WO2013100129A1 - Agent émulsifiant destiné à la production de particules de résine, procédé de production de particules de résine, et particules de résine - Google Patents

Agent émulsifiant destiné à la production de particules de résine, procédé de production de particules de résine, et particules de résine Download PDF

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WO2013100129A1
WO2013100129A1 PCT/JP2012/084078 JP2012084078W WO2013100129A1 WO 2013100129 A1 WO2013100129 A1 WO 2013100129A1 JP 2012084078 W JP2012084078 W JP 2012084078W WO 2013100129 A1 WO2013100129 A1 WO 2013100129A1
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group
resin particles
resin
anionic surfactant
producing
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PCT/JP2012/084078
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English (en)
Japanese (ja)
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川口　幸治
橋本　直也
浩太郎 吉岡
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三洋化成工業株式会社
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Priority to JP2013551856A priority Critical patent/JP5680768B2/ja
Publication of WO2013100129A1 publication Critical patent/WO2013100129A1/fr

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/0802—Preparation methods
    • G03G9/0804—Preparation methods whereby the components are brought together in a liquid dispersing medium
    • G03G9/0806—Preparation methods whereby the components are brought together in a liquid dispersing medium whereby chemical synthesis of at least one of the toner components takes place
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/087—Binders for toner particles
    • G03G9/08784—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775
    • G03G9/08791—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775 characterised by the presence of specified groups or side chains
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/087—Binders for toner particles
    • G03G9/08784—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775
    • G03G9/08793—Crosslinked polymers

Definitions

  • the present invention relates to an emulsifier for producing resin particles having a uniform particle size, a method for producing resin particles using the emulsifier for producing resin particles, and a resin particle obtained by this production method. More specifically, toners used in electrophotography, electrostatic recording and electrostatic printing, slush molding resins, powder coatings, spacers for manufacturing electronic components such as liquid crystal displays, standard particles for electronic measuring instruments, hot melt adhesives Further, the present invention relates to an emulsifier for producing resin particles useful for other molding materials, a method for producing resin particles using the emulsifier for producing resin particles, and a resin particle obtained by the production method.
  • a resin solution obtained by dissolving a resin in a solvent in advance is dispersed in an aqueous medium in the presence of an anionic surfactant such as polyoxyalkylene alkyl ether sulfate or a dispersing (auxiliary) agent such as a water-soluble polymer.
  • an anionic surfactant such as polyoxyalkylene alkyl ether sulfate or a dispersing (auxiliary) agent such as a water-soluble polymer.
  • Patent Document 4 a method for obtaining resin particles having a uniform particle diameter using a fine powder of inorganic carbonate such as calcium carbonate and silica as a dispersion stabilizer is known (Patent Document 4).
  • the inorganic fine powder is adhered to the resin particles obtained by these methods, and it is difficult to remove the inorganic powder. Even if a removal step is provided, the inorganic powder remaining in a small amount is resinous. There is a drawback that the performance of the particles such as electrical properties, thermal properties and chemical stability is impaired.
  • Patent Document 5 a method for obtaining resin particles having a uniform particle diameter using an anionic surfactant such as alkyl diphenyl ether sulfate is known (Patent Document 5).
  • the resin particles obtained by the method of Patent Document 5 still have a problem that the performance of the resin particles such as electrical characteristics, thermal characteristics, and chemical stability is not sufficient due to the remaining surfactant in the removal step.
  • the present invention has been made in view of the above circumstances in the prior art. That is, the object of the present invention is superior in emulsifying properties as compared with conventional emulsifiers for producing resin particles, and excellent in cleaning and removing properties in the subsequent cleaning process, so that it has performance such as electrical characteristics, thermal characteristics, and chemical stability. It is an object to provide an emulsifier for producing resin particles useful for obtaining resin particles having excellent and uniform particle diameter, a method for producing resin particles using the emulsifier for producing resin particles, and resin particles obtained by this production method. .
  • the present invention comprises an emulsifier (E) for producing resin particles comprising an anionic surfactant (X) containing two or more hydrophilic groups having different acidities in the molecule; A resin particle production method using the production emulsifier (E) and resin particles obtained by this production method.
  • E emulsifier
  • X anionic surfactant
  • Resin particles prepared using the emulsifier of the present invention have the following effects. 1. A resin dispersion and resin particles having a uniform particle size can be obtained without using inorganic fine powder and classification operation. 2. Resin particles having excellent powder flowability and storage stability can be obtained. 3. Resin particles excellent in heat resistance and resin particles that give a coating film excellent in mechanical properties by heat melting can be obtained. 4). Since the amount of the surfactant remaining in the resin particles is small, resin particles having excellent electrical characteristics can be obtained.
  • the resin (a) or its solvent solution and / or the resin (a) precursor (a0) or its solvent solution is dispersed in an aqueous medium and the precursor (a0) or its solvent solution is used, a precursor ( In the method for producing the resin particles (A) by removing the aqueous medium and, if necessary, the solvent, from the aqueous dispersion (D1) of the resin particles (A) formed by reacting a0), the aqueous particles
  • the medium contains an anionic surfactant (X) containing two or more hydrophilic groups having different acidities in the molecule, resin particles (A) having a uniform particle diameter can be obtained.
  • the pH when the aqueous dispersion (D1) of the resin particles (A) is formed is 2.0 to 6.5, and the pH when the aqueous medium is removed from the aqueous dispersion (D1). It is preferably 7.0 to 9.0 from the viewpoint of achieving both emulsifiability and washing removability.
  • the hydrophilic group of the anionic surfactant (X) in the present invention has two or more hydrophilic groups having different acidities in the molecule.
  • the pH of the aqueous medium at the time of resin particle production is adjusted to 2.0 to 6.5, Utilizing the fact that a hydrophilic group having a pKa of 3.0 or more is acidified, the HLB value of the anionic surfactant (X) can be changed, and the HLB value having excellent emulsifiability can be adjusted. it can.
  • the hydrophilicity of the acidified anionic surfactant remaining on the resin particle surface is adjusted by adjusting the pH of the washing water at the time of washing the resin particles to 7.0 to 9.0. Since the group is anionized, the HLB value of the anionic surfactant (X) increases and can be easily removed from the resin particles.
  • the anionic surfactant (X) has an HLB value (HLB-1) of 1 wt% aqueous solution at 25 ° C. at pH 2.0 to 6.5 (14.0 to 28.0). Preferably, it is 15.0 to 26.5, more preferably 17.0 to 26.0.
  • the HLB value (HLB-2) of 1 wt% aqueous solution at 25 ° C. at pH 7.0 to 9.0 is 18.0 to 35.0. More preferably, it is 20.0 to 34.0, and particularly preferably 22.0 to 33.0.
  • the HLB value (HLB-1) and pH of the anionic surfactant (X) at pH 2.0 to 6.5 in a 1 wt% aqueous solution at 25 ° C are 7. It is preferable that the ratio [(HLB-2) / (HLB-1)] of the HLB value (HLB-2) of (X) in 0 to 9.0 is 1.05 to 1.30.
  • Anionic surfactant (X) is a surfactant that is excellent in emulsifying properties during resin particle production and cleaning and removal from the resin particles. By using it during the resin particle manufacturing process, the particle size is uniform. Resin particles having excellent electrical characteristics can be obtained.
  • Acidity is generally represented by an acid dissociation index (pKa) in water at 25 ° C. (Refer to Chemical Handbook II, 4th edition; 1993, Maruzen Co., Ltd.).
  • hydrophilic group examples include a group having an acidic group having a pKa of less than 6.0 and a salt group thereof. Specifically, a carboxy group, a sulfo group, a sulfino group, a sulfeno group, a phosphono group, a phosphinico group. And groups having an acidic group such as a salt group thereof.
  • Two or more hydrophilic groups having different acidities include cases where the hydrophilic groups have the same structure, but differ depending on the structure of the bonded hydrophobic groups.
  • at least one hydrophilic group has a pKa of 3.0 to 6.0 and at least one hydrophilic group from the viewpoints of emulsifying properties and washing removal properties.
  • a hydrophilic group having a pKa of less than 3.0 is preferred. More preferably, the pKa of at least one hydrophilic group is 3.5 to 6.0, and the pKa of at least one hydrophilic group is less than 2.5.
  • the anionic surfactant (X) has two hydrophilic groups from the viewpoint of emulsifying properties and detergency, and has a hydrophilic group having a pKa of 3.0 to 6.0 and a pKa of less than 3.0. It preferably has a hydrophilic group. More preferably, it preferably has a carboxy group, a carboxylate group, a sulfo group or a sulfonate group, and more preferably has at least one group selected from the group consisting of a sulfo group and a sulfonate group in the molecule.
  • R1 is an aliphatic hydrocarbon group having 4 to 22 carbon atoms or an aromatic ring-containing hydrocarbon group having 6 to 36 carbon atoms
  • Z is a direct bond, —O (AO) mCO— or —NHCO—.
  • A represents an alkylene group having 2 to 8 carbon atoms
  • M + independently represents a hydrogen cation, an alkali metal cation, an ammonium cation or a lower alkanolamine cation
  • m is an integer of 0 to 100.
  • R 2 is an alkyl group having 1 to 22 carbon atoms
  • R 3 is an alkylene group having 1 to 22 carbon atoms
  • Q 1 and Q 2 -SO 3 - M + group, -OSO 3 - M + group, -O (AO) nSO 3 - M + group, or -COO - M + group
  • a is an alkylene group having 2 to 8 carbon atoms
  • n is an integer of 1 to 100.
  • Q 1 and Q 2 may be the same or different, and at least one has a —SO 3 ⁇ M + group.
  • R 1 in the general formula (1) is an aliphatic hydrocarbon group having 4 to 22 carbon atoms or an aromatic ring-containing hydrocarbon group having 6 to 36 carbon atoms.
  • the aliphatic hydrocarbon group having 4 to 22 carbon atoms include linear or branched alkyl groups (butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl, nonadecyl, Eicosyl and docosyl groups), linear or branched alkenyl groups (butenyl, hexenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tetradecenyl, hexadecenyl and octadecenyl groups,
  • a hydrocarbon group having 8 to 22 carbon atoms is preferable, a saturated hydrocarbon group having 12 to 18 carbon atoms is more preferable, and a branched saturated hydrocarbon group having 12 to 18 carbon atoms is particularly preferable.
  • the aromatic ring-containing hydrocarbon group having 6 to 36 carbon atoms include aryl groups (such as phenyl, naphthyl, styrylphenyl and benzylphenyl), arylalkyl groups (such as benzyl, 1-phenylethyl and 2-phenylethyl groups) and alkyl Aryl groups (such as methylphenyl, ethylphenyl, butylphenyl and nonylphenyl groups) can be mentioned.
  • an aromatic ring-containing hydrocarbon group having 12 to 30 carbon atoms is preferred, an aromatic ring-containing hydrocarbon group having 7 to 24 carbon atoms is more preferred, and an alkylaryl group having 12 to 24 carbon atoms is particularly preferred. is there.
  • R 1 is preferably a branched saturated hydrocarbon group having 12 to 18 carbon atoms and an alkylaryl group having 12 to 24 carbon atoms from the viewpoint of emulsifiability.
  • Z is a direct bond, —O (AO) mCO— or —NHCO—.
  • R 1 and the methine group are directly bonded without interposing the linking group Z.
  • A is an alkylene group having 2 to 8 carbon atoms (for example, ethylene, 1,2-propylene, 1,3-propylene, 1,2-butylene and 1,2-hexylene groups), and is preferable from the viewpoint of emulsification.
  • m is an integer of 0 to 100. From the viewpoint of emulsifiability, m is preferably 0 to 20, and more preferably 0 to 15.
  • M + is a hydrogen cation, an alkali metal cation, an ammonium cation, or a lower alkanolamine cation, specifically, an alkali metal (sodium, potassium, lithium, etc.) cation, ammonium, or mono-tetraalkyl
  • alkali metal sodium, potassium, lithium, etc.
  • Examples include substituted ammonium (alkyl group having 1 to 8 carbon atoms, for example, tetramethyl and tetraethyl) cations and cations obtained by adding protons to alkanolamines (monoethanolamine, diethanolamine, triethanolamine, etc.).
  • a hydrogen cation preferred are a hydrogen cation, an alkali metal cation and an ammonium cation, and more preferred is a combination of one cation selected from an alkali metal cation, an ammonium cation and a lower alkanolamine cation and a hydrogen cation, Particularly preferred is a combination of hydrogen cation and sodium cation or a combination of hydrogen cation and ammonium cation.
  • R2 is an alkyl group having 1 to 22 carbon atoms.
  • the alkyl group having 1 to 22 carbon atoms include linear or branched alkyl groups (methyl, ethyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl, nonadecyl , Eicosyl and docosyl groups) and cycloalkyl groups (such as cyclopentyl, cyclohexyl, cyclohexylmethyl and butylcyclohexyl groups) which may be substituted with linear or branched alkyl groups.
  • alkyl groups having 6 to 18 carbon atoms are preferred from the viewpoint of emulsifying properties.
  • R3 is an alkylene group having 1 to 22 carbon atoms.
  • the alkylene group having 1 to 22 carbon atoms include a methylene group, an ethylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, Examples include octylene group, nonylene group, decylene group, undecylene group, dodecylene group, tridecylene group, tetradecylene group, hexadecylene group, octadecylene group, nonadecylene group, eicosylene group, and docosylene group. From the viewpoint of emulsification, carbon is preferred.
  • Q 1 and Q 2 are —SO 3 ⁇ M + group, —OSO 3 ⁇ M + group, —O (AO) nSO 3 ⁇ M + group or —COO ⁇ M + group.
  • Q 1 and Q 2 may be the same or different, and at least one has a —SO 3 ⁇ M + group.
  • Q 1 is preferably a —COO ⁇ M + group
  • Q 2 is a —SO 3 ⁇ M + group.
  • A is an alkylene group having 2 to 8 carbon atoms (for example, ethylene, 1,2-propylene, 1,3-propylene, 1,2-butylene and 1,2-hexylene group), and is preferable from the viewpoint of emulsification.
  • Is an ethylene group and a 1,2-propylene group and when n is 2 or more, one kind of alkylene group may be used alone or two or more kinds of alkylene groups may be used together.
  • an ethylene group and a 1,2-propylene group are preferable, and a case where the ethylene group is 50 mol% or more is particularly preferable.
  • M + is a hydrogen cation, an alkali metal cation, an ammonium cation, or a lower alkanolamine cation, specifically an alkali metal (sodium, potassium, lithium, etc.) cation
  • alkali metal sodium, potassium, lithium, etc.
  • Examples include ammonium or mono-tetraalkyl-substituted ammonium (alkyl group having 1 to 8 carbon atoms, for example, tetramethyl and tetraethyl) cations and cations obtained by adding protons to alkanolamines (monoethanolamine, diethanolamine, triethanolamine, etc.).
  • alkali metal cations and ammonium cations and more preferred are sodium cations and ammonium cations.
  • N is an integer of 1 to 100, preferably 2 to 30 and more preferably 5 to 30 from the viewpoint of emulsifying properties.
  • the anionic surfactant (X) of the present invention can be produced by combining the following known reactions (1) to (4).
  • (1) Friedel-Crafts reaction Phenolic hydroxyl group-containing compounds (phenol, cumylphenol, naphthol, bisphenol A, etc.) are mixed with ⁇ -olefin, styrene, benzyl chloride, vinyltoluene or ⁇ -methylstyrene by Friedel-Crafts reaction, etc.
  • the catalyst aluminum chloride, zinc chloride, activated clay, or the like can be used. Examples of the reaction conditions include those described in JP-B-50-25526.
  • the obtained crude product can also be purified by filtration, extraction or the like.
  • the reaction of adding alkylene oxide (hereinafter abbreviated as AO) to a hydroxyl group of a hydroxyl group-containing compound or the above Friedel-Crafts reaction product can be carried out by a usual method, without catalyst or The reaction can be carried out in one step or in multiple steps at normal pressure or under pressure in the presence of a catalyst (especially in the latter half of the AO addition).
  • AO alkylene oxide
  • a method in which a higher alcohol and a catalyst are charged into a pressure reactor and AO is press-fitted may be mentioned.
  • the catalyst examples include alkali catalysts such as hydroxides of alkali metals (lithium, sodium, potassium, cesium, etc.); acids [perhalogen acids (perchloric acid, perbromic acid, periodic acid, etc.), sulfuric acid, phosphoric acid, and nitric acid. Etc., preferably perchloric acid] and salts thereof [preferably salts of divalent or trivalent metals (Mg, Ca, Sr, Ba, Zn, Co, Ni, Cu and Al)].
  • the reaction temperature is usually 50 to 150 ° C., and the reaction time is usually 2 to 20 hours.
  • both block addition (chip type, balance type, active secondary type, etc.) or random addition are mixed systems [chips after random addition: oxyethylene arbitrarily distributed in the molecule
  • the chain may have 0 to 50% by weight (preferably 5 to 40% by weight), and 0 to 30% by weight (preferably 5 to 25% by weight) of oxyethylene chains may be chipped at the molecular ends.
  • the catalyst can be removed and purified by neutralization and treatment with an adsorbent if necessary.
  • the half esterification product of the terminal hydroxyl group of the AO adduct obtained by the above (2) is obtained by half esterifying the produced AO adduct and maleic anhydride.
  • the reaction temperature is usually 25 to 70 ° C, preferably 40 to 60 ° C.
  • the sulfonation reaction of the half esterified product obtained in the above (3) can be carried out by a conventional method.
  • a method in which a half esterified product is reacted dropwise with an alkaline aqueous solution containing sodium sulfite at a temperature of 25 to 70 ° C. to effect sulfonation may be mentioned.
  • the emulsifier (E) for producing resin particles can contain an anionic surfactant (X) and water if necessary. From the viewpoint of handling, it is preferable to contain 0 to 70% by weight of water based on the weight of the emulsifier (E) for producing resin particles.
  • anionic surfactant (X ′), nonionic surfactant (N), and amphoteric surfactant (Y) described later may be contained.
  • the content of the anionic surfactant (X) is 70 to 100% by weight, from the viewpoint of the electrical characteristics and heat resistance of the resin particles. Preferably, it is 85 to 100% by weight, and more preferably 90 to 100% by weight.
  • the content of the anionic surfactant (X ′) is 0 to 10% by weight. From the viewpoint of the electrical characteristics and heat resistance of the resin particles To preferably 0 to 5% by weight.
  • the content of the nonionic surfactant (N) is 0 to 10% by weight, from the viewpoint of the electrical characteristics and heat resistance of the resin particles. Preferably, it is 0 to 5% by weight.
  • the content of the amphoteric surfactant (Y) is 0 to 10% by weight, which is preferable from the viewpoint of the electrical characteristics and heat resistance of the resin particles. Is 0 to 5% by weight.
  • the resin (a) in the present invention may be a thermoplastic resin or a thermosetting resin.
  • the resin (a) two or more of the above resins may be used in combination.
  • a vinyl resin, a polyester resin, a polyurethane resin, an epoxy resin, and a combination thereof are preferable from the viewpoint that fine spherical resin particles are easily obtained, and a polyester resin is particularly preferable.
  • the vinyl resin is a polymer obtained by homopolymerizing or copolymerizing vinyl monomers.
  • Examples of the vinyl monomer include the following (1) to (9).
  • Vinyl hydrocarbon monomers for example, ethylene, propylene, butene, isobutylene, pentene, heptene, diisobutylene, octene, dodecene, octadecene, butadiene, isoprene, 1,4-pentadiene, 1,6-hexadiene, 1, Examples include 7-octadiene, cyclohexene, and styrene.
  • carboxyl group-containing vinyl monomers and salts thereof for example, (meth) acrylic acid, (anhydrous) maleic acid, maleic acid monoalkyl ester, fumaric acid, fumaric acid monoalkyl ester, crotonic acid, itaconic acid, itaconic acid
  • examples thereof include monoalkyl ester, itaconic acid glycol monoether, citraconic acid, citraconic acid monoalkyl ester, cinnamic acid and salts thereof.
  • Phosphoric acid group-containing vinyl monomers and salts thereof for example, 2-hydroxyethyl (meth) acryloyl phosphate, phenyl-2-acryloyloxyethyl phosphate, and salts thereof.
  • Examples of the salts (2) to (4) include alkali metal salts (sodium salt and potassium salt), ammonium salts, amine salts and quaternary ammonium salts.
  • hydroxyl group-containing vinyl monomers for example, hydroxystyrene, N-methylol (meth) acrylamide, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate and (meth) allyl alcohol Etc.
  • Nitrogen-containing vinyl monomers for example, aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, (meth) acrylamide, N-methyl (meth) acrylamide, N-butylacrylamide , Quaternized products of tertiary amine group-containing vinyl monomers such as diacetone acrylamide, (meth) acrylonitrile, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylamide (methyl chloride, dimethyl sulfate, benzyl chloride and dimethyl carbonate) And the like quaternized with a quaternizing agent such as
  • Epoxy group-containing vinyl monomers examples thereof include glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, and p-vinylphenylphenyl oxide.
  • Halogen element-containing vinyl monomers for example, vinyl chloride, chlorostyrene, bromostyrene, chloroprene and the like.
  • Vinyl ester for example, vinyl acetate, vinyl propionate, vinyl butyrate, diallyl phthalate, vinyl methacrylate, methyl 4-vinylbenzoate, cyclohexyl methacrylate, 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, heptadecyl (meth) acrylate, etc.], dialkyl fumarate (2 Each alkyl group is a straight chain, branched chain or alicyclic group having 2 to 8 carbon atoms), dialkyl maleate (two alkyl groups are a straight chain, branched chain having 2 to 8 carbon atoms) Branched or alicyclic groups), poly(
  • Examples of the vinyl monomer copolymer include a polymer obtained by copolymerizing any of the above monomers (1) to (9) with two or more species in an arbitrary ratio.
  • polyester resin examples include a polycondensate of a polyol and a polycarboxylic acid or its acid anhydride or its lower alkyl ester.
  • the polyol is a diol (10) and a trivalent or higher polyol (11)
  • the polycarboxylic acid or its acid anhydride or its lower alkyl ester is a dicarboxylic acid (12) and a trivalent or higher polycarboxylic acid (13).
  • acid anhydrides or lower alkyl esters thereof examples include a polycondensate of a polyol and a polycarboxylic acid or its acid anhydride or its lower alkyl ester.
  • the polyol is a diol (10) and a trivalent or higher polyol (11)
  • the polycarboxylic acid or its acid anhydride or its lower alkyl ester is a dicarboxylic acid (12) and a trivalent or higher polycarboxylic acid (13).
  • the ratio of the polyol and the polycarboxylic acid is usually 2/1 to 1/1, preferably 1.5 / 1 to 1/1 / as the equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. 1, more preferably 1.3 / 1 to 1.02 / 1.
  • Diol (10) includes alkylene glycol (ethylene glycol, 1,3-propylene glycol, 1,6-hexanediol, dodecanediol, neopentyl glycol, etc.); alkylene ether glycol (diethylene glycol, triethylene glycol, dipropylene glycol, etc.) ); Alicyclic diol (1,4-cyclohexanedimethanol and hydrogenated bisphenol A, etc.); bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.); alkylene oxide (ethylene oxide, propylene oxide) of the above alicyclic diol Adducts; alkylene oxides of the above bisphenols (ethylene oxide, propylene oxide, butylene oxide, etc.) Additives; other examples include polylactone diols (poly ⁇ -caprolactone diol, etc.) and polybutadiene diols.
  • alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols preferred are alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols, and more preferred are alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms. It is a combination.
  • the trihydric or higher polyol (11) includes trihydric to octahydric or higher polyhydric aliphatic alcohols (such as glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, and sorbitol); trisphenols (such as trisphenol PA) ); Novolak resins (phenol novolak, cresol novolak, etc.); alkylene oxide adducts of the above trisphenols; alkylene oxide adducts of the above novolac resins; acrylic polyol [copolymerization of hydroxyethyl (meth) acrylate with other vinyl monomers Etc.].
  • trivalent to octavalent or higher polyhydric aliphatic alcohols and alkylene oxide adducts of novolak resins are preferred.
  • dicarboxylic acid (12) examples include alkylene dicarboxylic acids (succinic acid, adipic acid, sebacic acid, dodecenyl succinic acid, dodecanedicarboxylic acid, and octadecanedicarboxylic acid, etc.); alkenylene dicarboxylic acids (such as maleic acid and fumaric acid); Branched alkylene dicarboxylic acids of [dimer acid, alkenyl succinic acid (such as dodecenyl succinic acid, pentadecenyl succinic acid and octadecenyl succinic acid), alkyl succinic acid (such as decyl succinic acid, dodecyl succinic acid and octadecyl succinic acid); Group dicarboxylic acids (phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, etc.) and
  • Examples of the trivalent or higher polycarboxylic acid (13) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid).
  • dicarboxylic acid (12) or the trivalent or higher polycarboxylic acid (13) acid anhydrides or lower alkyl esters (methyl ester, ethyl ester, isopropyl ester, etc.) described above may be used.
  • polyurethane resin examples include polyisocyanate (14) and an active hydrogen group-containing compound [water, polyol ⁇ the diol (10) and trivalent or higher polyol (11), etc.) ⁇ , dicarboxylic acid (12), and trivalent or higher polycarboxylic acid. Acid (13) and polyamine (15) and the like] and the like.
  • polyisocyanate (14) examples 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.
  • 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 such as those having a urethane group, carbodiimide group, urea group, uretoimine group, or isocyanurate group) and two or more of these Of the mixture.
  • aromatic polyisocyanate examples include 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate (TDI), 2,4′- or 4,4′-.
  • aromatic polyisocyanate examples include diphenylmethane diisocyanate (MDI) and m- or p-isocyanatophenylsulfonyl isocyanate.
  • aliphatic polyisocyanate examples include hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6- And aliphatic polyisocyanates such as diisocyanatomethylcaproate and bis (2-isocyanatoethyl) fumarate.
  • HDI hexamethylene diisocyanate
  • dodecamethylene diisocyanate 1,6,11-undecane triisocyanate
  • 2,2,4-trimethylhexamethylene diisocyanate 2,2,4-trimethylhexamethylene diisocyanate
  • lysine diisocyanate 2,6- And aliphatic polyisocyanates such as diisocyanatomethylcaproate and bis (2-isocyanatoethyl) fumarate.
  • alicyclic polyisocyanate examples include isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4'-diisocyanate (hydrogenated MDI), and methylcyclohexylene diisocyanate (hydrogenated TDI).
  • IPDI isophorone diisocyanate
  • MDI dicyclohexylmethane-4,4'-diisocyanate
  • TDI methylcyclohexylene diisocyanate
  • araliphatic polyisocyanate examples include m- or p-xylylene diisocyanate (XDI) and ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethylxylylene diisocyanate (TMXDI).
  • modified polyisocyanate examples include 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 of these [for example, Combination of modified MDI and urethane-modified TDI (isocyanate-containing prepolymer)].
  • modified MDI urethane-modified MDI, carbodiimide-modified MDI, trihydrocarbyl phosphate-modified MDI, etc.
  • modified polyisocyanates such as urethane-modified TDI
  • mixtures of two or more of these for example, Combination of modified MDI and urethane-modified TDI (isocyanate-containing prepolymer)].
  • 6-15 aromatic polyisocyanates preferred are 6-15 aromatic polyisocyanates, aliphatic polyisocyanates having 4-12 carbon atoms and alicyclic polyisocyanates having 4-15 carbon atoms, and more preferred are TDI, MDI, HDI, hydrogenated MDI and IPDI.
  • polyamine 15 examples include aliphatic polyamines having 2 to 18 carbon atoms [alkylene diamines having 2 to 6 carbon atoms (ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, etc.), polyalkylenes (carbon 2-6) polyamines ⁇ diethylenetriamine, iminobispropylamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, etc. ⁇ and their alkyl (1 to 4 carbon atoms) or hydroxyalkyl ( C2-C4) Substituent ⁇ Dialkyl (C1-C3) aminopropylamine, trimethylhexamethylenediamine, aminoethylethanolamine, 2,5-dimethyl-2,5-hexamethylenediamine and Ruiminobispropylamine etc.]; aliphatic ring-containing aliphatic amines
  • Examples of the epoxy resin include a ring-opening polymer of polyepoxide (16), polyepoxide (16) and active hydrogen-containing compound [water, polyol ⁇ the diol (10) and trivalent or higher polyol (11) ⁇ , dicarboxylic acid (12).
  • Examples of the polyepoxide (16) include aromatic polyepoxy compounds, heterocyclic polyepoxy compounds, alicyclic polyepoxy compounds, and aliphatic polyepoxy compounds.
  • Examples of the aromatic polyepoxy compounds include glycidyl ethers and glycidyl ethers of polyhydric phenols, glycidyl aromatic polyamines, and glycidylates of aminophenols.
  • Examples of the glycidyl ether of polyhydric phenol include bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, and bisphenol B diglycidyl ether.
  • Examples of the glycidyl aromatic polyamine include N, N-diglycidylaniline.
  • heterocyclic polyepoxy compound examples include trisglycidylmelamine.
  • examples of the alicyclic polyepoxy compound include vinylcyclohexene dioxide and ethylene glycol bisepoxy dicyclopentyl ale.
  • examples of aliphatic polyepoxy compounds include polyglycidyl ethers of polyhydric aliphatic alcohols, polyglycidyl esters of polyhydric fatty acids, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, and glycerol polyglycidyl ether. And pentaerythritol polyglycidyl ether.
  • polyglycidyl ester of polyvalent fatty acid examples include diglycidyl oxalate and diglycidyl malate.
  • examples of the glycidyl aliphatic amine include N, N, N ′, N′-tetraglycidylhexamethylenediamine.
  • an aliphatic polyepoxy compound and an aromatic polyepoxy compound are preferable. Two or more of the polyepoxides of the present invention may be used in combination.
  • (a) When dispersing the resin (a) in an aqueous medium, it is preferable that (a) is liquid. When (a) is solid at room temperature, it is dispersed in a liquid state at a temperature higher than the melting point, a solvent solution of (a) is used, a precursor (a0) of (a) or a solvent solution thereof May be used.
  • the viscosity of the resin (a) or the solvent solution thereof, or the precursor (a0) or the solvent solution thereof is usually 10 to 50,000 mPa ⁇ s (measured with a B-type viscometer) from the viewpoint of particle size uniformity, preferably 100 to 10,000 mPa ⁇ s.
  • the temperature during dispersion is usually 0 to 150 ° C. (under pressure), preferably 5 to 98 ° C. When the viscosity of the dispersion is high, it is preferable to perform dispersion by lowering the viscosity to the above preferred range by increasing the temperature.
  • the solvent used in the solvent solution of the resin (a) and the solvent solution of the precursor (a0) is not particularly limited as long as the solvent can dissolve the resin (a) at room temperature or under heating, and specific examples include toluene, Aromatic hydrocarbon solvents such as xylene, ethylbenzene and tetralin; aliphatic or alicyclic hydrocarbon solvents such as n-hexane, n-heptane, mineral spirit and cyclohexane; methyl chloride, methyl bromide, methyl iodide, Halogen solvents such as methylene dichloride, chloroform, carbon tetrachloride, trichloroethylene and perchloroethylene; ester or ester ether solvents such as ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate and ethyl cellosolve acetate; diethyl ether, Tetra
  • the precursor (a0) of the resin (a) is not particularly limited as long as it can be converted into the resin (a) by a chemical reaction.
  • the resin (a) is a vinyl resin
  • (a0) Includes the above-mentioned vinyl monomers (which may be used alone or mixed) and solvent solutions thereof
  • the resin (a) is a condensation resin (for example, polyurethane resin, epoxy resin and polyester resin).
  • Etc. is exemplified by a combination of a prepolymer ( ⁇ ) having a reactive group and a curing agent ( ⁇ ).
  • “reactive group” means a group capable of reacting with the curing agent ( ⁇ ).
  • the method of reacting the precursor (a0) to make the resin (a) includes, for example, an oil phase comprising an oil-soluble initiator, monomers, and, if necessary, a solvent. And an anionic surfactant (X) and a water-soluble initiator are emulsified and dispersed, and a radical polymerization reaction is performed by heating (so-called emulsion polymerization method).
  • the method of forming the resin (a) by reacting the precursor (a0)
  • An oil phase containing a reactive group-containing prepolymer ( ⁇ ) and a curing agent ( ⁇ ) and optionally a solvent is emulsified and dispersed in an aqueous medium containing an anionic surfactant (X), and the reactive group-containing prepolymer is heated.
  • a method of forming a resin particle (A) comprising a resin (a) by reacting a polymer ( ⁇ ) with a curing agent ( ⁇ ); a reactive group-containing prepolymer ( ⁇ ) or a solvent solution thereof, an anionic surfactant A method in which a resin particle (A) comprising the resin (a) is formed by emulsifying and dispersing it in an aqueous medium containing (X) and adding a water-soluble curing agent ( ⁇ ) to react therewith; containing a reactive group Prepolymer ( ⁇ ) cures by reacting with water The reactive group-containing prepolymer ( ⁇ ) or a solvent solution thereof is reacted with water by emulsifying and dispersing it in an aqueous medium containing the anionic surfactant (X), and consists of (a) Examples thereof include a method of forming the resin particles (A).
  • Examples of the combination of the reactive group contained in the reactive group-containing prepolymer ( ⁇ ) and the curing agent ( ⁇ ) include the following (1) and (2).
  • the reactive group of the reactive group-containing prepolymer ( ⁇ ) is a functional group ( ⁇ 1) capable of reacting with an active hydrogen compound, and the curing agent ( ⁇ ) is an active hydrogen group-containing compound ( ⁇ 1). combination.
  • the combination of (1) is preferable from the viewpoint of the reaction rate in water.
  • the functional group ( ⁇ 1) capable of reacting with the active hydrogen compound includes an isocyanate group ( ⁇ 1a), a blocked isocyanate group ( ⁇ 1b), an epoxy group ( ⁇ 1c), an acid anhydride group ( ⁇ 1d) and An acid halide group ( ⁇ 1e) and the like can be mentioned.
  • ( ⁇ 1a), ( ⁇ 1b) and ( ⁇ 1c) are preferable, and ( ⁇ 1a) and ( ⁇ 1b) are particularly preferable.
  • the blocked isocyanate group ( ⁇ 1b) refers to an isocyanate group blocked with a blocking agent.
  • the blocking agent examples include oximes [acetooxime, methyl isobutyl ketoxime, diethyl ketoxime, cyclopentanone oxime, cyclohexanone oxime, methyl ethyl ketoxime, etc.]; lactams [ ⁇ -butyrolactam, ⁇ -caprolactam, ⁇ -valerolactam Etc.]; aliphatic alcohols having 1 to 20 carbon atoms [ethanol, methanol, octanol, etc.]; phenols [phenol, m-cresol, xylenol, nonylphenol, etc.]; active methylene compounds [acetylacetone, ethyl malonate, and ethyl acetoacetate] Etc.]; basic nitrogen-containing compounds [N, N-diethylhydroxylamine, 2-hydroxypyridine, pyridine N-oxide, 2-mercaptopyridine, etc.]; and mixtures of two or more thereof
  • Examples of the active hydrogen group-containing compound ( ⁇ 1) include polyamine ( ⁇ 1a), polyol ( ⁇ 1b), polymercaptan ( ⁇ 1c) and water ( ⁇ 1d) which may be blocked with a detachable compound. Of these, ( ⁇ 1a), ( ⁇ 1b) and ( ⁇ 1d) are preferred, ( ⁇ 1a) and ( ⁇ 1d) are more preferred, and a blocked polyamine ( ⁇ 1a) is particularly preferred. And ( ⁇ 1d). ( ⁇ 1a) is exemplified by those similar to polyamine (15).
  • Preferred as ( ⁇ 1a) are 4,4'-diaminodiphenylmethane, xylylenediamine, isophoronediamine, ethylenediamine, diethylenetriamine, triethylenetetramine, and mixtures thereof.
  • an amino group ( ⁇ 2a), a hydroxyl group (alcoholic hydroxyl group and a phenolic hydroxyl group) ( ⁇ 2b), a mercapto group ( ⁇ 2c), a carboxyl group ( ⁇ 2d), and an organic group ( ⁇ 2e) blocked with a compound from which they can be removed are preferred, and ( ⁇ 2b) is more preferred.
  • Examples of the organic group blocked with the compound from which the amino group can be removed include the same groups as in the case of ( ⁇ 1a).
  • Examples of the compound ( ⁇ 2) capable of reacting with an active hydrogen-containing group include polyisocyanate ( ⁇ 2a), polyepoxide ( ⁇ 2b), polycarboxylic acid ( ⁇ 2c), polyacid anhydride ( ⁇ 2d), and polyacid halide ( ⁇ 2e). It is done. Among these, ( ⁇ 2a) and ( ⁇ 2b) are preferable, and ( ⁇ 2a) is more preferable.
  • Examples of the aqueous medium in the present invention include water, a water-soluble solvent, and a mixture thereof, and among these, water is particularly preferable.
  • water-soluble solvents include lower alcohols (such as methanol, isopropanol, ethylene glycol and propylene glycol), dimethylformamide, tetrahydrofuran, cellosolves (such as methyl cellosolve, ethyl cellosolve and butyl cellosolve), and lower ketones (such as acetone and methyl ethyl ketone). Can be mentioned. These may be used alone or in combination of two or more.
  • the aqueous medium preferably contains a water-soluble polymer (P).
  • the water-soluble polymer (P) include cellulose compounds (methyl cellulose, hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, carboxymethyl cellulose, hydroxypropyl cellulose and saponified products thereof), gelatin, starch, dextrin, gum arabic, chitin, chitosan, polyvinyl alcohol.
  • Polyvinyl pyrrolidone polyethylene glycol, polyethyleneimine, polyacrylamide, acrylic acid (salt) -containing polymer (sodium polyacrylate, potassium polyacrylate, ammonium polyacrylate, partially neutralized sodium hydroxide of polyacrylic acid and acrylic acid Sodium-acrylic acid ester copolymer), sodium hydroxide (partial) neutralized product of styrene-maleic anhydride copolymer and water
  • Polyurethane reaction product of polyethylene glycol and polycaprolactone diol with polyisocyanate etc.
  • the aqueous medium of the present invention may further contain other anionic surfactant (X ′), nonionic surfactant (N) and amphoteric surfactant (Y ), Or a plasticizer (V).
  • X ′ anionic surfactant
  • N nonionic surfactant
  • Y amphoteric surfactant
  • V plasticizer
  • amphoteric surfactant (Y) a betaine-type amphoteric surfactant [coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine, lauryldimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine , Lauryl hydroxysulfobetaine and lauroylamidoethyl hydroxyethyl carboxymethyl betaine hydroxypropyl sodium phosphate] and amino acid type amphoteric surfactants [sodium ⁇ -laurylaminopropionate and the like].
  • the plasticizer (V) may be added to the aqueous medium as necessary during emulsification and dispersion, or may be added to the dispersion [in the oil phase containing the resin (a)].
  • the plasticizer (V) is not limited at all.
  • phthalate ester dibutyl phthalate, dioctyl phthalate, butyl benzyl phthalate, diisodecyl phthalate, etc.
  • aliphatic dibasic acid ester (di-2-dicarboxylic acid adipate) Ethylhexyl and 2-ethylhexyl sebacate)
  • trimellitic acid ester tri-2-ethylhexyl trimellitic acid and trioctyl trimellitic acid
  • phosphoric acid ester triethyl phosphate, tri-2-ethylhexyl phosphate and tricresyl phosphate
  • fatty acid esters butyl oleate
  • the value of the volume average particle size / number average particle size of the resin particles (A) is preferably 1.0 to 1.4, more preferably 1.0 to 1.2. Is more preferable.
  • the volume average particle size and the number average particle size can be measured simultaneously with Multisizer III (manufactured by Beckman Coulter, Inc.).
  • the amount of the anionic surfactant used is preferably 0.2 to 15% by weight, more preferably 0.5 to 10% by weight based on the weight of the aqueous medium. If the concentration of the surfactant in the aqueous medium is 0.2% by weight or more, the emulsion stability is good when the resin or resin precursor is emulsified and dispersed in the aqueous medium, and if the concentration is 15% by weight or less, the resin. Alternatively, when the resin solvent solution is emulsified and dispersed in an aqueous medium, the particle size does not become too small, the surfactant remaining in the resin particles does not increase, and the resin properties are not adversely affected.
  • the amount of the aqueous medium used when emulsifying and dispersing the resin or resin precursor is preferably 50 to 2000% by weight, more preferably 100 to 2000%, based on the weight of the resin or resin precursor or their solvent solution. 1000% by weight.
  • the amount of the aqueous medium used is 50% by weight or more, the dispersion is good, and when it is 2000% by weight or less, the amount of the surfactant remaining in the resin particles does not increase, and the resin characteristics may be adversely affected. Absent.
  • the amount of (P) used is preferably 0.01 to 3% by weight, preferably 0.05 to 1% by weight based on the weight of the aqueous medium from the viewpoint of emulsion stability. Is more preferable.
  • the resin (a) or its solvent solution or the resin (a) precursor (a0) or its solvent solution is emulsified and dispersed in an aqueous medium to obtain an aqueous dispersion (D1) of resin particles (A).
  • a dispersing device can be used.
  • the dispersion apparatus used in the present invention is not particularly limited as long as it is generally commercially available as an emulsifier or a disperser.
  • a homogenizer manufactured by IKA
  • polytron manufactured by Kinematica
  • TK auto homomixer Batch type emulsifiers such as Primix Co., Ltd., Ebara Milder (Ebara Manufacturing Co., Ltd.), TK Fillmix, TK Pipeline Homo Mixer (Primics Co., Ltd.), Colloid Mill (Shinko Pantech Co., Ltd.), Continuous emulsifiers such as slasher, trigonal wet pulverizer (manufactured by Mitsui Miike Chemical Co., Ltd.), Captron (manufactured by Eurotech) and fine flow mill (manufactured by Taiheiyo Kiko Co., Ltd.), microfluidizer (manufactured by Mizuho Industrial Co., Ltd.), High pressure emulsifiers such as Nanomizer (manufactured by Nanomizer) and APV Gaurin (manufactured by Ga
  • the temperature at the time of emulsification dispersion is usually 0 to 150 ° C. (under pressure), preferably 5 to 98 ° C.
  • the time for emulsification and dispersion is usually 1 minute to 2 hours, preferably 5 minutes to 1 hour.
  • the pH at which the aqueous dispersion (D1) of the resin particles (A) is formed is preferably 2.0 to 6.5, more preferably 3.0 to 6.2 from the viewpoint of emulsification. preferable.
  • Resin particles (A) can be obtained by removing the aqueous medium and, if necessary, the solvent from the aqueous dispersion (D1).
  • Examples of the method for removing the aqueous medium and, if necessary, the solvent from the aqueous dispersion (D1) include the following methods (1) to (3). From the viewpoint of the electrical characteristics of the resin particles, the following (2) is preferable. It is a method. (1) A method of drying the aqueous dispersion (D1) under reduced pressure or normal pressure. (2) A method in which the aqueous dispersion (D1) is subjected to solid-liquid separation with a centrifuge, a spatula filter, a filter press or the like, and the obtained powder is dried. (3) A method in which the aqueous dispersion (D1) is frozen and dried (so-called lyophilization).
  • the obtained powder when the obtained powder is dried, it can be carried out using known equipment such as a fluidized bed dryer, a vacuum dryer and a circulating dryer. Moreover, it can classify
  • the anionic surfactant (X) can be removed from the resin particles, and it is preferable to use wash water having a pH of 7.0 to 9.0. It is preferable from the viewpoint of washing and removing properties of the active agent (X). Under the conditions of pH 7.0 to 9.0, the HLB of the acidic group of the anionic surfactant (X) changes, so that the solubility in water is improved, and the anionic surfactant is improved from the resin particles. (X) can be easily removed.
  • the amount of the surfactant remaining in the resin particles is preferably 0 to 1.0% by weight based on the weight of the resin particles, from the viewpoint of the electrical characteristics and heat resistance of the resin particles, and 0 to 0.5% by weight. % Is more preferable.
  • Resin (a) or its solvent solution and / or precursor (a0) of resin (a) or its solvent solution is dispersed in an aqueous dispersion (D2) of resin particles (B) made of resin (b).
  • the aqueous dispersion (D2) is acidic within one molecule.
  • the pH when the aqueous dispersion (D3) of the resin particles (C) is formed is 2.0 to 6.5, and the pH when the aqueous medium is removed from the aqueous dispersion (D3) is It is preferably 7.0 to 9.0 from the viewpoint of achieving both emulsifiability and washing removability.
  • the resin particles (B) By adsorbing the resin particles (B) on the surface of the resin particles (A), it is possible to prevent the resin particles (A) or the resin particles (C) from uniting with each other. Since it becomes difficult for C) to break up, the particle size of the resin particles (C) can be converged to a constant value, and the uniformity of the particle size can be further improved.
  • any resin can be used as long as it can form an aqueous dispersion, and it may be a thermoplastic resin or a thermosetting resin.
  • resin (a) is mentioned, A preferable thing is also the same.
  • the ratio of the hydrophobic monomer to the hydrophilic monomer constituting the vinyl resin depends on the type of monomer selected, but generally the hydrophobic monomer is 10 mol% or more. It is preferable that it is 30 mol% or more. When the ratio of the hydrophobic monomer is less than 10 mol%, the vinyl resin becomes water-soluble and the particle size uniformity of (C) is impaired.
  • the hydrophilic monomer means a monomer that dissolves in water at an arbitrary ratio
  • the hydrophobic monomer means another monomer (a monomer that is basically not miscible with water).
  • the particle size of the resin particles (B) is usually smaller than the particle size of the resin particles (A). From the viewpoint of particle size uniformity, the particle size ratio [volume average particle size of the resin particles (B)] / [resin The value of the volume average particle diameter of the particles (A) is preferably in the range of 0.001 to 0.3. When the particle size ratio is larger than 0.3, (B) is not efficiently adsorbed on the surface of (A), so that the obtained particle size distribution of (C) tends to be wide.
  • the volume average particle size of the resin particles (B) can be adjusted as appropriate within the range of the above particle size ratio so as to be a particle size suitable for obtaining the resin particles (C) having a desired particle size.
  • a resin particle (C) having a volume average particle diameter of 1 ⁇ m it is preferably 0.0005 to 0.3 ⁇ m, more preferably 0.001 to 0.2 ⁇ m, and 10 ⁇ m of resin particles (C).
  • the volume average particle size can be measured with a laser type particle size distribution analyzer LA-920 (manufactured by Horiba, Ltd.) or Multisizer III (manufactured by Beckman Coulter, Inc.).
  • Examples of the method for obtaining the aqueous dispersion (D2) of the resin particles (B) made of the resin (b) include the same method as the above-described method for dispersing the resin (a) in an aqueous medium.
  • an aqueous medium used here the thing similar to the said aqueous medium is mentioned, A preferable thing is also the same.
  • a solvent when producing the aqueous dispersion (D3), the same solvents as those exemplified in the aqueous dispersion (D1) can be used, and preferred ones are also the same.
  • the aqueous dispersion (D3) it is preferable to contain the water-soluble polymer (P) in the aqueous dispersion (D2) as in the case of producing the aqueous dispersion (D1).
  • the value of the volume average particle size / number average particle size of the resin particles (C) is preferably 1.0 to 1.4, more preferably 1.0 to 1.2. Is more preferable.
  • the resin particles (C) From the viewpoint of particle size uniformity, powder fluidity, storage stability, etc. of the resin particles (C), it is preferable that 5% or more of the surface of the resin particles (A) is covered with the resin particles (B), More preferably, 30% or more of the surface of (A) is covered with (B).
  • the surface coverage can be determined based on the following equation from image analysis of an image obtained with a scanning electron microscope (SEM).
  • SEM scanning electron microscope
  • the resin particles (C) are preferably 40 to 99.99% by weight (A) and 0.01 to 60% by weight (B More preferably, it comprises 50 to 99.9% by weight of (A) and 0.1 to 50% by weight of (B).
  • the amount of the anionic surfactant (X) and the aqueous medium used when producing the aqueous dispersion (D3) is the same as the amount used when producing the aqueous dispersion (D1), and the preferred amount used is also the same. It is.
  • Examples of a method for producing the aqueous dispersion (D3) include a method for producing the above-described aqueous dispersion (D1).
  • the temperature at the time of dispersion and the time for dispersion are the same as the values for producing the aqueous dispersion (D1) described above.
  • the pH at which the aqueous dispersion (D3) of the resin particles (C) is formed is preferably 2.0 to 6.5, more preferably 3.0 to 6.2 from the viewpoint of emulsification. preferable.
  • the method for removing the aqueous medium and, if necessary, the solvent from the aqueous dispersion (D3) includes the same method as the method for removing the aqueous medium and, if necessary, the solvent from the aqueous dispersion (D1), and the pH is 7 It is preferable to use a wash water of 0.0 to 9.0 from the viewpoint of washability of the anionic surfactant (X).
  • Additives such as stabilizers and flame retardants may be mixed.
  • an additive it may be mixed when forming an aqueous dispersion in an aqueous medium, but added in advance with the resin (a) or the resin (b). More preferably, after mixing the agent, the mixture is added and dispersed in an aqueous medium.
  • the additive is not necessarily mixed when forming the particles in the aqueous medium, and may be added after the particles are formed.
  • the colorant may be added by a known dyeing method, or the additive may be contained together with a solvent and / or a plasticizer.
  • the entire amount of the product was charged into a glass reactor equipped with a heating / stirring / cooling device, and charged with 109 parts (1.11 moles) of maleic anhydride in a nitrogen atmosphere and reacted at a reaction temperature of 50 to 60 ° C. for 3 hours. It was.
  • the total amount of this product was added to an aqueous solution in which 147 parts (1.17 mole parts) of sodium sulfite and 2 parts of sodium hydroxide were dissolved in 772 parts of water at 50-60 ° C. under a nitrogen atmosphere, and the sulfonation reaction was carried out for 3 hours.
  • the entire amount of the product was charged into a glass reactor equipped with a heating / stirring / cooling device, and charged with 109 parts (1.11 moles) of maleic anhydride in a nitrogen atmosphere and reacted at a reaction temperature of 50 to 60 ° C. for 3 hours. It was. The total amount of this product was added to an aqueous solution in which 147 parts (1.17 mole parts) of sodium sulfite and 2 parts of sodium hydroxide were dissolved in 1119 parts of water in a nitrogen atmosphere at 50-60 ° C., and the sulfonation reaction was carried out for 3 hours.
  • the entire amount of the product was charged into a glass reactor equipped with a heating / stirring / cooling device, and charged with 109 parts (1.11 moles) of maleic anhydride in a nitrogen atmosphere and reacted at a reaction temperature of 50 to 60 ° C. for 3 hours. It was.
  • the total amount of this product was added to an aqueous solution obtained by dissolving 147 parts (1.17 mole parts) of sodium sulfite and 2 parts of sodium hydroxide in 713 parts of water in a nitrogen atmosphere at 50 to 60 ° C. and subjected to sulfonation reaction for 3 hours.
  • the entire amount of the product was charged into a glass reactor equipped with a heating / stirring / cooling device, and charged with 109 parts (1.11 moles) of maleic anhydride in a nitrogen atmosphere and reacted at a reaction temperature of 50 to 60 ° C. for 3 hours. It was. The total amount of this product was added to an aqueous solution in which 147 parts (1.17 mole parts) of sodium sulfite and 2 parts of sodium hydroxide were dissolved in 821 parts of water in a nitrogen atmosphere at 50 to 60 ° C. and subjected to sulfonation reaction for 3 hours.
  • the entire amount of the product was charged into a glass reactor equipped with a heating / stirring / cooling device, and charged with 109 parts (1.11 moles) of maleic anhydride in a nitrogen atmosphere and reacted at a reaction temperature of 50 to 60 ° C. for 3 hours. It was. The total amount of this product was added to an aqueous solution in which 147 parts (1.17 mole parts) of sodium sulfite and 2 parts of sodium hydroxide were dissolved in 729 parts of water in a nitrogen atmosphere at 50 to 60 ° C. and subjected to sulfonation reaction for 3 hours.
  • the entire amount of the product was charged into a glass reactor equipped with a heating / stirring / cooling device, and charged with 109 parts (1.11 moles) of maleic anhydride in a nitrogen atmosphere and reacted at a reaction temperature of 50 to 60 ° C. for 3 hours. It was.
  • the total amount of this product was added to an aqueous solution prepared by dissolving 147 parts (1.17 mole parts) of sodium sulfite and 2 parts of sodium hydroxide in 756 parts of water under a nitrogen atmosphere at 50 to 60 ° C. and subjected to sulfonation reaction for 3 hours.
  • the total amount of the product was charged into a glass reactor equipped with a heating and stirring / cooling device, and 61.5 parts (1.05 mol parts) of sulfamic acid was charged. After reacting at a reaction temperature of 100 ° C. for 12 hours, 321 parts of a 30% aqueous sodium hydroxide solution was intermittently added at 50-60 ° C. in 5 portions every 2 hours, and the gauge pressure ⁇ After topping at 0.02 MPa, it was diluted with 363 parts of water to obtain 957 parts of a 30% aqueous solution of polyoxyethylene (4 mol) -added styrene (1 mol) sulfated sodium salt (X′-1) of phenol.
  • Production Example 13 (Production of curing agent) In a reaction vessel equipped with a stir bar and a thermometer, 50 parts of ethylenediamine and 50 parts of methyl isobutyl ketone were charged and reacted at 50 ° C. for 5 hours. The obtained compound is defined as a curing agent ( ⁇ -1).
  • a urethane-modified polyester (1) having a molecular weight of 72,000 and a free isocyanate content of 0.7% was obtained.
  • 570 parts of bisphenol A ethylene oxide 2-mole adduct and 217 parts of terephthalic acid were polycondensed at 230 ° C. under normal pressure for 6 hours to obtain a modified number average molecular weight of 2,400, hydroxyl value of 51 and acid value of 5.
  • No polyester (2) was obtained. 200 parts of urethane-modified polyester (1) and 800 parts of polyester (2) were dissolved and mixed in 2,000 parts of ethyl acetate to obtain a resin solution (A-1).
  • the reaction and aging were carried out at 70 ° C. for 5 hours and at 90 ° C. for 5 hours to obtain resin fine particles (B-1) aqueous dispersion (D2-1) of amine-cured epoxy resin.
  • the volume average particle size of the resin fine particles (B-1) measured by LA-920 was 0.78 ⁇ m.
  • Examples 1 to 10 and Comparative Examples 1 to 3 Based on the formulation described in Table 1, anionic surfactants (X-1 to X-10, X′-1) and ion-exchanged water are mixed and stirred in a container to obtain emulsifiers (E-1 to E ⁇ 10, E′-1 to E′-3) were obtained. Further, after adding 500 parts of ion-exchanged water and mixing uniformly, the temperature was raised to 50 ° C., the pH was adjusted to 5.0 to 6.0, and the mixture was stirred at 12,000 rpm with a TK homomixer.
  • Examples 11 to 20 and Comparative Examples 4 to 6 Based on the formulation described in Table 2, anionic surfactants (X-1 to X-20, X'-1), ion-exchanged water and resin fine particle dispersion (D2-1) are mixed and stirred in a container. Further, after adding 500 parts of ion-exchanged water and mixing uniformly, the temperature was raised to 50 ° C., and the resin solution (A-1b) 300 prepared in Production Example 14 was stirred at 12,000 rpm with a TK homomixer. The mixture was stirred for 10 minutes and then transferred to a three-necked flask equipped with a stir bar and a thermometer.
  • anionic surfactants X-1 to X-20, X'-1
  • ion-exchanged water and resin fine particle dispersion (D2-1) are mixed and stirred in a container. Further, after adding 500 parts of ion-exchanged water and mixing uniformly, the temperature was raised to 50 ° C., and the resin solution (A-1b)
  • Ethyl acetate was distilled off at 50 ° C, and the temperature was raised to 98 ° C and reacted for 5 hours.
  • An aqueous dispersion (D3-1) of resin particles was obtained.
  • the aqueous dispersion (D3-1) was separated by filtration, washed with water, and dried to give resin particles of Examples 11 to 20 and Comparative Examples 4 to 6 (C-1 to C-10, C′-1 to C′ ⁇ ). 3) was obtained.
  • Examples 21 to 30 and Comparative Examples 7 to 9 Based on the formulation described in Table 3, a surfactant, ion-exchanged water, and resin fine particle dispersion (D2-1) were mixed and stirred in a container to obtain a resin fine particle aqueous dispersion. Next, 150 parts of the prepolymer ( ⁇ -1) obtained in Production Example 12, 6 parts of the curing agent ( ⁇ -1) obtained in Production Example 13 and 40 parts of ethyl acetate were mixed in a beaker. After adding 457 parts of resin fine particle dispersion (D2-1), the mixture was mixed for 10 minutes at 12,000 rpm using a TK homomixer.
  • Examples 31 to 40 and Comparative Examples 10 to 12 Based on the formulation described in Table 4, anionic surfactants (X-1 to X-10, X′-1), ion-exchanged water and resin fine particle dispersion (D2-1) were mixed and stirred in a container. Then, after adding 500 parts of ion-exchanged water and mixing uniformly, the temperature was raised to 50 ° C., the pH was adjusted to 5.0 to 6.0, and the mixture was stirred at 12,000 rpm with a TK homomixer.
  • anionic surfactants X-1 to X-10, X′-1
  • ion-exchanged water and resin fine particle dispersion D2-1
  • Example 14 After adding 300 parts of the resin solution (A-1b) prepared in Example 14 and stirring for 10 minutes, it was transferred to a three-necked flask equipped with a stirring bar and a thermometer, and ethyl acetate was distilled off at 50 ° C. The mixture was heated to 98 ° C. and reacted for 5 hours to obtain an aqueous dispersion of resin particles (D3-3). A 10% aqueous solution of sodium hydroxide was added to this aqueous dispersion (D3-3) to obtain a dispersion having a pH of 8.0 to 9.0, and then this aqueous dispersion (D3-3) was filtered off. By washing with water and drying, the resin particles of Examples 31 to 40 and Comparative Examples 10 to 12 (C-31 to C-40, C′-7 to C′-9) were obtained.
  • the resin particles obtained in Examples 1 to 40 and Comparative Examples 1 to 12 were dispersed in water, and the volume average particle size and number average particle size were measured with Multisizer III. The values of the volume average particle diameter and the volume average particle diameter / number average particle diameter obtained are shown in Tables 1 to 4.
  • the degree of aggregation serving as a measure of powder flowability was measured by the following method. The results are shown in Tables 1 to 4. The smaller the degree of aggregation, the better the powder fluidity.
  • Tables 1 to 4 show the residual surfactant contents in the resin particles obtained in Examples 1 to 40 and Comparative Examples 1 to 12.
  • the resin particles in the examples all have a uniform particle size, a low degree of aggregation, a good powder flowability, and a low surfactant residual ratio of the resin particles, electrical characteristics, thermal characteristics, and chemical stability. Was good.
  • the resin particles produced using the emulsifier of the present invention have a uniform particle size and excellent powder flowability, electrical characteristics, thermal characteristics and chemical stability without using inorganic fine powder.
  • To toner used in electrophotography, electrostatic recording and electrostatic printing, slush molding resin, powder paint, spacers for manufacturing electronic parts such as liquid crystal, standard particles for electronic measuring instruments, various hot melt adhesives, and others It is extremely useful for molding materials.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Developing Agents For Electrophotography (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

La présente invention concerne un agent émulsifiant qui est utile pour obtenir des particules de résine qui ont un diamètre particulaire uniforme et qui présentent d'excellentes propriétés telles que d'excellentes caractéristiques électriques, d'excellentes caractéristiques thermiques et une excellente stabilité chimique; un procédé de production de particules de résine, qui utilise l'agent émulsifiant selon l'invention pour produire les particules de résine; et des particules de résine qui sont obtenues par le biais du procédé de production selon l'invention. La présente invention concerne ainsi un agent émulsifiant destiné à la production de particules de résine, ledit agent émulsifiant contenant un tensioactif (X) anionique contenant deux groupes hydrophiles ou plus ayant différents degrés d'acidité dans chaque molécule, de préférence un tensioactif anionique contenant un groupe hydrophile ayant un pKa situé dans la plage allant de 3,0 à 6,0 et un groupe hydrophile ayant un pKa inférieur à 3,0; un procédé de production de particules de résine, qui utilise l'agent émulsifiant selon l'invention; et des particules de résine qui sont obtenues par le biais du procédé de production selon l'invention.
PCT/JP2012/084078 2011-12-28 2012-12-28 Agent émulsifiant destiné à la production de particules de résine, procédé de production de particules de résine, et particules de résine WO2013100129A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016117895A (ja) * 2014-12-22 2016-06-30 三洋化成工業株式会社 樹脂粒子の製造方法
JP2018194610A (ja) * 2017-05-15 2018-12-06 花王株式会社 電子写真用トナーの製造方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008076519A (ja) * 2006-09-19 2008-04-03 Fuji Xerox Co Ltd 静電荷像現像用トナー、静電荷像現像用トナーの製造方法、静電荷像現像剤、画像形成方法、及び画像形成装置
WO2008133166A1 (fr) * 2007-04-20 2008-11-06 Kao Corporation Procédé de fabrication d'une émulsion de résine
JP2009235269A (ja) * 2008-03-27 2009-10-15 Sanyo Chem Ind Ltd 樹脂粒子及びその製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008076519A (ja) * 2006-09-19 2008-04-03 Fuji Xerox Co Ltd 静電荷像現像用トナー、静電荷像現像用トナーの製造方法、静電荷像現像剤、画像形成方法、及び画像形成装置
WO2008133166A1 (fr) * 2007-04-20 2008-11-06 Kao Corporation Procédé de fabrication d'une émulsion de résine
JP2009235269A (ja) * 2008-03-27 2009-10-15 Sanyo Chem Ind Ltd 樹脂粒子及びその製造方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016117895A (ja) * 2014-12-22 2016-06-30 三洋化成工業株式会社 樹脂粒子の製造方法
JP2018194610A (ja) * 2017-05-15 2018-12-06 花王株式会社 電子写真用トナーの製造方法

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