-resistant reaction vessel equipped with a stirrer and a thermometer, charge 5.0 parts of hydrotalcite, 45 parts of a granulating agent (polyvinyl alcohol), and 90 parts of water up to 40% of the volume of the pressure-resistant reaction vessel, and seal it. The mixture was heated with stirring, and the temperature in the system was raised to 80 ° C. After raising the temperature, carbon dioxide was supplied to 15 MPa, and the mixture was stirred for 10 minutes. Then, the nozzle attached to the lower part of the container was fully opened to open the dispersion liquid (L-58) in which particles containing porous silica (P-60) were dispersed. Obtained. The median diameter of the particles (P-60) was 0.11 μm, and the amount of coarse particles was 0.0% by volume. Further, the median diameter of the particles (P-60) after standing at 10 ° C. for 24 hours was 0.11 μm, and the increase in coarse particles was 0.0% by volume. Note that LB-550 was used for measurement of the median diameter.

Table 14 shows the evaluation results of Examples 59 and 60.

<Comparative Production Example 1>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introducing tube, 16 parts of 1,6-hexanediol, 16 parts of sebacic acid, and 0.05 part of titanium dihydroxybis (triethanolaminate) as a condensation catalyst are placed. The reaction was carried out for 8 hours at 180 ° C. while distilling off the water produced under a nitrogen stream. Next, while gradually raising the temperature to 225 ° C., the reaction was carried out for 4 hours while distilling off the generated water and 1,6-hexanediol under a nitrogen stream, and further the reaction was carried out under a reduced pressure of 5 to 20 mmHg, and measurement by GPC When Mw reached 6000, the resin was taken out to obtain [Crystalline Resin 1]. The melting point of [Crystalline Resin 1] was 65 ° C. as measured by DSC.

<Comparative Production Example 2> Production of Particle Aiding Agent In a pressure-resistant reaction vessel equipped with a stirrer and a thermometer, 454 parts of xylene, 150 parts of low molecular weight polyethylene [Sanwax LEL-400 manufactured by Sanyo Chemical Industries, softening point 128 ° C.] 150 parts After substitution with nitrogen, the mixture was heated to 170 ° C. and sufficiently dissolved, and 716 parts of styrene, 46 parts of butyl acrylate, 88 parts of acrylonitrile, 34 parts of di-t-butylperoxyhexahydroterephthalate, and 119 parts of xylene were added. The mixed solution was polymerized dropwise at 170 ° C. over 3 hours, and further kept at this temperature for 30 minutes. Next, the solvent was removed to obtain [Particulate Aid 1]. Mw of [Particulation aid 1] was 5200.

<Comparative Example 1>
In a pressure-resistant reaction vessel equipped with a stir bar and a thermometer, 43.2 parts of {[crystalline resin 1] (melting point): 65 ° C.} are charged into the pressure-resistant reaction vessel, sealed and heated with stirring, The temperature was raised to 70 ° C. After raising the temperature, carbon dioxide is supplied to 6 MPa to dissolve [Crystalline Resin 1], and the mixture is stirred for 10 minutes. The nozzle attached to the bottom of the container is fully opened and opened to the atmosphere (0.1 MPa). Carbon was vaporized and removed to obtain particles (RP-1) containing [crystalline resin 1]. The median diameter of particles (RP-1) by LA-920 was 10.34 μm, and the amount of coarse particles was 4.1% by volume. Further, the median diameter of the particles (RP-1) after standing at 10 ° C. for 24 hours was 10.34 μm, the change rate of the median system was 0%, and the increase amount of coarse particles was 0.0% by volume.

<Comparative example 2>
Into a pressure-resistant reaction vessel equipped with a stir bar and a thermometer, 196.8 parts of acetone and {crystalline resin 1] (melting point): 65 ° C.} 43.2 parts are charged to 40% of the volume of the pressure-resistant reaction vessel and sealed. Then, the mixture was heated with stirring, and the system temperature was raised to 70 ° C. After heating, carbon dioxide was supplied to 6 MPa and stirred for 10 minutes, and then the nozzle attached to the bottom of the container was fully opened and opened to the atmosphere (0.1 MPa) to vaporize and remove carbon dioxide, [ A dispersion liquid (RL-1) in which particles (RP-2) containing crystalline resin 1] were dispersed was obtained. The median diameter of particles (RP-2) by LA-920 was 8.90 μm, and the amount of coarse particles was 3.2% by volume. In addition, the median diameter of the particles (RP-2) after standing at 10 ° C. for 24 hours was 10.20 μm, the change rate of the median diameter was 14.6%, and the increase in coarse particles was 0.2% by volume. .

<Comparative Example 3>
Into a pressure-resistant reaction vessel equipped with a stir bar and a thermometer, 196.8 parts of acetone, {[crystalline resin 1] (melting point): 65 ° C.} 43.2 parts are charged to 40% of the volume of the pressure-resistant reaction vessel, The mixture was sealed and heated with stirring, and the temperature in the system was raised to 70 ° C. After raising the temperature and supplying carbon dioxide to 10 MPa and stirring for 10 minutes, the nozzle attached to the bottom of the container is fully opened and opened to the atmosphere (0.1 MPa) to vaporize and remove carbon dioxide, A dispersion liquid (RL-2) in which particles (RP-3) containing crystalline resin 1] were dispersed was obtained. The median diameter of particles (RP-3) by LA-920 was 0.51 μm, and the amount of coarse particles was 0% by volume. Further, the median diameter of the particles (RP-3) after standing at 10 ° C. for 24 hours was 3.62 μm, the change rate of the median diameter was 609.8%, and the increase in coarse particles was 1.5% by volume. .

<Comparative example 4>
24.0 parts of [Particulation Aid 1] obtained in Comparative Production Example 2, paraffin wax (HNP-9, melting point: 76 ° C., manufactured by Nippon Seiwa) 48.0 parts and 168 parts of acetone were charged to 40% of the volume of the pressure-resistant reaction vessel, sealed and heated with stirring, and the system temperature was raised to 80 ° C. After raising the temperature and supplying carbon dioxide to 8 MPa and stirring for 10 minutes, the nozzle attached to the bottom of the container is fully opened and opened to the atmosphere (0.1 MPa) to vaporize and remove carbon dioxide, A dispersion liquid (RL-3) in which particles (RP-4) containing paraffin wax were dispersed was obtained. The median diameter of particles (RP-4) by LA-920 was 7.6 μm, and the amount of coarse particles was 3.2% by volume. The median diameter of the particles (RP-4) after standing at 10 ° C. for 24 hours was 11.3 μm, the change rate of the median diameter was 48.7%, and the increase in coarse particles was 0.3% by volume. It was.

<Comparative Example 5>
24.0 parts of [Particulation Aid 1] obtained in Comparative Production Example 2, paraffin wax (HNP-9, melting point: 76 ° C., manufactured by Nippon Seiwa) 48.0 parts and 168 parts of acetone were charged to 40% of the volume of the pressure-resistant reaction vessel, sealed and heated with stirring, and the system temperature was raised to 80 ° C. After raising the temperature and supplying carbon dioxide to 10 MPa and stirring for 10 minutes, the nozzle attached to the bottom of the container is fully opened and opened to the atmosphere (0.1 MPa) to vaporize and remove carbon dioxide, A dispersion liquid (RL-4) in which particles (RP-5) containing paraffin wax were dispersed was obtained. The median diameter of the particles by LA-920 (RP-5) was 0.45 μm, and the amount of coarse particles was 0.2% by volume. Further, the median diameter of the particles (RP-5) after standing at 10 ° C. for 24 hours was 1.62 μm, the change rate of the median diameter was 260.0%, and the increase in coarse particles was 4.1% by volume. It was.

<Comparative Example 6>
In an experimental apparatus using the line blending method shown in FIG. 1 (as a line blending apparatus (M1), a static mixer (manufactured by Noritake Company Limited; inner diameter 3.4 mm, number of elements 27) was used), first, acetone 196. 8 parts, {[Crystalline Resin 1] (melting point): 65 ° C.} 43.2 parts are charged, sealed, heated with stirring, and heated to a system temperature of 70 ° C. to prepare a solution of Crystalline Resin 1 did. Carbon dioxide was introduced from the cylinder B1 and the pump P2 at a flow rate of 0.4 L / h, and the valve V1 was adjusted to 6 MPa. Next, the solution of the crystalline resin 1 is introduced from the tank T1 and the pump P1 at a flow rate of 0.5 L / h, and while maintaining 6 MPa and 70 ° C., the mixed liquid line-blended with M1 is fed into the T2 (0 To 1 MPa), the carbon dioxide was vaporized and removed to obtain a dispersion liquid (RL-5) in which particles (RP-6) containing the crystalline resin 1 were dispersed. The median diameter of the particles by LA-920 (RP-6) was 9.50 μm, and the amount of coarse particles was 2.9% by volume. Further, the median diameter of the particles (RP-6) after standing at 10 ° C. for 24 hours was 11.50 μm, the change rate of the median diameter was 21.1%, and the increase in coarse particles was 1.4% by volume. It was.

<Comparative Example 7>
In an experimental apparatus using the line blending method shown in FIG. 1 (as a line blending apparatus (M1), a static mixer (manufactured by Noritake Company Limited; inner diameter 3.4 mm, number of elements 27) was used), first, acetone 196. 8 parts, {[Crystalline Resin 1] (melting point): 65 ° C.} 43.2 parts are charged, sealed, heated with stirring, and heated to a system temperature of 70 ° C. to prepare a solution of Crystalline Resin 1 did. Carbon dioxide was introduced from the cylinder B1 and the pump P2 at a flow rate of 0.7 L / h, and the valve V1 was adjusted to 10 MPa. Next, the solution of the crystalline resin 1 is introduced from the tank T1 and the pump P1 at a flow rate of 0.83 L / h, and while maintaining 10 MPa and 70 ° C., the mixed liquid line-blended with M1 is fed into the T2 (0 To 1 MPa), carbon dioxide was vaporized and removed to obtain a dispersion liquid (RL-6) in which particles (RP-7) containing the crystalline resin 1 were dispersed. The median diameter of the particles (RP-7) by LA-920 was 0.41 μm, and the amount of coarse particles was 0% by volume. Further, the median diameter of the particles (RP-7) after standing at 10 ° C. for 24 hours was 3.21 μm, the change rate of the median diameter was 682.9%, and the increase in coarse particles was 1.5% by volume. It was.

<Comparative Example 8>
In an experimental apparatus using the line blending method shown in FIG. 1 [as the line blending apparatus (M1), a static mixer (manufactured by Noritake Co., Ltd .; inner diameter: 3.4 mm, element number: 27) was used], first, acetone at 168. 0 parts, 24.0 parts of [Particulation Aid 1] obtained in Comparative Production Example 2, and 48.0 parts of paraffin wax (HNP-9, melting point: 76 ° C., Nippon Seiwa Co., Ltd.) were charged, sealed, and stirred. While heating, the temperature in the system was raised to 80 ° C. to prepare a paraffin wax solution. Carbon dioxide was introduced from the cylinder B1 and the pump P2 at a flow rate of 0.55 L / h, and the valve V1 was adjusted to 8 MPa. Next, a paraffin wax solution was introduced from the tank T1 and the pump P1 at a flow rate of 0.65 L / h, and while maintaining 8 MPa and 80 ° C., the mixed liquid line-blended with M1 was fed into the T2 (0.1 MPa from the nozzle). ) Was vaporized and removed to obtain a dispersion liquid (RL-7) in which particles (RP-8) containing paraffin wax were dispersed. The median diameter of particles (RP-8) by LA-920 was 5.6 μm, and the amount of coarse particles was 3.5% by volume. The particle (RP-8) after standing at 10 ° C. for 24 hours had a median diameter of 10.54 μm, a change rate of the median diameter of 88.2%, and an increase in coarse particles was 0.6% by volume. It was.

<Comparative Example 9>
In an experimental apparatus using the line blending method shown in FIG. 1 [as the line blending apparatus (M1), a static mixer (manufactured by Noritake Co., Ltd .; inner diameter: 3.4 mm, element number: 27) was used], first, acetone at 168. 0 parts, 24.0 parts of [Particulation Aid 1] obtained in Comparative Production Example 2, and 48.0 parts of paraffin wax (HNP-9, melting point: 76 ° C., Nippon Seiwa Co., Ltd.) were charged, sealed, and stirred. While heating, the temperature in the system was raised to 80 ° C. to prepare a paraffin wax solution. Carbon dioxide was introduced from the cylinder B1 and the pump P2 at a flow rate of 0.70 L / h, and the valve V1 was adjusted to 10 MPa. Next, a paraffin wax solution was introduced from the tank T1 and the pump P1 at a flow rate of 0.83 L / h, and while maintaining 10 MPa and 80 ° C., the mixed liquid line-blended with M1 was transferred from the nozzle into T2 (0.1 MPa). ) To vaporize and remove carbon dioxide to obtain a dispersion liquid (RL-8) in which particles containing paraffin wax (RP-9) are dispersed. The median diameter of the particles by LA-920 (RP-9) was 0.41 μm, and the amount of coarse particles was 0.1% by volume. The particle (RP-9) after standing at 10 ° C. for 24 hours had a median diameter of 3.24 μm, a change rate of the median diameter of 690.2%, and an increase in coarse particles was 3.4% by volume. It was.

Table 15 shows the evaluation results of Comparative Examples 1 to 9.

In each example and comparative example, each characteristic was evaluated by the following method.

[Current capacity]
To the obtained dispersion, 10% by weight of polyvinylidene fluoride as a binder is added to graphite or carbon nanotubes contained in the dispersion, dried, and then formed into a pellet together with nickel as a current collector. It was created.

Lithium metal as the counter electrode, polypropylene porous membrane as the separator, and LiClO ₄ dissolved in a mixed solvent of propylene carbonate and dimethoxyethane (volume ratio of 1: 1) as the electrolyte solution at a rate of 1 mol / l Copper foil was used as the body.

The battery was charged and discharged at a constant current of 1 mA, and the discharge capacity was defined as the current capacity. The end of charging was when the equilibrium potential reached 2 mV of lithium, and the end of discharging was when the battery voltage exceeded 1.5 V in the energized state.

[Conductivity of molded products]
Volume resistivity test piece (100 × 100 × 2 mm) was measured at 23 ° C. and humidity of 50% RH using a superinsulator [DSM-8103 (SME-8310 for flat plate material electrode, Toa Denki Kogyo)] Measured with (Conforms to ASTM D257)

[Conductivity of coating film]
Surface resistivity test piece (100 × 100 × 2 mm) was measured at 23 ° C. and humidity of 50% RH by a super insulation meter [DSM-8103 (SME-8310 for flat plate material electrode, Toa Denki Kogyo)] Measured with (Conforms to ASTM D257)

[Formability]
Molding was performed under the same conditions as molding with a single thermoplastic resin, and the surface condition of the molded product was compared with a molded product with a single thermoplastic resin according to the following criteria.
○: The surface of the molded product is equivalent to a molded product of a single thermoplastic resin. ×: The surface of the molded product is uneven compared to the molded product of a single thermoplastic resin.

[Coating properties]
The coating was performed under the same conditions as the coating with a monomer (dipentaerythritol pentaacrylate) alone, and the surface condition of the coating film was compared with the coating film with a monomer alone according to the following criteria.
○: The surface of the coating film is equivalent to the coating film of the monomer alone. ×: The coating film surface is uneven compared to the coating film of the monomer alone.

[Dust generation of molded products]
A test piece (diameter 10 × height 20 mm) was molded, and a constant load of 0.5 kg was used at 23 ° C. and 50% RH using a reciprocating friction wear tester [AFT-15, Olintec Co., Ltd.]. The trace of dropping off of the conductive composition adhered to the mount by reciprocating friction on the mount was evaluated.
○: When there is almost no trace of the conductive composition falling on the mount △: When some trace of the conductive composition is dropped ×: When the trace of the conductive composition can be clearly confirmed

[Dust generation of coating film]
A test piece (diameter 10 × height 0.1 mm) was molded, and a reciprocating friction and abrasion tester [AFT-15, Olintec Co., Ltd.] was used, and 0.5 kg was used under conditions of 23 ° C. and 50% RH. The trace of falling off of the conductive composition adhered to the mount by reciprocating friction on the mount under a constant load was evaluated.
○: When there is almost no trace of the conductive composition falling on the mount △: When some trace of the conductive composition is dropped ×: When the trace of the conductive composition can be clearly confirmed

[Evaluation of UV shielding efficiency]
Polymethylmethacrylate is added to the resulting dispersion so that the polymethylmethacrylate is 9 parts by weight with respect to 1 part of titanium oxide, so that the solid content concentration is 15% by weight. Methyl ethyl ketone was added to prepare a preparation solution.
The spectral transmittance at a wavelength of 390 nm or 380 nm of the preparation solution was measured, and the shielding rate (%) was calculated according to the following formula.
Shielding rate (%) = 100-spectral transmittance (390 nm or 380 nm)

[Low exothermicity (tan δ index)]
Using a viscoelasticity measuring device (Rheometrics), tan δ was measured at a temperature of 60 ° C., a dynamic strain of 5%, and a frequency of 15 Hz. The reciprocal of tan δ of a comparative rubber composition using a pre-rubber composition that does not use the dispersion liquid of the present invention was expressed as an index using the following formula, where the reciprocal of 100 was 100. A larger index value indicates a lower exothermic property and a smaller hysteresis loss.
Low exothermic index = {(tan δ of comparative rubber composition) / (tan δ of test vulcanized rubber composition)} × 100

[Attenuation performance]
Cylindrical hollow part in the center, outer diameter is 225mm, rigid rigid plate [iron plate] and elastic elastic plate [vulcanized rubber plate (G '= 0.4MPa)] are laminated alternately The seismic isolation structure plug was press-fitted into the hollow portion of the laminated body thus manufactured to produce the seismic isolation structure. The volume of the seismic isolation structure plug before press-fitting was 1.01 times the volume of the hollow portion of the laminate.
Then, the seismic isolation structure thus produced was subjected to a shear deformation with a specified displacement by exciting it in the horizontal direction with a reference surface pressure applied in the vertical direction under the condition of a temperature of 20 ° C. Was generated. The vibration displacement was set such that the total thickness of the laminate was 100%, the strain was 50 to 250%, the vibration frequency was 0.33 Hz, and the vertical surface pressure was 10 MPa.
In this test, first, an intercept load Qd (horizontal load value at zero displacement) at strains of 50%, 100%, and 250% was obtained. The intercept load Qd is expressed by the following formula using the loads Qd1 and Qd2 at the point where the hysteresis curve intersects the vertical axis:
Qd = (Qd1 + Qd2) / 2
Calculated from Furthermore, using the section load Qd and the cross-sectional area S of the plug, the following formula:
τd = Qd / S
From this, the intercept stress τd (horizontal stress value at zero displacement) was calculated. It shows that the damping performance of the seismic isolation structure plug is superior as τd increases.

[Bounce height of corners (curl resistance)]
About the said cured coating film apply | coated on the easily-adhesive PET film, the average value (mm) of the square jumping height was measured.

[Magnetic interaction ΔM]
About each produced magnetic tape, (DELTA) M was measured with the following method using VSM (vibration sample type magnetometer).
The residual magnetization Id (H) measured by direct current demagnetization is measured by the following method. DC demagnetization is performed and the external magnetic field is set to 0 Oe. After that, when 200 Oe (159 kA / m) of magnetic field is applied in the direction opposite to the direction of direct current demagnetization, the residual magnetization when Io is returned to 0 Oe is applied, and further 200 Oe + 200 Oe (400 Oe (318 kA / m)) is applied. Then, assuming that the residual magnetization upon returning to 0 Oe is Id (400 Oe), these operations are performed in increments of 200 Oe to increase the magnetic field. On the other hand, the residual magnetization Ir (H) starting from AC demagnetization is measured by performing the same operation as described above in increments of 200 Oe. The residual magnetization is all absolute values (positive values), the applied magnetic field is 10 kOe (796 kA / m), the residual magnetization Ir (∞) is measured, and ΔM in each magnetic field is obtained by the following equation (1). Among them, the value having the largest absolute value was taken as ΔM.
ΔM = {Id (H) + 2Ir (H) −Ir (∞)} / Ir (∞) (1)

[SNR]
A magnetic signal was recorded in the longitudinal direction of the tape on each of the produced magnetic tapes under the following conditions and reproduced by an MR head. The reproduced signal was subjected to frequency analysis using a spectrum analyzer manufactured by Shiba-Soku, and the ratio of the output of 300 kfci and the noise integrated in the range of 0 to 600 kfci was defined as SNR.
<Recording and playback conditions>
Recording: recording track width 5 μm, recording gap 0.17 μm, head Bs 1.8T
Playback: Playback track width 0.4μm, sh-sh distance 0.08μm
Recording wavelength: 300 kfi

[Thermal stability]
According to the method of [SNR], the output when recording / reproduction is performed at a recording density of 200 kfci is set to an initial value of 100%, the same track is reproduced after two weeks, and the output decrease is displayed as a demagnetizing factor in percentage. .

By mixing the dispersoid and the compressed fluid by the method for producing particles of the present invention, it is possible to promote primary particle formation and obtain particles in which the solid dispersoid is refined. It is suitable for various applications such as paints, inks, electronic circuits, abrasives, cosmetics, foods, pharmaceuticals.

T1: Dissolution tank (maximum operating pressure 20 MPa, maximum operating temperature 200 ° C., with stirrer)
T2: pressure tank B1: carbon dioxide cylinder P1: solution pump P2: carbon dioxide pump M1: static mixer (pressure vessel for reaction)
V1: Valve

Claims

A method for producing particles (P) containing a substance (A), comprising the step of volume-expanding a mixture (X) comprising a solid raw material (B) containing the substance (A) and a compressible fluid (F) as constituent components. The method for producing particles (P), wherein the substance (A) is not melted and / or not dissolved in the mixture (X) immediately before volume expansion.
The method for producing particles (P) according to claim 1, wherein the mixture (X) further comprises a medium (M).
The method for producing particles (P) according to claim 2, wherein the medium (M) contains one or more selected from the group consisting of water, a solvent (S), a monomer, and a polymer.
The method for producing particles (P) according to any one of claims 1 to 3, wherein the mixture (X) further comprises a particle forming aid (D).
The method for producing particles (P) according to claim 4, wherein the particle forming aid (D) is liquid in the mixture (X).
The method for producing particles (P) according to any one of claims 1 to 5, wherein the compressive fluid (F) is supercritical carbon dioxide, subcritical carbon dioxide, or liquid carbon dioxide.
The method for producing particles (P) according to any one of claims 1 to 6, wherein the substance (A) is an inorganic substance.
The method for producing particles (P) according to claim 7, wherein the substance (A) comprises an inorganic substance containing a metal element and / or a non-metal element.
The method for producing particles (P) according to any one of claims 1 to 6, wherein the substance (A) is an organic substance.
The method for producing particles (P) according to claim 9, wherein the substance (A) has a melting point.
The method for producing particles (P) according to claim 9 or 10, wherein the substance (A) has a glass transition point.
The method for producing particles (P) according to any one of claims 9 to 11, wherein the substance (A) is a colorant.
The method for producing particles (P) according to any one of claims 1 to 12, wherein the solid raw material (B) has voids.
The method for producing particles (P) according to any one of claims 1 to 13, wherein the content of the polymerization inhibitor is 1000 ppm or less based on the weight of the mixture (X).
Particles (P) produced by the production method according to any one of claims 1 to 14.
A dispersion containing particles (P) produced by the production method according to any one of claims 1 to 14.