WO2022091912A1 - Particules de résine à base de vinyle - Google Patents

Particules de résine à base de vinyle Download PDF

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WO2022091912A1
WO2022091912A1 PCT/JP2021/038803 JP2021038803W WO2022091912A1 WO 2022091912 A1 WO2022091912 A1 WO 2022091912A1 JP 2021038803 W JP2021038803 W JP 2021038803W WO 2022091912 A1 WO2022091912 A1 WO 2022091912A1
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vinyl
structural unit
resin particles
derived
mass
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PCT/JP2021/038803
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English (en)
Japanese (ja)
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晃哉 遠藤
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東邦化学工業株式会社
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Priority to JP2022559056A priority Critical patent/JPWO2022091912A1/ja
Priority to CN202180074378.4A priority patent/CN116368178A/zh
Publication of WO2022091912A1 publication Critical patent/WO2022091912A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to vinyl-based resin particles, and more particularly to vinyl-based resin particles for producing a porous membrane used for making a thermosetting resin or the like porous.
  • polyimide and / or polyamide-imide porous membranes have been studied as filters used as gas or liquid separation membranes, separators for lithium ion batteries, fuel cell electrolyte membranes, or low dielectric constant materials.
  • a varnish in which fine particles such as silica particles are dispersed in a polymer solution of polyamic acid or polyimide is applied onto a substrate, and then applied as necessary.
  • a method is known in which a polyimide film containing fine particles is obtained by heating the film, and then fine particles such as silica particles in the polyimide film are removed using hydrofluoric acid to make the polyimide film porous (see Patent Document 1). ..
  • organic fine particles are often prepared in an aqueous solvent and are often distributed as a fine particle dispersion containing water. Therefore, when using organic fine particles, if a varnish containing polyamic acid or polyimide is prepared using a fine particle dispersion liquid containing water, a varnish containing water is inevitably obtained.
  • the varnish contains water and fine particles, it contains a lump of polyamic acid that embraces the fine particles because the orientation of the polyamic acids is hindered by the poor compatibility between the polyamic acid and the solvent containing water and the presence of the fine particles.
  • a mixture having a non-uniform composition that can cause poor formation of the coating film is likely to be formed, which may lead to a decrease in film strength.
  • the dried organic fine particles have poor dispersion stability and solvent resistance to an organic solvent that dissolves polyamic acid, aggregates are generated, and pores are uniformly formed, and the polyimide porous membrane has good air permeability. There are problems such as difficulty in obtaining.
  • the present invention has been made in view of the above problems, and has excellent dispersion stability and solvent resistance to organic solvents, suppresses the generation of aggregates and gelation, and is uniform and fine on a thermosetting resin film or the like. It is an object of the present invention to provide novel vinyl-based resin particles capable of forming pores.
  • the present invention is intended for the following [1] to [9].
  • It is a polymer having a structural unit (A1) derived from a monofunctional vinyl-based monomer, a structural unit (A2) derived from a polyfunctional vinyl-based monomer, and a structural unit (B) derived from a reactive emulsifier.
  • Vinyl-based resin particles for manufacturing porous membranes The ratio of the structural unit (A1) is 88 to 99% by mass, the ratio of the structural unit (A2) is 0.9 to 10% by mass, and the ratio of the structural unit (B) is 0.1 to 2% by mass.
  • Structural unit (A) derived from vinyl-based monomer and A polymer having a structural unit (b1) derived from a compound represented by the following general formula (I), which is different from the structural unit (A).
  • Vinyl-based resin particles for manufacturing porous membranes [During the ceremony, m represents an integer of 1 to 3 and represents R represents a group represented by the following formula (i) or formula (ii). (In the formula, R 1 represents a hydrogen atom or a methyl group), AO represents an alkyleneoxy group having 2 to 4 carbon atoms, and n represents an integer of 0 to 100.
  • X represents a hydrogen atom or -SO 3 M, -COOM and -PO 3 M (in the formula, M represents an alkali metal atom, an alkaline earth metal atom, an ammonium group or an organic ammonium group).
  • the structural unit (A) derived from the vinyl-based monomer includes a structural unit (A1) derived from a monofunctional vinyl-based monomer and a structural unit (A2) derived from a polyfunctional vinyl-based monomer.
  • the structural unit (A1) derived from the monofunctional vinyl-based monomer includes a structural unit (a1) derived from the monofunctional styrene-based monomer.
  • the structural unit (A1) derived from the monofunctional vinyl-based monomer includes a structural unit (a2) derived from the monofunctional (meth) acrylic monomer.
  • the proportion of the polyfunctional vinyl-based monomer (A2) is 0.9% by mass to 10% by mass with respect to the total mass of the structural units of the polymer.
  • the vinyl-based resin particle according to any one of [1] and [4] to [7].
  • a polymerization initiator in an aqueous dispersion medium, It is characterized in that a vinyl-based monomer and a compound represented by the following general formula (I) different from the vinyl-based monomer are emulsion-polymerized.
  • m represents an integer of 1 to 3 and represents R represents a group represented by the following formula (i) or formula (ii).
  • R 1 represents a hydrogen atom or a methyl group
  • AO represents an alkyleneoxy group having 2 to 4 carbon atoms
  • n represents an integer of 0 to 100.
  • X represents a hydrogen atom or -SO 3 M, -COOM and -PO 3 M (in the formula, M represents an alkali metal atom, an alkaline earth metal atom, an ammonium group or an organic ammonium group).
  • the vinyl-based resin particles of the present invention suppress the generation of aggregates, gelation and increase in viscosity in a mixture with an organic solvent that dissolves a thermosetting resin (for example, polyamic acid which is a precursor of a polyimide resin). It has mixing stability, and the dissolution and shape change of particles are suppressed even in an organic solvent, so that the solvent resistance can be excellent. Therefore, when the vinyl-based resin particles of the present invention are used as a porous material for a thermosetting resin, it is difficult for the particles to dissolve or aggregate even in a mixture with the thermosetting resin material, and a film obtained from the resin material. In the above, uniform and fine pores can be easily formed, and a porous body (porous film) can be produced.
  • a thermosetting resin for example, polyamic acid which is a precursor of a polyimide resin.
  • FIG. 1 shows electron micrographs of resin particles after a solvent resistance test ((a) Example 1, (b) Example 2, (c) Example 3, and (d) Example 4).
  • FIG. 2 shows an electron micrograph of the resin particles after the solvent resistance test ((a) Comparative Example 1 and (b) Comparative Example 2).
  • FIG. 3 shows an SEM image of the porous membrane ((a) Example 5, (b) Example 6, (c) Example 7, (d) Example 8).
  • FIG. 4 shows an SEM image of the porous membrane (Comparative Example 3).
  • the present invention is a vinyl-based polymer having a structural unit (A) derived from a vinyl-based monomer and a structural unit (b1) derived from a compound represented by the general formula (I) described later as essential.
  • Targets resin particles the vinyl-based resin particles (polymer) of the present invention is a monomer component containing a vinyl-based monomer and a compound represented by the general formula (I), which constitutes each of the above-mentioned structural units. It can be a copolymer (copolymer) of (mixture).
  • the vinyl-based resin particles of the present invention can be suitably used as a porous material for a thermosetting resin, that is, as vinyl-based resin particles for producing a porous membrane.
  • a structural unit (A1) derived from a monofunctional vinyl-based monomer described later and a structural unit (A2) derived from a polyfunctional vinyl-based monomer described later will be described later.
  • the target is vinyl-based resin particles, which are polymers having a structural unit (B) derived from a reactive emulsifier.
  • the (meth) acrylic monomer means both an acrylic monomer and a methacrylic monomer.
  • (meth) acrylic acid alkyl ester refers to acrylic acid alkyl ester and methacrylic acid alkyl ester.
  • structural unit derived from vinyl-based monomer "structural unit derived from monofunctional styrene-based monomer”
  • structural unit derived from monofunctional (meth) acrylic monomer "structural unit derived from monofunctional (meth) acrylic monomer”
  • Notations such as “structural unit derived from polyfunctional vinyl-based monomer” are vinyl-based monomer, monofunctional styrene-based monomer, monofunctional (meth) acrylic-based monomer, polyfunctional vinyl-based monomer. However, each indicates a structural unit formed when polymerized, and does not represent those monomers themselves.
  • the polymer which is the vinyl-based resin particles of the present invention has a structural unit (A) derived from the vinyl-based monomer.
  • the structural unit (A) is distinguished from the structural unit (B) derived from the reactive emulsifier described later and the structural unit (b1) derived from the compound represented by the general formula (I).
  • the structural unit (A) can include a structural unit (A1) derived from a monofunctional vinyl-based monomer and a structural unit (A2) derived from a polyfunctional vinyl-based monomer, and is also monofunctional vinyl-based.
  • the structural unit (A1) derived from the monomer includes a structural unit (a1) derived from a monofunctional styrene-based monomer and a structural unit (a2) derived from a monofunctional (meth) acrylic monomer. be able to.
  • the structural unit (A) includes both a structural unit (A1) derived from a monofunctional vinyl-based monomer and a structural unit (A2) derived from a polyfunctional vinyl-based monomer.
  • the structural unit (a1) is, but is not limited to, a structural unit represented by the following formula, for example.
  • Ra 1 represents an alkyl group having 1 to 10 carbon atoms
  • M 1 represents an alkali metal atom, a group 2 metal atom, an ammonium group, or an organic ammonium group.
  • p represents 0 or an integer of 1 to 5, and a plurality of Ra1s may be the same or different from each other.
  • Examples of the monofunctional styrene-based monomer constituting the structural unit (a1) include styrene, ⁇ -methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-dimethylstyrene, 2, Styrene such as 5-dimethylstyrene and 2,4,6-trimethylstyrene and derivatives thereof; styrene sulfonates such as sodium styrene sulfonate and ammonium styrene sulfonate can be mentioned. Among these, styrene, ⁇ -methylstyrene, and sodium styrene sulfonate can be mentioned as suitable ones.
  • the structural unit (a2) to be used may be included.
  • the structural unit derived from the (meth) acrylic monomer has the property of being easily decomposed (depolymerized) in the monomer unit regardless of whether it is monofunctional or polyfunctional and has excellent thermal decomposition properties, and the vinyl resin particles of the present invention. The thermal decomposition temperature of the resin can be lowered.
  • the structural unit (a2) is, but is not limited to, a structural unit represented by the following formula, for example.
  • R a21 , R a22 , and R a23 independently represent a hydrogen atom or a methyl group
  • R a24 represents a hydrogen atom and an alkyl group having 1 to 10 carbon atoms.
  • Examples of the monofunctional (meth) acrylic monomer constituting the structural unit (a2) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and (meth). ) Isopropyl acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, 3-methylbutyl (meth) acrylate, (meth) ) N-hexyl acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, etc.
  • (Meta) acrylic acid esters having a number of 1 to 18 can be mentioned.
  • methyl (meth) acrylate and ethyl (meth) acrylate are preferable as the (meth) acrylate-based monomer from the viewpoint that resin particles having the same particle size can be easily obtained.
  • Methyl (meth) acrylate is particularly preferred.
  • the structural unit (A2) derived from the polyfunctional vinyl-based monomer in addition to the structural unit (A1) derived from the monofunctional vinyl-based monomer as the structural unit (A), the structural unit (A2) derived from the polyfunctional vinyl-based monomer is used. Can be included.
  • the structural unit (A2) derived from the polyfunctional vinyl-based monomer By containing the structural unit (A2) derived from the polyfunctional vinyl-based monomer, the solvent resistance of the obtained vinyl-based resin particles is enhanced, and the varnish composition (polyimide varnish) described later due to the swelling of the vinyl-based resin particles. It is possible to suppress a decrease in the viscosity of the resin, and it is easy to obtain vinyl-based resin particles having a high compressive strength and a uniform particle size.
  • the structural unit (A2) include a structural unit (a3) derived from a polyfunctional (meth) acrylic monomer and a structural unit (a4) derived from a polyfunctional (poly) vinyl monomer. Can be done.
  • the structural unit (a3) derived from the polyfunctional (meth) acrylic monomer is not limited, but has, for example, a partial structure represented by the following formula. Can be mentioned.
  • R a21 , R a22 , and R a23 each independently represent a hydrogen atom or a methyl group.
  • polyfunctional (meth) acrylic monomer constituting the structural unit (a3) include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, and 1,3-butylene.
  • Alkyldi (meth) acrylates having 2 to 50 moles of alkylene oxide groups; ethoxylated glycerintri (meth) acrylates, propylene oxide-modified glycerol tri (meth) acrylates, ethylene oxide-modified trimethylolpropanetri (meth) acrylates, tris.
  • Tri (meth) acrylates of polyhydric alcohols having 1 to 10 carbon atoms such as methylol propanetri (meth) acrylates, pentaerythritol monohydroxytri (meth) acrylates, and trimethylolpropanetriethoxytri (meth) acrylates; pentaerythritol tetra Tetra (meth) acrylates of polyhydric alcohols with 1 to 10 carbon atoms such as (meth) acrylates, dipentaerythritol tetra (meth) acrylates and ditrimethylolpropanetetra (meth) acrylates; pentaerythritol penta (meth) acrylates, di.
  • Penta (meth) acrylates of polyhydric alcohols with 1 to 10 carbon atoms such as pentaerythritol (monohydroxy) penta (meth) acrylate; polyhydric alcohols with 1 to 10 carbon atoms such as pentaerythritol hexa (meth) acrylate Hexa (meth) acrylate and the like can be mentioned, but the present invention is not limited thereto.
  • polyfunctional (poly) vinyl-based monomer constituting the structural unit (a4) include polyfunctional aliphatic vinyl-based monomers such as isoprene and butadiene; cyclopentadiene and cyclo.
  • Polyfunctional alicyclic vinyl-based monomer such as hexadiene;
  • Polyfunctional aromatic vinyl-based monomer such as divinylbenzene, divinyltoluene, divinylnaphthalene; divinyl adipate, divinyl maleate, divinyl phthalate, divinyl isophthalate, etc.
  • Polyfunctional vinyl ester-based monomer such as diallyl maleate, diallyl phthalate, diallyl isophthalate, diallyl adipate; divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, etc.
  • Polyfunctional vinyl ether-based monomer Polyfunctional allyl ether-based monomer such as diallyl ether, diallyl oxyetane, triallyl oxyetane; Polyfunctional vinyl ketone-based monomer such as divinyl ketone and diallyl ketone; Dialyl amine, diallyl isocyanurate , Multifunctional nitrogen-containing vinyl monomers such as diallyl cyanurate, methylenebis (meth) acrylamide, and bismaleimide; Multifunctional silicon-containing vinyl monomers such as dimethyldivinylsilane, divinylmethylphenylsilane, and diphenyldivinylsilane. However, it is not limited to these.
  • ethylene glycol di (meth) acrylate and 1,3-butylene glycol are examples of the polyfunctional vinyl-based monomer constituting the structural unit (A2).
  • Di (meth) acrylate, 1,4-butylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, divinylbenzene, divinyltoluene and the like are preferable.
  • ethylene glycol di (meth) acrylate trimethylolpropane tri (meth) acrylate, and 1,3-butylene glycol di (meth) acrylate are mentioned. Of these, ethylene glycol di (meth) acrylate is preferable.
  • the structural unit (A2) derived from the polyfunctional vinyl-based monomer is preferably 1% by mass to 10% by mass with respect to the total mass of the structural unit (A).
  • the polymer which is the vinyl resin particles of the present invention has the structural units (A1) [(a1), (a2)] and (A2) [(a3), (a4) as long as the effects of the present invention are not impaired. )] May contain structural units derived from other vinyl-based monomers (polymerizable monomers). That is, the vinyl-based resin particles of the present invention can be a copolymer of a monomer component (mixture) containing other polymerizable monomers.
  • other polymerizable monomers include monofunctional (meth) acrylonitrile-based single amounts such as (meth) acrylonitrile.
  • Body Monofunctional heterocycle-containing vinyl-based monomer such as N-vinylimidazole and N-vinyl-2-pyrrolidone; Simple such as vinyl acetate (vinyl acetate), isopropenyl acetate, vinyl propionate, vinyl decanoate and the like.
  • Monofunctional vinyl ester-based monomer Monofunctional vinyl ether-based monomer such as ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, cyclohexyl vinyl ether, ethylene glycol vinyl ether; Other monofunctional vinyl compounds such as vinyl cyclopentane, vinyl cyclohexane, ethyl vinyl benzene, etc.
  • Monomer Monofunctional (meth) acrylic acid-based monomer such as (meth) acrylic acid and itaconic acid; Monofunctional (meth) acrylamide-based monomer such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide. Examples thereof include, but are not limited to, monomers.
  • the reactive emulsifier is not particularly limited as long as it is an emulsifier reactive with the above-mentioned monomer or its polymer, but has a radically polymerizable double bond, a hydrophilic functional group, and a hydrophobicity in its molecular structure. Examples thereof include those having each group and having emulsifying, dispersing, and wetting functions similar to general emulsifiers.
  • Examples of the structure of the radically polymerizable double bond in the molecular structure include 1-propenyl group, 2-methyl-1-propenyl group, allyl group, methallyl group, vinyl group, acryloyl group, metaacryloyl group and the like. Can be mentioned.
  • hydrophilic functional group in the molecular structure examples include anionic groups such as sulfate group, nitrate group, phosphate group, borate group and carboxyl group (-OSO 3- , -NO 3- , -OPO 3- , and so on. -B (OH) 4- , -COO- , etc.); Cationic groups such as amino groups ( -NH 3+ , etc.); Polyoxyalkylene chains such as polyoxyethylene, polyoxymethylene, polyoxypropylene; hydroxy groups, etc. Can be mentioned.
  • hydrophobic group in the molecular structure examples include an alkyl group, an alkenyl group, a phenyl group, an alkylphenyl group, a styrrified phenyl group, a naphthyl group and the like.
  • Reactive emulsifiers are classified into anionic emulsifiers, nonionic emulsifiers, cationic emulsifiers, amphoteric emulsifiers and the like according to the type of hydrophilic functional group contained in the molecular structure. Further, the radically polymerizable double bond, the hydrophilic functional group, and the hydrophobic group in the molecular structure of the reactive emulsifier can each have a plurality of types of structures and functional groups.
  • the reactive emulsifier preferably has at least a polyoxyalkylene chain and a sulfuric acid group as hydrophilic functional groups inside the molecular structure.
  • the trade name generally commercially available as such a reactive emulsifier is not particularly limited, but for example, Adecaria Soap SR, ER, SE, NE, PP (ADEKA Corporation), Aqualon HS, BC, KH. (Daiichi Kogyo Seiyaku Co., Ltd.), Latemul PD (Kao Co., Ltd.), Eleminor JS, RS (Sanyo Kasei Kogyo Co., Ltd.), Antox MS (Nippon Emulsifier Co., Ltd.) and the like.
  • the polymer which is the vinyl resin particles of the present invention can have a structural unit (b1) derived from the compound represented by the following general formula (I).
  • the compound represented by the following general formula (I) has a hydrophobic group and a hydrophilic group in the molecule, and also has a copolymerizable unsaturated group. Therefore, the compound represented by the following general formula (I) also functions as a reactive (copolymerizable) emulsifier (corresponding to the above-mentioned reactive emulsifier), and various problems in the conventional emulsion polymerization, for example, during emulsion polymerization.
  • m represents an integer of 1 to 3, and preferably represents 2 from the viewpoint of emulsifying property.
  • AO represents an alkyleneoxy group having 2 to 4 carbon atoms.
  • the alkyleneoxy group having 2 to 4 carbon atoms include an ethyleneoxy group, a propyleneoxy group, and a butyleneoxy group.
  • ethyleneoxy group is preferable as AO. Since the ethyleneoxy group is more hydrophilic than other alkyleneoxy groups and can form a resin emulsion having a dense hydration layer, the stability of the resin particles in the aqueous dispersion medium can be further improved.
  • n represents the number of repetitions of the alkyleneoxy unit (that is, the number of moles of the alkyleneoxy group added).
  • n is an integer of 0 to 100, preferably an integer of 5 to 50, and more preferably an integer of 5 to 30, from the viewpoint of the stability of the resin particles in the aqueous dispersion medium.
  • X represents a hydrogen atom or -SO 3 M, -COOM and -PO 3 M (in the formula, M represents an alkali metal atom, an alkaline earth metal atom, an ammonium group or an organic ammonium group).
  • M represents an alkali metal atom, an alkaline earth metal atom, an ammonium group or an organic ammonium group.
  • the alkali metal atom include a sodium atom and a potassium atom.
  • Examples of the alkaline earth metal atom include a calcium atom and a barium atom.
  • X is preferably a hydrogen atom, -SO 3 NH 4 , -SO 3 Na, or -SO 3 K, and more preferably -SO 3 NH 4 .
  • R represents a polymerizable unsaturated group, specifically a group represented by the following formula (i) or formula (ii), and in the formula, R 1 represents a hydrogen atom or a methyl group.
  • Examples of the structural unit (b1) derived from the compound represented by the general formula (I) include the following structures.
  • m, R 1 , AO, n, and X are as defined above.
  • m, R 1 , AO, n, and X are as defined above.
  • a compound represented by the following formula (I-1) can be mentioned.
  • m, AO, n, and X are as defined above.
  • the ratio of the structural unit (A) when the total structural unit of the polymer is 100% by mass from the viewpoint of copolymerizability at the time of polymerization, for example, the ratio of the structural unit (A) is 98.0.
  • the mass% to 99.9% by mass and the ratio of the structural unit (B) (for example, the structural unit (b1)) can be 0.1% by mass to 2.0% by mass.
  • the ratio of the structural unit (A1) when the total structural unit of the vinyl resin particles (polymer) is 100% by mass, the ratio of the structural unit (A1) is 88 to 99% by mass, and the ratio of the structural unit (A2) is 0.9 to.
  • the ratio of the structural unit (B) can be 10% by mass and 0.1 to 2% by mass.
  • the ratio of the structural unit (B) may be read as the ratio of the structural unit (b1), or the total of the structural unit (b1) and the structural unit (B) other than the structural unit (b1). It may be read as a ratio.
  • the ratio of the structural unit (a1) derived from the monofunctional styrene-based monomer in the structural unit (A) is set. 10% by mass to 99% by mass, the ratio of the structural unit (a2) derived from the monofunctional (meth) acrylic monomer is 0% by mass to 80% by mass, and the structural unit derived from the polyfunctional vinyl-based monomer ( The ratio of A2) can be 1% by mass to 10% by mass, and the ratio of other structural units derived from the polymerizable monomer can be 0% by mass to 5% by mass (total of 100% by mass).
  • the vinyl-based resin particles of the present invention can be obtained by emulsion polymerization of a monomer component containing the vinyl-based monomer and a reactive emulsifier (for example, a compound represented by the general formula (I)). can.
  • a reactive emulsifier for example, a compound represented by the general formula (I)
  • the emulsification polymerization method is preferable in that particles having a small particle size can be easily obtained.
  • vinyl-based monomer various monomers mentioned in the above description [monofunctional vinyl-based monomer (monofunctional styrene-based monomer, monofunctional (meth) acrylic-based monomer), Polyfunctional vinyl-based monomers (polyfunctional (meth) acrylic monomers, polyfunctional (poly) vinyl-based monomers), and other polymerizable monomers] can be used as the reactive emulsifiers of the above-mentioned compounds and the like. Can be exemplified respectively.
  • a preferred embodiment of emulsion polymerization is to use a polymerization mixture containing the above-mentioned monomer component, a polymerization initiator, and optionally other additives (surfactant, protective colloid agent, chain transfer agent, pH adjuster, etc.) for emulsion polymerization.
  • the emulsion polymerization step may be included, and if desired, an aging step of aging the reaction solution obtained in the emulsion polymerization step may be included.
  • the emulsion polymerization is usually carried out in an aqueous dispersion medium, and the aqueous dispersion medium is not particularly limited, and examples thereof include water and a mixed solution of water and an alcohol solvent. From the viewpoint of stability (non-aggregation) of the vinyl-based resin particles formed after emulsion polymerization, water is preferable as the aqueous dispersion medium.
  • the amount of the aqueous dispersion medium used can be appropriately set so that the content of the vinyl-based resin particles present in the system after emulsion polymerization is a desired ratio. For example, the content of the vinyl resin particles existing in the system is set to 1% by mass to 70% by mass, 10% by mass to 60% by mass, 20% by mass to 50% by mass, and the amount of the aqueous dispersion medium used is appropriate. Just set it.
  • the polymerization initiator used for the emulsion polymerization is not particularly limited, and a known polymerization initiator can be used.
  • a known polymerization initiator can be used.
  • Azo compounds such as tetrahydrate; persulfates such as potassium persulfate and ammonium persulfate; peroxides such as hydrogen peroxide, benzoyl peroxide, parachlorobenzoyl peroxide, lauroyl peroxide, ammonium peroxide and the like.
  • peroxides such as hydrogen peroxide, benzoyl peroxide, parachlorobenzoyl peroxide, lauroyl peroxide, ammonium peroxide and the like.
  • the present invention is not limited to these examples.
  • azo compounds and peroxides are preferably used because they can also function as a decomposition accelerator, that is, they can have a function of promoting thermal decomposition when vinyl-based resin particles are applied as a porous material.
  • the amount of the polymerization initiator used is not particularly limited, but is preferably 0.05 parts by mass or more per 100 parts by mass of the monomer component, from the viewpoint of increasing the polymerization rate and reducing the residual amount of the unreacted monomer. Is 0.1 part by mass or more, and can be, for example, 5 parts by mass or less from the viewpoint of polymerization stability.
  • the reactive emulsifier and the compound represented by the general formula (I) also serve as an emulsifier and can satisfactorily initiate and complete emulsion polymerization.
  • a surfactant (emulsifier) generally used for emulsion polymerization may be further used as another additive as long as the effect is not impaired.
  • an anionic surfactant or a cationic surfactant and / or other nonionic surfactant may be used in combination.
  • anionic surfactants include fatty acid sekken; sekken rosinate; alkyl sulfates such as ammonium dodecyl sulfate and sodium dodecyl sulphate; alkyl sulfonates such as ammonium dodecyl sulfonate and sodium dodecyl sulfonate; Alkylaryl sulfonates such as ammonium dodecylbenzene sulfonate, sodium dodecylbenzene sulfonate, sodium dodecylnaphthalene sulfonate; polyoxyalkylene alkyl sulfate; polyoxyalkylene aryl sulfate; polyoxyalkylene alkylaryl sulfate; dialkylsulfosuccinic acid Salts; arylsulfonic acid-formalin condensates; fatty acid salts such as
  • Examples of the cationic surfactant include stearyltrimethylammonium, cetyltrimethylammonium, and lauryltrimethylammonium.
  • Examples of the nonionic surfactant include polyoxyalkylene alkylphenyl ether, polyoxyalkylene alkyl ether, alkyl polyglucoside, polyglycerin alkyl ether, polyoxyalkylene fatty acid ester, polyglycerin fatty acid ester, total ruby monofatty acid ester and the like. Be done.
  • the amount used is, for example, 0.05 parts by mass or more, 0.1 parts by mass or more, or 0.3 parts by mass with respect to 100 parts by mass of the monomer component.
  • the number may be 10 parts by mass or more, and the upper limit thereof may be, for example, 10 parts by mass, 8 parts by mass or less, and 5 parts by mass or less.
  • a known protective colloidal agent may be used in combination as another additive.
  • the protective colloid agent include fully saponified polyvinyl alcohol, partially saponified polyvinyl alcohol, hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose, polyacrylic acid, and gum arabic.
  • a known chain transfer agent or pH adjuster may be used in combination.
  • the chain transfer agent include octyl mercaptan, dodecyl mercaptan, mercaptoethanol, thioglycolic acid, allyl alcohol, isopropyl alcohol, sodium hypophosphite and the like.
  • the pH adjusting agent include inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid; organic acids such as citric acid, succinic acid, apple acid and lactic acid; and inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate.
  • Alkanolamines such as monoethanolamine, diethanolamine, triethanolamine, isopropanol, aliphatic amines such as ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, aromatic polyamines such as phenylenediamine and tolylenediamine, piperazine.
  • Organic bases such as heterocyclic polyamines such as aminoethylpiperazine and the like.
  • the amount of each monomer used can be appropriately set.
  • the ratio of the vinyl-based monomer to the total amount of all the monomers (total 100% by mass) is 98.0% by mass to 99.9% by mass, and is represented by a reactive emulsifier (for example, the general formula (I)).
  • the proportion of the compound) can be 0.1% by mass to 2.0% by mass.
  • the ratio of the monofunctional vinyl-based monomer is 88% by mass to 99% by mass
  • the ratio of the polyfunctional vinyl-based monomer is 0.9% by mass with respect to the total amount of all the monomers (total 100% by mass).
  • the ratio of the reactive emulsifier can be from% to 10% by mass, and the ratio of the reactive emulsifier can be from 0.1 to 2% by mass.
  • the monofunctional styrene-based monomer is 10% by mass to 99% by mass
  • the monofunctional (meth) acrylic monomer is 0% by mass to 80% by mass, and more.
  • the functional vinyl-based monomer may be 1% by mass to 10% by mass, and the other polymerizable monomer may be 0% by mass to 5% by mass.
  • the emulsion polymerization may be carried out by a known emulsion polymerization method, and for example, a monomer dropping method, a pre-emulsion method, a batch charging polymerization method and the like can be adopted. From the viewpoint of industrial productivity, it is preferable to adopt the pre-emulsion method because it can be polymerized stably and a polymer (resin particles) having few aggregates can be obtained.
  • the method for charging the above-mentioned monomer component, polymerization initiator, and other additives is not particularly limited and may be appropriately set.
  • a vinyl-based monomer is pre-emulsified with a reactive emulsifier (for example, a compound represented by the general formula (I)) and an aqueous dispersion medium such as water.
  • a reactive emulsifier for example, a compound represented by the general formula (I)
  • an aqueous dispersion medium such as water.
  • the remaining polymerization mixture may be dropped or the like.
  • the remaining monomer component and the remaining monomer component may be performed.
  • the emulsion polymerization step is repeated by two or more steps, that is, in an embodiment including, for example, a first emulsion polymerization step and a second emulsion polymerization step, a core portion is formed by the first emulsion polymerization step, and a subsequent second emulsion polymerization step is carried out.
  • the shell portion By forming the shell portion on the surface of the core portion, the core-shell type resin particles can be formed.
  • the second emulsion polymerization step may be performed a plurality of times, and when the second second emulsion polymerization step is performed, the surface of the shell portion formed by the first second emulsion polymerization step is newly formed. Resin particles on which a shell portion is formed can be obtained.
  • the composition of the monomer component used in each step can be changed, and the monomer component used in each step can be changed to 1. It may be a monomer of the seed. That is, in the first emulsion polymerization step and the second emulsion polymerization step, different monomers (one kind) may be used, or a mixture of monomers and a monomer (one kind) may be used. Alternatively, a mixture of different monomers may be used in each step. When a mixture of monomers of the same type is used, a mixture in which the mixing ratio of the monomers is changed can be used.
  • the monofunctional styrene-based monomer, the polyfunctional vinyl-based monomer, and the reactive emulsifier (for example, represented by the general formula (I)) are represented.
  • the monofunctional styrene-based monomer, the monofunctional (meth) acrylic-based monomer, and the polyfunctional vinyl-based monomer among the monofunctional vinyl-based monomers are used.
  • a mixture containing a monomer and a reactive emulsifier for example, a compound represented by the general formula (I) can be used.
  • the polymerization temperature in the emulsion polymerization may be appropriately set depending on the polymerization initiator and the like used, and may be, for example, 30 ° C to 90 ° C or 50 ° C to 80 ° C.
  • the polymerization time may be appropriately set according to the reaction rate obtained from the charged amount of the monomer component and the residual amount in the reaction solution, but is usually about 1 hour to 12 hours, for example, about 2 hours to 8 hours. be.
  • the aging step after the emulsion polymerization step, the unreacted monomers are reduced, or the dispersion containing the polymer particles (vinyl-based resin particles) obtained by the emulsion polymerization is stabilized. It is done for the purpose of doing so.
  • the aging temperature in the aging step can be, for example, 50 ° C. to 90 ° C., and can be, for example, 70 ° C. to 85 ° C. By keeping the aging temperature within the above range, it can be expected that the amount of the unreacted monomer mixture can be reduced while suppressing the aggregation of particles.
  • the aging time may be appropriately set according to the reaction rate obtained from the total amount of the monomer components charged and the residual amount of the monomer components in the reaction solution, but is usually 1 hour to 12 hours, preferably 1 to 12 hours. It takes about 2 to 8 hours.
  • a surfactant may be added if necessary for the purpose of facilitating the suppression of aggregation of the polymer particles during aging.
  • the surfactant used in the aging step it is preferable to use the surfactant mentioned in the emulsion polymerization step described above, and it is also possible to use an anionic surfactant or a nonionic surfactant. ..
  • the amount of the surfactant used in the aging step is, for example, 0.05 parts by mass or more and 0.1 parts by mass or more with respect to 100 parts by mass of the total amount of the monomer components attached to the emulsion polymerization step. , 0.3 parts by mass or more, and for example, 10 parts by mass or less, 8 parts by mass or less, and 5 parts by mass.
  • the vinyl-based resin particles of the present invention are obtained in the form of a dispersion (also referred to as a dispersion liquid) containing the formed polymer in an aqueous dispersion medium.
  • a dispersion also referred to as a dispersion liquid
  • the content of the vinyl-based resin particles (polymer) in the aqueous dispersion medium is not particularly limited, but may be, for example, 10 to 80% by mass, 20 to 70% by mass, 30 to 60% by mass, or the like.
  • a vinyl-based monomer containing a monofunctional vinyl-based monomer and a polyfunctional vinyl-based monomer for example, the vinyl-based monomer is used.
  • a method for producing an aqueous dispersion of vinyl-based resin particles which comprises a step of emulsion polymerization of a different reactive emulsifier such as a compound represented by the general formula (I), is also targeted.
  • the vinyl-based resin particles of the present invention are preferably particles having a median diameter D 50 of 0.05 ⁇ m to 2.0 ⁇ m.
  • a value of 50% volume diameter based on a volume measured by a dynamic light scattering method can be adopted.
  • the particle size of the vinyl-based resin particles is compared. It can be a small range.
  • the median diameter is less than 0.2 ⁇ m, the particle size may be too small to contribute to the formation of sufficient pores. Further, if it exceeds 1.5 ⁇ m, there is a possibility that the mechanical strength of the thermosetting resin to be punctured is lowered.
  • the vinyl-based resin particles of the present invention preferably have a pyrolysis temperature lower than the pyrolysis temperature of the thermosetting resin described later under atmospheric pressure.
  • the thermal decomposition temperature is a condition according to JIS K7120 (thermogravimetric analysis method for plastics), and the weight reduction due to thermal decomposition of a sample is measured by a thermogravimetric analyzer (TGA). Means the starting temperature.
  • TGA thermogravimetric analyzer
  • TGA thermogravimetric analyzer
  • the thermal decomposition temperature of the vinyl-based resin particles of the present invention under a nitrogen atmosphere is, for example, 340 to 440 ° C, preferably 370 to 410 ° C.
  • the vinyl-based resin particles are obtained as a dispersion (dispersion liquid) dispersed in an aqueous dispersion medium through the emulsion polymerization step described above, and are used as a dispersion of various solvents depending on the use of the resin particles. can do.
  • the aqueous dispersion medium can be solvent-substituted and used as a form of the dispersion dispersed in the organic solvent (organic solvent dispersion).
  • the aqueous dispersion medium or the organic solvent can be removed from the dispersion dispersed in the aqueous dispersion medium or the organic solvent to obtain vinyl-based resin particles (powder), which can also be used.
  • the method for removing the aqueous dispersion medium and the organic solvent include a freeze-drying method, a hot-air drying method, and a spray-drying method.
  • the obtained resin particles (powder) can be dispersed again in an aqueous dispersion medium or an organic solvent and used as an aqueous solvent dispersion or an organic solvent dispersion.
  • organic solvent examples include lower alcohols such as methanol, ethanol and isopropanol; linear amides such as N, N-dimethylformamide (DMF) and N, N-dimethylacetamide (DMAc); N-methyl-2- Cyclic amides such as pyrrolidone (NMP); ethers such as ⁇ -butyrolactone (GBL); glycols such as ethyl cellosolve and ethylene glycol, acetonitrile and the like can be mentioned. This substitution can be carried out by a usual method such as a distillation method or an ultrafiltration method. At this time, the content of the vinyl-based resin particles in the organic solvent dispersion can be appropriately set according to the intended use.
  • linear amides such as N, N-dimethylformamide (DMF) and N, N-dimethylacetamide (DMAc)
  • NMP N-methyl-2- Cyclic amides
  • NMP pyrrolidone
  • GBL ⁇ -
  • the content of the resin particles is 1% by mass or more based on the total mass of the organic solvent dispersion. It can be 70% by mass, 10% by mass to 60% by mass, and 20% by mass to 50% by mass. If the proportion of the resin particles in the organic solvent dispersion is less than 1% by mass, it is not economical, and if it is more than 70% by mass, the resin particles may aggregate or settle without becoming a stable dispersion, which will be described later. There is a risk that handling will deteriorate when mixed with a thermosetting resin.
  • the viscosity of the organic solvent dispersion can be, for example, about 0.6 mPa ⁇ s to 100 mPa ⁇ s at 20 ° C.
  • the dispersion may further contain other compounds such as surfactants.
  • thermosetting resin The vinyl-based resin particles of the present invention are suitably used for making a thermosetting resin porous. That is, according to the present invention, it is possible to provide a porous material made of the vinyl-based resin particles.
  • thermosetting resin include polyimide resin and diallyl phthalate resin.
  • a polyimide resin can be mentioned as a suitable example.
  • thermosetting resin porous Method for producing a porous body
  • the method for making a thermosetting resin porous (method for producing a porous body) using the vinyl-based resin particles of the present invention is not particularly limited.
  • a varnish composition containing a polyimide precursor, a polyamic acid, vinyl-based resin particles of the present invention, and a solvent is first applied onto a substrate to form a coating film.
  • the coating film is dried, that is, the solvent is removed from the coating film to form a film (precursor film of a polyimide porous film) containing a polyimide precursor and vinyl resin particles (precursor film of polyimide porous film).
  • a film precursor film of a polyimide porous film
  • vinyl resin particles precursor film of polyimide porous film
  • Precursor film forming step the film (precursor film of the polyimide porous film) is fired to convert the polyimide precursor into polyimide, and vinyl-based resin particles are removed (thermally decomposed) (removal step of removing vinyl-based resin particles).
  • Polyimide porous film can be obtained.
  • the removal step (firing step) for removing the vinyl-based resin particles can be carried out at a temperature at which the polyimide precursor can be converted into polyimide and the vinyl-based resin particles can be decomposed and disappeared.
  • the film (precursor film of the polyimide porous film) is peeled off from the substrate (peeling step), and the unfired film is fired (the vinyl-based resin particles are removed).
  • the removal step) may be performed.
  • a specific example of the method for making the thermosetting resin porous will be described, but the method is not limited to the following method.
  • This step is a step of applying a varnish composition containing a polyamic acid as a polyimide precursor, the vinyl-based resin particles of the present invention, and a solvent onto a substrate to form a coating film.
  • the substrate include PET films, SUS substrates, glass substrates and the like.
  • a product obtained by polymerizing an arbitrary tetracarboxylic acid dianhydride and a diamine can be used without particular limitation.
  • the tetracarboxylic acid dianhydride and the diamine can be appropriately selected from compounds conventionally used as raw materials for synthesizing polyamic acids.
  • the tetracarboxylic acid dianhydride may be an aromatic tetracarboxylic acid dianhydride or an aliphatic tetracarboxylic acid dianhydride
  • the diamine may be an aromatic diamine or an aliphatic. It may be diamine.
  • the means for producing the polyamic acid is not particularly limited, and a known method such as a method of reacting a tetracarboxylic acid dianhydride component with a diamine component in a solvent can be used.
  • the amount of the tetracarboxylic acid dianhydride and the diamine used is not particularly limited, but for example, 0.50 mol or more and 1.50 mol or less of the diamine is used with respect to 1 mol of the tetracarboxylic acid dianhydride. Can be a percentage.
  • the reaction solution of polyamic acid can be used as it is as a polyamic acid-containing liquid for preparing a varnish composition.
  • the solvent used in the varnish composition examples include water, an organic solvent, or a combination thereof.
  • the organic solvent used in the varnish composition is preferably a compound that exhibits neutrality or weak basicity in water from the viewpoint of avoiding hydrolysis of the polyamic acid.
  • Preferable examples of the organic solvent include, for example, various organic solvents mentioned in the above-mentioned organic solvent dispersion of resin particles.
  • a dispersant may be further added to the varnish composition for the purpose of uniformly dispersing the vinyl resin particles.
  • a dispersant When a dispersant is used, it can be used in an amount of, for example, 0.01% by mass or more and 5% by mass or less with respect to the fine particles.
  • the varnish composition can be produced by mixing the above-mentioned various components in predetermined amounts, and the specific procedure thereof is not particularly limited.
  • the varnish composition is made of vinyl so that, for example, the ratio of vinyl resin particles / polyamic acid is 0.5 to 4.0 (mass ratio) when the polyamic acid-fine particle composite film (precursor film) described later is used. It can contain based resin particles and polyamic acid. Alternatively, these components can be contained so that the volume ratio of the vinyl resin particles / polyamic acid is, for example, 1.0 to 5.0 when the composite film is formed.
  • the solid content concentration of the varnish composition is not particularly limited, but may be, for example, 1% by mass or more, 5% by mass or more, and 10% by mass or more, and the upper limit thereof is, for example, 60% by mass or less. Yes, for example, it can be 30% by mass or less.
  • the solid content concentration referred to here means the concentration of a component other than the solvent, and even a liquid component is included in the weight as a solid content.
  • the viscosity of the varnish composition is not particularly limited as long as a coating film having a desired film thickness can be formed. For example, the viscosity of the varnish composition can be 300 cP or more and 20,000 cP or less.
  • This step is a step of removing the solvent from the coating film obtained in the above step to form a precursor film of the polyimide porous film.
  • the above-mentioned varnish composition is applied onto a substrate to form a coating film, and then 0 ° C. or higher and 100 ° C. or lower, preferably 10 ° C. or higher at normal pressure. It may be dried at 100 ° C. or lower.
  • the precursor film may be formed directly on the substrate, or may be formed on a lower film different from the precursor film formed on the substrate. Further, after forming a precursor film using the above-mentioned varnish composition, an upper film different from the precursor film may be further formed on the upper layer.
  • both the embodiment in which the lower layer film is provided on the substrate and the embodiment in which the upper layer film is provided on the precursor film are included in the precursor film forming step.
  • a peeling step of peeling the precursor film from the substrate may be included.
  • the substrate is not required to have heat resistance that can withstand the temperature at which the precursor film is fired.
  • Step of removing vinyl-based resin particles (firing step)>
  • the vinyl-based resin particles of the present invention are thermally decomposed and removed at the same time as the precursor film of the above-mentioned polyimide porous film is imidized by firing or the like, or during the imidization process, or after the imidization. It is a process.
  • a polyimide porous film can be obtained by forming uniform and fine pores in the polyimide resin film.
  • the vinyl-based resin particles may be removed while imidizing the polyamic acid, or may be performed after the polyamic acid is imidized.
  • the method for imidizing the polyamic acid is not particularly limited.
  • the imidization may be either thermal imidization or chemical imidization.
  • chemical imidization a method such as immersing a precursor membrane containing a polyamic acid in acetic anhydride or a mixed solvent of acetic anhydride and isoquinoline can be used.
  • calcination which is thermal imidization, is preferable because it is not necessary to remove the imidizing agent by washing.
  • calcination related to thermal imidization will be described.
  • the firing temperature varies depending on the structure of the polyamic acid, but is preferably 120 ° C. or higher and 500 ° C. or lower, more preferably 150 ° C. or higher and 450 ° C. or lower, and more preferably 300 ° C. or higher and 450 ° C. or lower.
  • the firing conditions are, for example, a method of raising the temperature from room temperature to about 400 ° C. to 450 ° C. in about 3 hours and then holding the temperature at the same temperature for about 2 to 30 minutes, or stepwise from room temperature in increments of, for example, 50 ° C. Drying-heat including continuous or stepwise temperature raising operation such as raising the temperature to 400 ° C. to 450 ° C.
  • the imidization method can also be used.
  • the precursor film or the laminated film containing the precursor film is once peeled off from the substrate, and the firing step is performed, the end portion of the precursor film or the laminated film is made of SUS. It is also possible to adopt a method of fixing to a mold or the like to prevent deformation due to firing.
  • the film thickness of the polyimide porous film obtained after firing can be obtained by measuring the thicknesses of a plurality of locations with a micrometer or the like and averaging them. What kind of average film thickness is preferable depends on the use of the polyimide porous membrane, but for example, when it is used for a separator or the like, it is preferably 5 ⁇ m or more and 500 ⁇ m or less, more preferably 10 ⁇ m or more and 100 ⁇ m or less, and 15 ⁇ m or more and 30 ⁇ m or less. Is even more preferable. When used for a filter or the like, it is preferably 5 ⁇ m or more and 500 ⁇ m or less, more preferably 10 ⁇ m or more and 300 ⁇ m or less, and further preferably 20 ⁇ m or more and 150 ⁇ m or less.
  • the polyimide porous film thus obtained is a non-transparent or yellow or brown colored porous film.
  • the polyimide porous membrane is a porous membrane in which spherical pores communicate with each other throughout the membrane, and the front and back surfaces communicate with each other.
  • the present invention will be described below with reference to examples. However, the present invention is not limited to these Examples and Comparative Examples.
  • the test method for vinyl-based resin particles is as follows.
  • ⁇ Mesian diameter> For a dispersion liquid (resin particle aqueous dispersion) in which resin particles are dispersed in water, a dynamic light scattering (DLS) particle size distribution measuring device Nanotrac (registered trademark) Wave II (trade name, Microtrac Bell Co., Ltd.) ) was used to obtain a volume-based particle size distribution, which was determined as the median diameter (D50) in the particle size distribution.
  • DLS dynamic light scattering
  • ⁇ Mixed stability test> The aqueous dispersion of resin particles was dried in a hot air convection dryer at 105 ° C., and 1 g of the obtained resin particle powder and 5 g of N, N-dimethylacetamide were measured in a sample bottle and dispersed in an ultrasonic cleaner for 30 minutes. Processed. The state of the obtained resin particle dispersion (organic solvent dispersion) was visually confirmed, and the mixing stability of the resin particles with the organic solvent was evaluated according to the following evaluation criteria. ⁇ Evaluation criteria ⁇ ⁇ : It does not gel and maintains fluidity. (Good) ⁇ : Not gelled, but loses fluidity. (usually) X: Gelled or resin particles are dissolved. (Defective)
  • ⁇ Pyrolysis temperature> The aqueous dispersion of resin particles was dried in a hot air convection dryer at 105 ° C., and 10 mg of the obtained resin particle powder was subjected to a differential thermal balance Thermoplus EVO2 (registered trademark) TG8121 (trade name, manufactured by Rigaku Co., Ltd.). JIS compliant conditions, alumina as a reference, nitrogen flow rate 100 ml / min, temperature rise rate 10 ° C / min, temperature rise from 25 ° C to 600 ° C, thermal decomposition start temperature is read from the obtained TG curve, and this is vinyl-based. The thermal decomposition temperature of the resin particles was used.
  • Example 1 In a glass container having an internal capacity of 1.0 L equipped with a stirrer, a thermometer, a temperature controller, a condenser, and a dropping device, 383.0 g of ion-exchanged water was placed and nitrogen gas was introduced while stirring to perform nitrogen substitution. After that, it was heated with a mantle heater and the temperature was controlled at 72 ⁇ 2 ° C. to obtain a polymerization vessel.
  • styrene as a monofunctional monomer (styrene monomer manufactured by Asahi Kasei Co., Ltd.) 378.6 g, ethylene glycol dimethacrylate (Mitsubishi) as a polyfunctional monomer 22.2 g of Acryester ED manufactured by Chemical Co., Ltd. was added and stirred to obtain a monomer emulsion in which styrene and ethylene glycol dimethacrylate were emulsified in ion-exchanged water.
  • the remaining monomer emulsion and the polymerization initiator aqueous solution were each sent to the polymerization vessel over 240 minutes by a liquid feed pump, and the dropping polymerization was carried out.
  • the liquid feeding line was co-washed with 9.0 g of ion-exchanged water.
  • the mixture was cooled to 40 ° C. to obtain a crosslinked polymer aqueous dispersion (resin particle aqueous dispersion) having a solid content of 40%.
  • Example 2 Polymerization was carried out in the same manner as in Example 1 except that 374.2 g of styrene and 4.4 g of methyl methacrylate were used instead of 378.6 g of styrene in Example 1, and trimethylolpropane trimethacrylate was used instead of ethylene glycol dimethacrylate.
  • a crosslinked polymer aqueous dispersion resin particle aqueous dispersion
  • Example 3 Instead of 378.6 g of styrene in Example 1, 388.8 g of styrene was contained, and instead of 22.2 g of ethylene glycol dimethacrylate, a divinylbenzene mixture (DVB570 manufactured by Nittetsu Chemical & Materials Co., Ltd., 57% divinylbenzene was contained. Polymerization was carried out in the same manner as in Example 1 except that 12.0 g (divinylbenzene: 6.84 g, ethylvinylbenzene: 5.16 g) (containing 43% of ethylvinylbenzene) was used, and a crosslinked polymer having a solid content of 40% was used. An aqueous dispersion (resin particle aqueous dispersion) was obtained.
  • a divinylbenzene mixture (DVB570 manufactured by Nittetsu Chemical & Materials Co., Ltd., 57% divinylbenzene was contained.
  • Example 4 In addition, 364.7 g of styrene and 4.0 g of methyl methacrylate were used instead of 378.6 g of styrene in Example 1, and 32.1 g of 1,3-butylene glycol dimethacrylate was used instead of 22.2 g of ethylene glycol dimethacrylate.
  • Example 4 was polymerized in the same manner as in Example 1 to obtain a crosslinked polymer aqueous dispersion (resin particle aqueous dispersion) having a solid content of 40%.
  • Comparative Example 1 Nitrogen gas was introduced into a glass container having an internal capacity of 1.0 L equipped with a stirrer, a thermometer, a temperature controller, a condenser, and a dropping device, and nitrogen exchange was performed while stirring. After nitrogen substitution, 0.6 g of a 40% aqueous solution of triethanolamine lauryl sulfate (Alscope LS-40T manufactured by Toho Chemical Industry Co., Ltd.) was added as an emulsifier, heated with a mantle heater, and the temperature was controlled at 72 ⁇ 2 ° C to form a polymerization vessel. ..
  • the remaining monomer emulsion and the remaining polymerization initiator aqueous solution were each sent to the polymerization vessel over 300 minutes by a liquid feed pump, and the dropping polymerization was carried out.
  • the mixture was cooled to 40 ° C. to obtain a non-crosslinked polymer aqueous dispersion (resin particle aqueous dispersion) having a solid content of 40%.
  • Comparative Example 2 In place of 12.8 g of the polyoxyethylene styrenated propenylphenyl ether sulfate ammonium salt (25% aqueous solution) in Example 1, 8.0 g of lauryl sulfate triethanolamine (40% aqueous solution) was used, and 392.8 g of styrene and ethylene were used. Polymerization was carried out in the same manner as in Example 1 except that glycol dimethacrylate was changed to 8.0 g to obtain a crosslinked polymer aqueous dispersion (resin particle aqueous dispersion) having a solid content of 40%.
  • crosslinked polymer aqueous dispersion resin particle aqueous dispersion
  • Example 5 Production of polyimide porous membrane (1)> ⁇ Preparation of varnish composition> The crosslinked polymer aqueous dispersion (resin particle dispersion) of Example 1 was spray-dried using a spray dryer ADL-311S-A (manufactured by Yamato Kagaku Co., Ltd.) to obtain powdery vinyl-based resin particles.
  • the varnish composition was applied onto a polyethylene terephthalate film and then dried at 90 ° C. for 5 minutes to obtain a precursor film of a polyimide porous film. After the obtained precursor film was peeled off from the polyethylene terephthalate film, the precursor film was fired at 420 ° C. for 5 minutes in a firing furnace to imidize the polyamic acid while thermally decomposing the vinyl resin particles.
  • the polyimide porous film of Example 5 was obtained.
  • the air permeability can be, for example, within 250 seconds or 200 seconds. The lower the value, the more preferable, so the lower limit is not particularly set, but considering the handleability of the porous membrane sample, it can be, for example, 30 seconds or more. If the garley air permeability is within 250 seconds, it can be judged that it can be applied as a separator for a lithium ion battery because it exhibits sufficiently high ion permeability.
  • the vinyl-based resin particles according to the present invention have high air permeability and are polyimide porous having uniform spherical pores having a diameter equivalent to the median diameter of the particles.
  • a quality film can be produced, which is useful as a porous material for thermosetting resins.

Abstract

L'invention a pour but de fournir de nouvelles particules de résine à base de vinyle qui présentent une excellente stabilité de dispersion et une excellente résistance aux solvants pour des solvants organiques, qui éliminent la gélification et la génération d'agrégats, et qui permettent de former de fins pores uniformes dans un film d'une résine thermodurcissable, etc. La solution selon l'invention porte sur des particules de résine à base de vinyle qui constituent un polymère présentant un motif constitutif (A) dérivé d'un monomère à base de vinyle et un motif constitutif (b1) dérivé d'un composé représenté par la formule générale (I) différent du motif constitutif (A), à utiliser pour fabriquer une résine thermodurcissable poreuse. [Dans la formule, m représente un nombre entier compris entre 1 et 3, R représente un groupe insaturé polymérisable, AO représente un groupe alkylèneoxy en C2-4, n représente un nombre entier compris entre 0 et 100, X représente un atome d'hydrogène ou un groupe hydrophile anionique choisi dans le groupe constitué par -SO3M, -COOM et -PO3M (dans la formule, M représente un atome de métal alcalin, un atome de métal alcalino-terreux, un groupe d'ammonium ou un groupe d'ammonium organique.).]
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