WO2018061374A1 - Particules de résine conductrice et utilisation desdites particules - Google Patents

Particules de résine conductrice et utilisation desdites particules Download PDF

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Publication number
WO2018061374A1
WO2018061374A1 PCT/JP2017/024195 JP2017024195W WO2018061374A1 WO 2018061374 A1 WO2018061374 A1 WO 2018061374A1 JP 2017024195 W JP2017024195 W JP 2017024195W WO 2018061374 A1 WO2018061374 A1 WO 2018061374A1
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conductive resin
resin particles
particles
conductive
weight
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PCT/JP2017/024195
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English (en)
Japanese (ja)
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浩平 田中
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積水化成品工業株式会社
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Priority to KR1020197004208A priority Critical patent/KR102248989B1/ko
Priority to JP2018541923A priority patent/JP6722766B2/ja
Priority to CN201780060713.9A priority patent/CN109791813B/zh
Publication of WO2018061374A1 publication Critical patent/WO2018061374A1/fr

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    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C08J3/126—Polymer particles coated by polymer, e.g. core shell structures
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/283—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing one or more carboxylic moiety in the chain, e.g. acetoacetoxyethyl(meth)acrylate
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/285—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety
    • C08F220/286—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety and containing polyethylene oxide in the alcohol moiety, e.g. methoxy polyethylene glycol (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/124—Intrinsically conductive polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/285—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety
    • C08F220/288—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety and containing polypropylene-co-ethylene oxide in the alcohol moiety

Definitions

  • the present invention relates to conductive resin particles and uses thereof. More specifically, the present invention relates to conductive resin particles that can be suitably used in applications intended to express conductivity by bringing conductive resin particles into close contact with each other (conductive resin composition, Coating agent, film, and gap material).
  • Patent Document 1 A conductive particle powder made of one or more conductive fillers selected from products or alloys is disclosed.
  • the conductive particle powder has a hard conductive layer made of one or more conductive fillers selected from metals, metal oxides or alloys, the conductive resin particles are compressed.
  • the conductive resin particles are brought into close contact with each other, the adhesion between the conductive resin particles and the close contact between the conductive member (for example, electrode) and the conductive resin particles to be electrically connected by the conductive resin particles. Since the contact area between the conductive resin particles and the contact area between the conductive member and the conductive resin particles is small, the resistance during compression is high and good conductivity cannot be obtained.
  • the present invention has been made in view of the above-described conventional problems, and its purpose is to provide conductive resin particles having good conductivity, and a conductive resin composition, a coating agent, a film, and a gap material using the same. It is to provide.
  • the conductive resin particle of the present invention is a conductive resin particle having a core particle made of a polymer and a shell made of a conductive polymer that coats the core particle in order to solve the above problem.
  • the compressive strength at 10% compressive deformation is 0.1 to 30 MPa.
  • the core particles and the shell are both made of a polymer, and the compressive strength at the time of 10% compression deformation is 30 MPa or less. Therefore, the conductive resin particles are flexible and greatly deformed at the time of compression. Therefore, when the conductive resin particles are compressed and the conductive resin particles are brought into close contact with each other, the conductive member (for example, the conductive member intended to be electrically connected with the conductive resin particles or the conductive resin particles) The adhesion between the electrode) and the conductive resin particles is improved, and the contact area between the conductive resin particles and the contact area between the conductive member and the conductive resin particles are increased, so that the resistance during compression can be reduced. Good electrical conductivity can be obtained.
  • the conductive member for example, the conductive member intended to be electrically connected with the conductive resin particles or the conductive resin particles
  • the conductive resin composition of the present invention is characterized by containing the conductive resin particles of the present invention and a matrix resin in order to solve the above-mentioned problems.
  • the conductive resin composition having the above-described configuration includes the conductive resin particles of the present invention having good conductivity, the conductive resin composition having the above-described configuration is excellent in conductivity and antistatic properties. A molded product can be obtained.
  • the coating agent of the present invention is characterized by containing the conductive resin particles of the present invention and a binder resin in order to solve the above-mentioned problems.
  • the coating agent having the above-described configuration includes the conductive resin particles of the present invention having good conductivity, by applying the coating agent having the above-described configuration on a substrate, a conductive product (for example, a conductive film) or A product that can be suitably used as an antistatic product (for example, an antistatic film) can be obtained.
  • a conductive product for example, a conductive film
  • an antistatic product for example, an antistatic film
  • the film of the present invention is characterized by including the conductive resin particles of the present invention in order to solve the above problems.
  • the film having the above structure contains the conductive resin particles of the present invention having good conductivity, it can be suitably used as a conductive film or an antistatic film.
  • the gap material of the present invention is characterized by including the conductive resin particles of the present invention in order to solve the above-mentioned problems.
  • the gap material having the above-described structure includes the conductive resin particles of the present invention having good conductivity, it has conductivity and exhibits an antistatic function.
  • the present invention has the effect of providing conductive resin particles having good conductivity, and a conductive resin composition, coating agent, film, and gap material using the same.
  • the conductive resin particle of the present invention is a conductive resin particle having a core particle made of a polymer and a shell made of a conductive polymer that coats the core particle, and has a compressive strength at 10% compression deformation. 0.1 to 30 MPa.
  • the compressive strength at the time of 10% compression deformation of the conductive resin particles is 0.1 to 30 MPa, but preferably 0.1 to 17 MPa.
  • Conductive resin particles having a compressive strength at 10% compressive deformation of less than 0.1 MPa are inferior in mechanical strength and may be destroyed during use.
  • Conductive resin particles having a compressive strength of 10 MPa or less at 10% compressive deformation are obtained by compressing the conductive resin particles and bringing the conductive resin particles into close contact with each other.
  • compression strength at 10% compression deformation refers to compression strength at 10% compression deformation (hereinafter referred to as “10% compression strength”) obtained by the measurement method described in the section of Examples described later. ).
  • the conductive resin particles preferably have a volume average particle diameter of 1 to 200 ⁇ m.
  • the conductive resin particles have a volume average particle diameter of 1 ⁇ m or more, dispersibility in various solvents when used in a conductive paste or the like is improved, and good handling properties can be obtained.
  • the conductive resin particles have a volume average particle diameter of 200 ⁇ m or less, when the conductive resin particles are in close contact with each other, or when the conductive member and the conductive resin particles are in close contact, these The contact with each other is improved, and more conductive paths can be obtained.
  • “volume average particle diameter” means the volume average particle diameter obtained by the measurement method described in the Examples section described later.
  • the variation coefficient of the volume-based particle diameter of the conductive resin particles is preferably 10% or more, and more preferably in the range of 20% to 50%.
  • Conductive resin particles having a volume-based particle diameter variation coefficient of 10% or more (particularly 20% or more) are compared with conductive resin particles having the same composition and a volume-based particle diameter variation coefficient of 15% or less.
  • When the conductive resin particles are compressed so that the conductive resin particles are brought into close contact with each other in order to contain many conductive resin particles having a fine particle size (a particle size that is significantly smaller than the volume average particle size).
  • the conductive resin particles having many fine particle diameters enter between the other conductive resin particles to improve the filling rate.
  • volume-based variation coefficient of particle diameter means the variation coefficient of volume-based particle diameter obtained by the measurement method described in the section of Examples described later. It shall be.
  • the restoration rate of the conductive resin particles is preferably 15% or more and less than 30%, more preferably 15% or more and 25% or less, and further preferably 15% or more and 20% or less. Since the restoration rate of the conductive resin particles is 15% or more, even when the compressive stress is reduced after the conductive resin particles are compressed, the shape of the conductive resin particles is restored and the conductive resin is restored. The adhesion between particles can be maintained. Therefore, good electrical conductivity can be obtained stably. When the restoration rate of the conductive resin particles is less than 30%, it becomes easy to maintain the shape after the conductive resin particles are compressed, and as a result, good adhesion can be maintained.
  • the conductivity of the conductive resin particles of the present invention is preferably 5.0 ⁇ 10 ⁇ 3 to 5.0 ⁇ 10 ⁇ 1 (S / cm), preferably 9 ⁇ 10 ⁇ 3 to 1 ⁇ 10 ⁇ 1 ( S / cm) is more preferable, and 1 ⁇ 10 ⁇ 2 to 5 ⁇ 10 ⁇ 2 (S / cm) is even more preferable.
  • the conductivity of the conductive resin particles is not less than the lower limit of the above range, conductive resin particles having good conductivity can be realized.
  • the core particles may be a condensation polymer such as polyurethane or silicone polymer, but are preferably made of a vinyl monomer polymer.
  • the vinyl monomer may be a compound having at least one ethylenically unsaturated group (in a broad sense) and is a monofunctional vinyl monomer having one ethylenically unsaturated group. It may be a polyfunctional vinyl monomer having two or more ethylenically unsaturated groups.
  • Examples of the monofunctional vinyl monomers include monofunctional (meth) acrylic acid ester monomers described in detail later; styrene monomers such as styrene, p-methylstyrene, and ⁇ -methylstyrene; acetic acid And vinyl ester monomers such as vinyl. Of these, monofunctional (meth) acrylic acid ester monomers are preferred as monofunctional vinyl monomers.
  • (meth) acrylic acid means acrylic acid and / or methacrylic acid
  • (meth) acrylate” means acrylate and / or methacrylate.
  • polyfunctional vinyl monomer the following general formula (I) (Wherein R 1 is hydrogen or a methyl group, and n is an integer of 1 to 4), a monomer represented by the general formula (II), the following general formula (II) (Wherein R 2 is hydrogen or a methyl group, and m is an integer of 5 to 15), 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol Di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycerin di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, diethylene glycol di (meth) acrylate phthalate , Caprolactone-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified hydroxypivalate ester ne
  • Examples thereof include polyfunctional (meth) acrylic acid ester monomers having an unsaturated group; aromatic divinyl monomers such as divinylbenzene, divinylnaphthalene, and derivatives thereof.
  • aromatic divinyl monomers such as divinylbenzene, divinylnaphthalene, and derivatives thereof.
  • the monomer represented by the general formula (I), the monomer represented by the general formula (II), and urethane acrylate are preferable.
  • These vinyl monomers can be used alone or in combination of two or more.
  • the core particles are composed of a monofunctional (meth) acrylic acid ester monomer and the following general formula (I) (Wherein R 1 is hydrogen or a methyl group, and n is an integer of 1 to 4), and a monomer mixture (vinyl monomer) polymer is included. It is preferable that Since this polymer is a polymer having a crosslinked structure, it is possible to impart resilience to the core particles. Therefore, when this polymer is contained in the core particles, conductive resin particles having a good restoration rate can be realized.
  • the monofunctional (meth) acrylate monomer is not particularly limited.
  • Acrylic esters such as ethylhexyl; methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, isobornyl methacrylate, 2-hydroxyethyl methacrylate, 2-methoxyethyl methacrylate, glycidyl methacrylate, methacryl Tetrahydrofurfuryl acid, diethylaminoethyl methacrylate, trifluoroethyl methacrylate, heptadecafluorodecyl methacrylate, n-butyl methacrylate, t-butyl
  • alkyl acrylates having an alkyl group with 1 to 12 carbon atoms are preferred, and alkyl acrylates with an alkyl group having 1 to 8 carbon atoms are more preferred.
  • the 10% compressive strength of the core particles can be lowered, so that it becomes easy to realize conductive resin particles having a 10% compressive strength that is not more than the upper limit of the above-described range.
  • the content of the monofunctional (meth) acrylate monomer in the monomer mixture is preferably 70 to 99 parts by weight with respect to 100 parts by weight of the monomer mixture.
  • Examples of the monomer represented by the general formula (I) include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and tetraethylene glycol di (meth) acrylate. Is mentioned.
  • ethylene glycol di (meth) acrylate is particularly preferable, and when ethylene glycol di (meth) acrylate is used as the monomer represented by the general formula (I), The solvent resistance of the conductive resin particles can be more effectively improved with respect to the addition amount.
  • the content of the monomer represented by the general formula (I) in the monomer mixture is preferably 1 to 30 parts by weight with respect to 100 parts by weight of the monomer mixture.
  • the polymer of the monomer mixture contained in the core particle includes the following general formula (II ) (Wherein R 2 is hydrogen or a methyl group, and m is an integer of 5 to 15).
  • Examples of the monomer represented by the general formula (II) include pentaethylene glycol di (meth) acrylate, hexaethylene glycol di (meth) acrylate, heptaethylene glycol di (meth) acrylate, and octaethylene glycol di (meth). ) Acrylate, nonaethylene glycol di (meth) acrylate, decaethylene glycol di (meth) acrylate, tetradecaethylene glycol di (meth) acrylate, pentadecaethylene glycol di (meth) acrylate and the like.
  • the content of the monomer represented by the general formula (II) in the monomer mixture is preferably 1 to 20 parts by weight with respect to 100 parts by weight of the monomer mixture. More preferably, it is a part.
  • the monomer mixture may contain a monomer other than the monomers described above.
  • the monomer mixture may contain other monofunctional vinyl monomers copolymerizable with the monofunctional (meth) acrylic acid ester monomer.
  • examples of other monofunctional vinyl monomers copolymerizable with the monofunctional (meth) acrylic acid ester monomer include the aforementioned styrene monomers and the aforementioned vinyl ester monomers. . These other monofunctional vinyl monomers can be used alone or in combination of two or more.
  • the monomer mixture may contain other polyfunctional vinyl monomers other than those represented by the general formula (I) and the general formula (II).
  • other polyfunctional vinyl monomers include the above-mentioned polyfunctional (meth) acrylic acid ester monomers and the above-mentioned aromatic divinyl monomers.
  • the said vinylic monomer contains the monomer which has hydrophilic groups, such as a carboxy group and a hydroxy group, as a part, and contains the (meth) acrylic acid ester which has an alkylene oxide group.
  • the hydrophilic groups such as a carboxy group and a hydroxy group
  • the (meth) acrylic acid ester which has an alkylene oxide group Is more preferable.
  • hydrophilicity can be provided to the core particle surface.
  • the shell is formed by oxidative polymerization of the monomer in the dispersion liquid in which the core particles are dispersed in the aqueous medium, the core particles can be easily dispersed into the primary particles in the aqueous medium.
  • Individual core particles can be coated with a shell.
  • the (meth) acrylic acid ester having an alkylene oxide group include compounds represented by the following general formula.
  • R 3 represents H or CH 3
  • R 4 and R 5 are different and represent an alkylene group selected from C 2 H 4 , C 3 H 6 , C 4 H 8 , and C 5 H 10.
  • P is 0 to 50
  • q is 0 to 50 (provided that p and q are not 0 at the same time)
  • R 6 represents H or CH 3 .
  • a commercially available product can be used as the (meth) acrylic acid ester having an alkylene oxide group.
  • Examples of commercially available products include the Bremer (registered trademark) series manufactured by NOF Corporation. Further, in the Blemmer (registered trademark) series, Blemmer (registered trademark) 50 PEP-300 (R 3 is CH 3 , R 4 is C 2 H 5 , R 5 is C 3 H 6 , p and q are p on average.
  • Blemmer® PP-1000 R 3 is CH 3 , R 4 Is C 2 H 5 , R 5 is C 3 H 6 , p is 0, q is a mixture of 4 to 6 on average, R 6 is H)
  • Blemmer® PME-400 R 3 is CH is 3, R 4 is C 2 H 5, R 5 is C 3 H 6, a mixture of p is on average 9, q is 0, R 6 CH 3 a is), and the like are suitable.
  • the amount of the (meth) acrylic acid ester having an alkylene oxide group is preferably 40% by weight or less, more preferably 1 to 15% by weight, more preferably 2% by weight based on the total amount of the vinyl monomer. More preferred is ⁇ 10% by weight, and especially preferred is 3 to 7% by weight.
  • the polymerization stability may be lowered and the number of coalesced particles may be increased.
  • the vinyl monomer preferably includes a urethane acrylate oligomer as a polyfunctional vinyl monomer together with a monofunctional vinyl monomer such as a (meth) acrylate monomer.
  • a monofunctional vinyl monomer such as a (meth) acrylate monomer.
  • the urethane acrylate oligomer preferably exhibits a glass transition temperature (Tg) (measured from viscoelasticity) of 0 to 30 ° C. when cured alone. When Tg is less than 0 ° C., the core particles may become sticky. When Tg is 30 ° C. or lower, conductive resin particles having high recoverability can be obtained.
  • Tg shown when the urethane acrylate oligomer is cured alone is more preferably 0 to 28 ° C., and further preferably 0 to 25 ° C.
  • the urethane acrylate oligomer preferably exhibits a pencil hardness of H to HB when cured alone.
  • conductive resin particles having a higher restoration rate can be obtained.
  • Examples of commercially available urethane acrylate oligomers include “New Frontier (registered trademark) RST-402” and “New Frontier (registered trademark) RST-” of New Frontier (registered trademark) RST series manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
  • New Frontier (registered trademark) series urethane acrylate oligomer such as “201”, and UF series “UF-A01P” manufactured by Kyoeisha Chemical Co., Ltd.
  • the core particle of the present invention is made of a polymer of a vinyl monomer, it can be obtained by polymerizing the vinyl monomer.
  • the polymerization method known methods for obtaining resin particles such as emulsion polymerization, dispersion polymerization, suspension polymerization, seed polymerization and the like can be used.
  • the suspension polymerization is a method of polymerizing a vinyl monomer in an aqueous medium.
  • the aqueous medium include water and a mixture of water and a water-soluble organic solvent (for example, a lower alcohol having 5 or less carbon atoms).
  • the above suspension polymerization may be performed in the presence of a polymerization initiator, if necessary.
  • the polymerization initiator include oil-soluble properties such as benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxydicarbonate, cumene hydroperoxide, and t-butyl hydroperoxide.
  • peroxides include oil-soluble azo compounds such as 2,2′-azobisisobutyronitrile and 2,2′-azobis (2,4-dimethylvaleronitrile). These polymerization initiators can be used alone or in combination of two or more. The amount of the polymerization initiator used is about 0.1 to 1 part by weight with respect to 100 parts by weight of the vinyl monomer.
  • the suspension polymerization may be performed in the presence of a dispersant and / or a surfactant as necessary.
  • a dispersant include poorly water-soluble inorganic salts such as calcium phosphate and magnesium pyrophosphate; water-soluble polymers such as polyvinyl alcohol, methyl cellulose, and polyvinyl pyrrolidone.
  • surfactant examples include anionic surfactants such as sodium oleate, sodium lauryl sulfate, sodium dodecylbenzene sulfonate, alkyl naphthalene sulfonate, and alkyl phosphate ester salt; polyoxyethylene alkyl ether, polyoxy Nonionic surfactants such as ethylene alkylphenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxysorbitan fatty acid ester, polyoxyethylene alkylamine, glycerin fatty acid ester; amphoteric surfactants such as lauryl dimethylamine oxide, etc. Can be mentioned.
  • anionic surfactants such as sodium oleate, sodium lauryl sulfate, sodium dodecylbenzene sulfonate, alkyl naphthalene sulfonate, and alkyl phosphate ester salt
  • polyoxyethylene alkyl ether polyoxy Noni
  • the above dispersants and surfactants can be used alone or in combination of two or more.
  • a poorly water-soluble phosphate dispersant such as calcium phosphate and magnesium pyrophosphate
  • an anionic surfactant such as alkyl sulfate and alkyl benzene sulfonate.
  • the amount of the dispersant used is preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the vinyl monomer, and the amount of the surfactant used is 0 with respect to 100 parts by weight of the aqueous medium. It is preferably 0.01 to 0.2 parts by weight.
  • an oil phase containing the vinyl monomer is prepared, and the aqueous phase in which the oil phase is dispersed is heated while the prepared oil phase is dispersed in an aqueous phase containing an aqueous medium.
  • a polymerization initiator is mixed with the said vinylic monomer, and an oil phase is prepared.
  • a dispersing agent and / or surfactant a dispersing agent and / or surfactant are mixed with an aqueous medium, and an aqueous phase is prepared.
  • the volume average particle diameter of the core particles can be appropriately controlled by adjusting the mixing ratio of the oil phase and the aqueous phase, the amount of dispersant, the amount of surfactant used, the stirring conditions, and the dispersion conditions.
  • Examples of the method for dispersing the oil phase in the aqueous phase include a method in which the oil phase is directly added to the aqueous phase and the oil phase is dispersed as droplets in the aqueous phase by stirring force of a propeller blade or the like; A method in which an oil phase is directly added to a phase and the oil phase is dispersed in an aqueous phase using a homomixer that is a disperser using a high shear force composed of a rotor and a stator; There are various methods such as a method of directly adding and dispersing the oil phase in the aqueous phase using an ultrasonic disperser or the like.
  • the oil phase is directly added to the aqueous phase, and using a high-pressure disperser such as a microfluidizer or nanomizer (registered trademark), the droplets of the mixture collide with each other or the mixture collides with the machine wall.
  • a high-pressure disperser such as a microfluidizer or nanomizer (registered trademark)
  • the oil phase is dispersed as a droplet in the aqueous phase using an MPG; the oil phase is pressed into the aqueous phase through an MPG (microporous glass) porous film, etc. This is preferable because the diameters can be more uniform.
  • the polymerization temperature is preferably about 40 to 90 ° C.
  • the time for maintaining this polymerization temperature is preferably about 0.1 to 10 hours.
  • the polymerization reaction may be performed in an inert gas atmosphere that is inert to the reactant (oil phase) in the polymerization reaction system, such as a nitrogen atmosphere. If the boiling point of the vinyl monomer is near or below the polymerization temperature, use a pressure-resistant polymerization facility such as an autoclave so that the vinyl monomer does not volatilize. It is preferable to perform suspension polymerization in
  • the desired core particles can be obtained by decomposing and removing the dispersant with an acid or the like, and performing filtration, water washing, dehydration, drying, pulverization, classification, and the like.
  • seed particles are added to an aqueous emulsion composed of a vinyl monomer and an aqueous medium.
  • the aqueous medium include water and a mixed medium of water and a water-soluble solvent (for example, a lower alcohol having 5 or less carbon atoms).
  • the aqueous medium preferably contains a surfactant.
  • a surfactant any of an anionic surfactant, a cationic surfactant, a nonionic surfactant, and a zwitterionic surfactant can be used.
  • anionic surfactant examples include fatty acid soaps such as sodium oleate and castor oil potash soap, alkyl sulfate salts such as sodium lauryl sulfate and ammonium lauryl sulfate, alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate, alkyl Naphthalene sulfonate, alkane sulfonate, dialkylsulfosuccinate such as sodium di (2-ethylhexyl) sulfosuccinate, alkenyl succinate (dipotassium salt), alkyl phosphate ester salt, naphthalene sulfonate formalin condensate, poly Oxyethylene alkyl phenyl ether sulfate, polyoxyethylene alkyl ether sulfate such as sodium polyoxyethylene lauryl ether sulfate, polyoxyethylene alkyl sulfate Ether
  • cationic surfactant examples include alkylamine salts such as laurylamine acetate and stearylamine acetate, and quaternary ammonium salts such as lauryltrimethylammonium chloride.
  • zwitterionic surfactant examples include lauryl dimethylamine oxide and phosphate ester or phosphite ester surfactants. You may use the said surfactant individually or in combination of 2 or more types. Of the above surfactants, anionic surfactants are preferred from the viewpoint of dispersion stability during polymerization.
  • the aqueous emulsion can be prepared by a known method.
  • an aqueous emulsion can be obtained by adding a vinyl monomer to an aqueous medium and dispersing it with a fine emulsifier such as a homogenizer, an ultrasonic processor, or a nanomizer.
  • the vinyl monomer may contain a polymerization initiator as necessary.
  • the polymerization initiator may be premixed with the vinyl monomer and then dispersed in an aqueous medium, or a mixture of both separately dispersed in an aqueous medium.
  • the particle diameter of the vinyl monomer droplets in the obtained aqueous emulsion is preferably smaller than the seed particles because the vinyl monomers are efficiently absorbed by the seed particles.
  • the seed particles may be added directly to the aqueous emulsion, or may be added in a form in which the seed particles are dispersed in an aqueous dispersion medium.
  • the vinyl monomers are absorbed into the seed particles. This absorption can usually be carried out by stirring the aqueous emulsion after addition of seed particles at room temperature (about 20 ° C.) for 1 to 12 hours. Further, absorption may be promoted by heating the aqueous emulsion to about 30 to 50 ° C.
  • the seed particles swell by absorbing the vinyl monomer.
  • the mixing ratio of the vinyl monomer to the seed particles is preferably in the range of 5 to 150 parts by weight of the vinyl monomer with respect to 1 part by weight of the seed particles, and in the range of 10 to 120 parts by weight. More preferably.
  • the mixing ratio of the vinyl monomer to the seed particles is small, the increase in particle diameter due to polymerization is small, and thus productivity may be lowered.
  • the mixing ratio of the vinyl monomer to the seed particles increases, the vinyl monomer may not be completely absorbed by the seed particles, and may be suspended and polymerized uniquely in an aqueous medium to generate abnormal particles. The end of absorption can be determined by confirming the enlargement of the particle diameter by observation with an optical microscope.
  • a polymerization initiator can be added to the aqueous emulsion as necessary.
  • the polymerization initiator include benzoyl peroxide, lauroyl peroxide, orthochlorobenzoyl peroxide, orthomethoxybenzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, t-butylperoxy-2-ethylhexano , Organic peroxides such as di-t-butyl peroxide, 2,2′-azobisisobutyronitrile, 1,1′-azobiscyclohexanecarbonitrile, 2,2′-azobis (2,4- And azo compounds such as dimethylvaleronitrile).
  • the polymerization initiator is preferably used in the range of 0.1 to 3 parts by weight with respect to 100 parts by weight of the vinyl monomer.
  • the core particles are obtained by polymerizing the vinyl monomer absorbed in the seed particles.
  • the polymerization temperature is appropriately selected according to the type of vinyl monomer and polymerization initiator.
  • the polymerization temperature is preferably in the range of 25 to 110 ° C, more preferably in the range of 50 to 100 ° C.
  • the polymerization reaction is preferably performed by raising the temperature after the monomer and the polymerization initiator are completely absorbed by the seed particles.
  • the core particles are centrifuged as necessary to remove the aqueous medium, washed with water and a solvent, and then dried and isolated.
  • a polymer dispersion stabilizer may be added in order to improve the dispersion stability of the core particles.
  • the polymer dispersion stabilizer for example, polyvinyl alcohol, polycarboxylic acid, celluloses (hydroxyethyl cellulose, carboxymethyl cellulose, etc.), polyvinyl pyrrolidone and the like can be used.
  • these polymer dispersion stabilizers and inorganic water-soluble polymer compounds such as sodium tripolyphosphate can be used in combination.
  • polyvinyl alcohol and polyvinyl pyrrolidone are preferable as the polymer dispersion stabilizer.
  • the addition amount of the polymer dispersion stabilizer is preferably 1 to 10 parts by weight with respect to 100 parts by weight of the vinyl monomer.
  • water-soluble polymerization inhibitors such as nitrites, sulfites, hydroquinones, ascorbic acids, water-soluble vitamin Bs, citric acid, and polyphenols may be used. Good.
  • the shell is made of a conductive polymer.
  • the conductive polymer may be a polyaniline polymer, a polyisothianaphthene polymer, or the like, but it is easy to form a more uniform shell, and conductive resin particles having desired conductivity can be obtained. Therefore, the polymer is preferably a polymer of at least one monomer selected from the group consisting of a nitrogen-containing heteroaromatic compound and a sulfur-containing heteroaromatic compound.
  • nitrogen-containing heteroaromatic compound examples include pyrrole, indole, imidazole, pyridine, pyrimidine, pyrazine, and alkyl-substituted products thereof (for example, alkyl having 1 to 4 carbon atoms such as methyl group, ethyl group, propyl group, butyl).
  • alkyl-substituted products thereof for example, alkyl having 1 to 4 carbon atoms such as methyl group, ethyl group, propyl group, butyl.
  • a substituted group), a halogen-substituted product for example, a substituted group by a halogen group such as a fluoro group, a chloro group, and a bromo group
  • a derivative such as a nitrile-substituted product.
  • a polymer of pyrrole and a derivative of pyrrole is preferable as the nitrogen-containing heteroaromatic compound because a more uniform shell is easily formed and conductive resin particles having desired conductivity can be obtained.
  • pyrrole derivatives include 3,4-dimethylpyrrole.
  • thiophene and thiophene derivatives are preferable as the nitrogen-containing aromatic compound because conductive resin particles having desired conductivity can be obtained.
  • thiophene derivatives include 3,4-ethylenedioxythiophene, 3-methylthiophene, and 3-octylthiophene. These monomers can be used alone to form a homopolymer, or two or more types can be used in combination to form a copolymer.
  • the thickness of the shell is preferably in the range of 30 to 300 nm, and more preferably in the range of 50 to 200 nm. If the thickness of the shell is within the above range, sufficient conductivity can be obtained.
  • the thickness fluctuation of the shell is preferably 50% or less, and more preferably 40% or less.
  • the conductive polymer constituting the shell is at least one monomer selected from the group consisting of a nitrogen-containing heteroaromatic compound and a sulfur-containing heteroaromatic compound (hereinafter, simply “single”).
  • a polymer called “mer” it can be produced by a method in which the core particle is coated with the monomer polymer.
  • the core particles are coated with the monomer polymer by dispersing the core particles in an aqueous medium containing an oxidizing agent to form a dispersion (emulsion or suspension).
  • a method is preferred in which a monomer is added and stirred, and the surface of the core particles is coated with the monomer polymer by oxidative polymerization.
  • the amount of the monomer added may be set according to the desired conductivity, and is preferably in the range of 1 to 30 parts by weight, preferably 3 to 20 parts by weight, with respect to 100 parts by weight of the core particles. Is more preferable.
  • the addition amount of the monomer is 1 part by weight or more with respect to 100 parts by weight of the core particle, and the entire surface of the core particle is uniformly coated with the polymer of the monomer to obtain desired conductivity. Is possible.
  • the addition amount of the monomer 30 parts by weight or less with respect to 100 parts by weight of the core particles the added monomer is polymerized alone, and other than the intended conductive resin particles can be obtained. Can be prevented.
  • the oxidizing agent includes inorganic acids such as hydrochloric acid, sulfuric acid and chlorosulfonic acid, organic acids such as alkylbenzenesulfonic acid and alkylnaphthalenesulfonic acid, metal halogens such as ferric chloride and aluminum chloride. And halogen acids such as potassium perchlorate, potassium persulfate, ammonium persulfate, sodium persulfate, peroxides such as hydrogen peroxide, and the like. These may be used alone or in combination.
  • an alkali metal salt of an inorganic peracid is preferable. Specific examples of the alkali metal salt of inorganic peracid include potassium persulfate and sodium persulfate.
  • the amount of the oxidizing agent used is preferably 0.5 to 2.0 molar equivalents relative to the total amount of monomers.
  • the amount of the oxidizing agent used 0.5 mole equivalent or more with respect to the total amount of the monomer, the entire surface of the core particle is uniformly coated with the shell containing the monomer polymer, and the desired conductivity is obtained. Can be obtained.
  • the use amount of the oxidizing agent 2.0 mol equivalent or less with respect to the total amount of the monomer the added monomer is polymerized alone, and other than the intended conductive resin particles can be obtained. Can be prevented.
  • the aqueous medium to which the oxidizing agent is added is not particularly limited as long as it can dissolve or disperse the monomer, but water or water and methanol, ethanol, n-propanol, isopropanol, n- Examples include alcohols such as butanol and t-butanol; ethers such as diethyl ether, isopropyl ether, butyl ether, methyl cellosolve, and tetrahydrofuran; and mixed media with ketones such as acetone, methyl ethyl ketone, and diethyl ketone.
  • the aqueous medium to which the oxidizing agent is added preferably has a pH of 3 or more. If the pH is 3 or more, the entire surface of the core particle is uniformly covered with a shell containing a monomer polymer, and desired conductivity can be obtained. For stable coating, it is more preferable to adjust the pH to a range of 3 to 10.
  • Surfactant A surfactant may be added to the aqueous medium.
  • the surfactant any of an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant can be used.
  • anionic surfactant examples include fatty acid soaps such as sodium oleate and castor oil potash soap, alkyl sulfate salts such as sodium lauryl sulfate and ammonium lauryl sulfate, alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate, alkyl Sulfonates, alkyl naphthalene sulfonates, alkane sulfonates, dialkyl sulfosuccinates, alkyl phosphate esters, naphthalene sulfonate formalin condensates, polyoxyethylene alkylphenyl ether sulfates, polyoxyethylene alkyl sulfates Etc.
  • fatty acid soaps such as sodium oleate and castor oil potash soap
  • alkyl sulfate salts such as sodium lauryl sulfate and ammonium lauryl sulfate
  • nonionic surfactant examples include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxysorbitan fatty acid ester, polyoxyethylene alkylamine, glycerin fatty acid ester, Examples thereof include oxyethylene-oxypropylene block polymers.
  • cationic surfactant examples include alkylamine salts such as laurylamine acetate and stearylamine acetate, and quaternary ammonium salts such as lauryltrimethylammonium chloride.
  • the zwitterionic surfactant examples include lauryl dimethylamine oxide, phosphate ester-based or phosphite-based surfactant. You may use the said surfactant individually or in combination of 2 or more types.
  • the addition amount of the surfactant is preferably in the range of 0.0001 to 1 part by weight with respect to 100 parts by weight of the aqueous medium.
  • a polymer dispersion stabilizer may be added to the aqueous medium.
  • the polymer dispersion stabilizer include polyacrylic acid, copolymers thereof and neutralized products thereof, and polymethacrylic acid, copolymers thereof and neutralized products thereof, polyvinylpyrrolidone, hydroxypropylcellulose (HPC) and the like. Is mentioned.
  • the polymer dispersion stabilizer may be used in combination with the above-described surfactant.
  • the core particles are dispersed in an aqueous medium containing an oxidizing agent to form a dispersion, and a monomer is added to the dispersion.
  • a monomer is added to the dispersion.
  • conductive resin particles in which the core particles are coated with the polymer of the monomer are obtained.
  • the temperature of oxidative polymerization is preferably in the range of ⁇ 20 to 40 ° C., and the time of oxidative polymerization is preferably in the range of 0.5 to 10 hours.
  • the emulsion in which the conductive resin particles are dispersed is centrifuged as necessary to remove the aqueous medium, washed with water and a solvent, and then dried and isolated.
  • the method for coating the core particle with the polymer the method of oxidative polymerization of the monomer by mixing the monomer in an aqueous medium containing the core particle and the oxidizing agent has been described.
  • the method for coating the polymer is not limited to this method.
  • a method of coating the core particles with a polymer using a dry method may be employed.
  • the dry method include a method using a ball mill, a method using a V-type mixer, a method using a high-speed fluidized dryer, a method using a hybridizer, and a mechano-fusion method.
  • the conductive resin particles of the present invention can be suitably used in applications intended to develop conductivity by bringing conductive resin particles into close contact with each other.
  • the conductive resin particle of the present invention is a conductive paste for electrical connection in an electronic circuit board or the like (in which conductive particles are dispersed in a binder resin).
  • Conductive ink that can form a conductive film for electrical connection (contained with conductive particles dispersed in a solution in which binder resin is dissolved in a solvent), conductivity of conductive rollers used for transfer rollers, etc. It can be used as conductive particles used for elastic layers (those in which conductive particles are dispersed in an elastic body), antiblocking agents, and the like.
  • the conductive resin composition of the present invention contains the conductive resin particles of the present invention and a matrix resin.
  • the conductive resin composition of the present invention can be produced by mixing the conductive resin particles of the present invention with a matrix resin.
  • the matrix resin examples include polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polyamide 6, polyamide 66, polyamide 12, ABS resin (acrylonitrile-butadiene-styrene copolymer resin), AS resin (acrylonitrile-styrene copolymer resin), polyethylene, Polypropylene, polyacetal, polyamide imide, polyether sulfone, polyimide, polyphenylene oxide, polyphenylene sulfide, polystyrene, thermoplastic polyurethane elastomer, thermoplastic polyester elastomer, thermoplastic polyamide elastomer, polyvinyl chloride, polyvinylidene fluoride, ethylene tetrafluoroethylene Polymer (ETFE resin), tetrafluoroethylene perfluoroa Kill vinyl ether copolymer (PFA resin), one or more of a mixture of a thermoplastic resin such as polyether ketone may be used.
  • the conductive resin particles are preferably added in an amount of 1 to 200 parts by weight with respect to 100 parts by weight of the matrix resin.
  • Suitable functional fillers may be appropriately added to the conductive resin composition depending on the function required for the target molded product.
  • the functional filler include reinforcing fibers such as glass fibers and carbon fibers, flame retardants, matting agents, heat stabilizers, light stabilizers, colorants, and lubricants.
  • the conductive resin composition of the present invention is formed into a molded product by mixing (kneading) the matrix resin, conductive resin particles, and other functional fillers as appropriate, and molding the mixture into a required shape by hot pressing. be able to.
  • the matrix resin, conductive resin particles, and other functional fillers contained as appropriate are mixed (kneaded) appropriately in a heated state and formed into pellets. It can be used as a molded product by extrusion molding or injection molding. By these, the molded article excellent in electroconductivity and antistatic property can be obtained.
  • the coating agent of the present invention contains the conductive resin particles of the present invention and a binder resin.
  • the binder resin is not particularly limited as long as it is used in the field according to required properties such as transparency, dispersibility of conductive resin particles, light resistance, moisture resistance, and heat resistance. It is not something.
  • the binder resin include (meth) acrylic resins; (meth) acrylic-urethane resins; urethane resins; polyvinyl chloride resins; polyvinylidene chloride resins; melamine resins; styrene resins; Resins; phenolic resins; epoxy resins; polyester resins; silicone resins such as alkylpolysiloxane resins; (meth) acrylic-silicone resins, silicone-alkyd resins, silicone-urethane resins, silicone-polyester resins Modified silicone resins such as fluorinated resins such as polyvinylidene fluoride and fluoroolefin vinyl ether polymers.
  • the binder resin is preferably a curable resin capable of forming a crosslinked structure by a crosslinking reaction from the viewpoint of improving the durability of the coating agent.
  • the curable resin can be cured under various curing conditions.
  • the curable resin is classified into an ionizing radiation curable resin such as an ultraviolet curable resin and an electron beam curable resin, a thermosetting resin, a hot air curable resin, and the like depending on the type of curing.
  • thermosetting resin examples include thermosetting urethane resin composed of acrylic polyol and isocyanate prepolymer, phenol resin, urea melamine resin, epoxy resin, unsaturated polyester resin, and silicone resin.
  • the ionizing radiation curable resin synthesized from polyfunctional (meth) acrylate resin such as polyhydric alcohol polyfunctional (meth) acrylate; diisocyanate, polyhydric alcohol, and (meth) acrylic acid ester having a hydroxy group And polyfunctional urethane acrylate resins.
  • the ionizing radiation curable resin is preferably a polyfunctional (meth) acrylate resin, and more preferably a polyhydric alcohol polyfunctional (meth) acrylate having three or more (meth) acryloyl groups in one molecule.
  • polyhydric alcohol polyfunctional (meth) acrylate having 3 or more (meth) acryloyl groups in one molecule specifically, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, 1,2,4-cyclohexanetetra (meth) acrylate, pentaglycerol triacrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetra (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol triacrylate, tripentaerythritol hexaacrylate, etc. That. Two or more kinds of the ionizing radiation curable resins may be used
  • polyether resins having an acrylate functional group polyester resins, epoxy resins, alkyd resins, spiroacetal resins, polybutadiene resins, polythiol polyene resins, and the like can also be used.
  • a photopolymerization initiator is added to the ultraviolet curable resin to obtain a binder resin.
  • a photoinitiator it is preferable to use what was suitable for the ultraviolet curable resin to be used.
  • Examples of the photopolymerization initiator include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, ⁇ -hydroxyalkylphenones, ⁇ -aminoalkylphenones, anthraquinones, thioxanthones, azo compounds, peroxides (Described in JP-A No. 2001-139663), 2,3-dialkyldione compounds, disulfide compounds, fluoroamine compounds, aromatic sulfoniums, onium salts, borate salts, active halogen compounds, ⁇ -acyloximes
  • Examples include esters.
  • acetophenones examples include acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, 1-hydroxydimethylphenyl ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-4-methylthio-2-morpholinopropio.
  • examples include phenone and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone.
  • benzoins examples include benzoin, benzoin benzoate, benzoin benzene sulfonate, benzoin toluene sulfonate, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.
  • benzophenones examples include benzophenone, 2,4-dichlorobenzophenone, 4,4-dichlorobenzophenone, p-chlorobenzophenone, and the like.
  • phosphine oxides examples include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
  • Examples of the ketals include benzylmethyl ketals such as 2,2-dimethoxy-1,2-diphenylethane-1-one.
  • Examples of the ⁇ -hydroxyalkylphenones include 1-hydroxycyclohexyl phenyl ketone.
  • Examples of the ⁇ -aminoalkylphenones include 2-methyl-1- [4- (methylthio) phenyl] -2- (4-morpholinyl) -1-propanone.
  • radical photopolymerization initiators include trade names “Irgacure (registered trademark) 651” (2,2-dimethoxy-1,2-diphenylethane-1-one) manufactured by BASF Japan Ltd., manufactured by BASF Japan Ltd. Trade name “Irgacure (registered trademark) 184”, and trade name “Irgacure (registered trademark) 907” (2-methyl-1- [4- (methylthio) phenyl] -2- (4-morpholinyl) manufactured by BASF Japan Ltd. ) -1-propanone) and the like.
  • the amount of the photopolymerization initiator used is usually in the range of 0.5 to 20% by weight, preferably in the range of 1 to 5% by weight with respect to 100% by weight of the binder resin.
  • thermoplastic resin As the binder resin, a thermoplastic resin can be used in addition to the curable resin.
  • the thermoplastic resin include cellulose derivatives such as acetylcellulose, nitrocellulose, acetylbutylcellulose, ethylcellulose, and methylcellulose; homopolymers and copolymers of vinyl acetate, homopolymers and copolymers of vinyl chloride, and vinylidene chloride.
  • Vinyl resins such as homopolymers and copolymers; acetal resins such as polyvinyl formal and polyvinyl butyral; homopolymers and copolymers of acrylate esters, homopolymers and copolymers of methacrylate esters, etc.
  • Acrylic resin polystyrene resin; polyamide resin; linear polyester resin; polycarbonate resin.
  • the coating agent may further contain water and / or an organic solvent.
  • the organic solvent is not particularly limited as long as it can be easily applied to the base film by including it in the coating agent. It is not something.
  • the organic solvent include aromatic solvents such as toluene and xylene; alcohol solvents such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, and propylene glycol monomethyl ether; Ester solvents such as ethyl acetate and butyl acetate; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone and cyclohexanone; 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, ethylene glycol dimethyl ether, ethylene Glycol ethers such as glycol diethyl ether, diethylene glycol diethyl ether,
  • the film of the present invention contains the conductive resin particles of the present invention.
  • the film of the present invention has, for example, a configuration in which a coating agent containing conductive resin particles and a binder resin is applied onto a base film.
  • the film having this configuration can be suitably used as a conductive film or an antistatic film.
  • the base film is preferably transparent.
  • the transparent base film include polyester polymers such as polyethylene terephthalate (hereinafter abbreviated as “PET”) and polyethylene naphthalate, cellulose polymers such as diacetyl cellulose and triacetyl cellulose (TAC), and polycarbonate polymers.
  • PET polyethylene terephthalate
  • TAC triacetyl cellulose
  • polycarbonate polymers such as polycarbonate
  • a film made of a polymer such as a polymer or an amide polymer such as nylon or aromatic polyamide is also included.
  • imide polymer sulfone polymer, polyether sulfone polymer, polyether ether ketone polymer, polyphenyl sulfide polymer, vinyl alcohol polymer, vinylidene chloride polymer, vinyl butyral
  • films made of polymers such as polymers, arylate polymers, polyoxymethylene polymers, epoxy polymers and blends of the above polymers.
  • the substrate film a film having a particularly low birefringence is preferably used.
  • the film which further provided the easily bonding layer in the film which consists of these polymers can also be used as the said base film.
  • the easy-adhesion layer can be formed of a resin such as a (meth) acrylic resin, a copolymerized polyester resin, a polyurethane resin, a styrene-maleic acid graft polyester resin, or an acrylic graft polyester resin.
  • a resin such as a (meth) acrylic resin, a copolymerized polyester resin, a polyurethane resin, a styrene-maleic acid graft polyester resin, or an acrylic graft polyester resin.
  • (meth) acryl means acryl or methacryl.
  • the thickness of the base film can be determined as appropriate, but is generally within the range of 10 to 500 ⁇ m and within the range of 20 to 300 ⁇ m from the viewpoints of workability such as strength and handling, and thin layer properties. Preferably, it is more preferably in the range of 30 to 200 ⁇ m.
  • an additive may be added to the base film.
  • the additive include an ultraviolet absorber, an infrared absorber, an antistatic agent, a refractive index adjuster, and an enhancer.
  • the coating agent can be applied to the base film by bar coating, blade coating, spin coating, reverse coating, die coating, spray coating, roll coating, gravure coating, micro gravure coating, lip coating, air knife coating. And known coating methods such as a dipping method.
  • the binder resin contained in the coating agent is an ionizing radiation curable resin
  • the solvent is dried and further irradiated with active energy rays to cure the ionizing radiation curable resin. You can do it.
  • Examples of the active energy ray include ultraviolet rays emitted from a light source such as a xenon lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, a carbon arc lamp, and a tungsten lamp; Electron beams, ⁇ rays, ⁇ rays, ⁇ rays and the like extracted from electron beam accelerators such as a type, a resonant transformation type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type can be used.
  • a light source such as a xenon lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, a carbon arc lamp, and a tungsten lamp
  • Electron beams, ⁇ rays, ⁇ rays, ⁇ rays and the like extracted from electron beam accelerators such as a type
  • the thickness of the layer in which conductive resin particles are dispersed in the binder resin (antiglare layer) formed by coating (and curing) of the coating agent is not particularly limited, and depends on the particle diameter of the conductive resin particles. Although it is determined appropriately, it is preferably in the range of 1 to 10 ⁇ m, more preferably in the range of 3 to 7 ⁇ m.
  • the film of the present invention is not limited to the above-described configuration, and a film-shaped resin composition similar to a coating agent containing conductive resin particles and a binder resin may be formed. Good.
  • the film having this configuration can be suitably used as a conductive film or an antistatic film.
  • the gap material of the present invention includes the conductive resin particles of the present invention.
  • the gap material of the present invention provides a uniform gap between various substrates such as in-plane spacers for liquid crystal display elements, seal spacers for liquid crystal display elements, spacers for EL (electroluminescence) display elements, spacers for touch panels, ceramics and plastics. It is used as a gap distance holding spacer such as a gap holding material that can be held. Since the gap material of the present invention includes the conductive resin particles of the present invention having a good electrical conductivity, the gap material has electrical conductivity and exhibits an antistatic function.
  • the coefficient of variation of the volume-based particle diameter of the conductive resin particles is preferably 20% or less, more preferably less than 10%. preferable.
  • the present invention is not limited to this.
  • the volume average particle diameter of the conductive resin particles, the coefficient of variation of the volume-based particle diameter, the 10% compressive strength, and the method of measuring the conductivity in the following Examples and Comparative Examples will be described.
  • volume average particle diameter of the conductive resin particles and the coefficient of variation (CV value) of the volume-based particle diameter were measured by the Coulter method as follows.
  • the volume average particle diameter of the conductive resin particles is measured with a Coulter Multisizer TM 3 (measurement device manufactured by Beckman Coulter, Inc.). The measurement shall be performed using an aperture calibrated according to the Multisizer TM 3 User's Manual issued by Beckman Coulter, Inc.
  • the aperture used for the measurement is appropriately selected depending on the size of the conductive resin particle to be measured.
  • Current (aperture current) and Gain (gain) are appropriately set according to the size of the selected aperture. For example, when an aperture having a size of 50 ⁇ m is selected, the current (aperture current) is set to ⁇ 800 and the gain (gain) is set to 4.
  • conductive resin particles in 10 ml of a 0.1% by weight nonionic surfactant aqueous solution was touch mixer (manufactured by Yamato Kagaku Co., Ltd., “TOUCHMIXER MT-31”) and an ultrasonic cleaner ( Dispersed using “ULTRASONIC CLEANER VS-150” manufactured by VervoCrea Co., Ltd., and used as a dispersion.
  • touch mixer manufactured by Yamato Kagaku Co., Ltd., “TOUCHMIXER MT-31”
  • an ultrasonic cleaner Dispersed using “ULTRASONIC CLEANER VS-150” manufactured by VervoCrea Co., Ltd., and used as a dispersion.
  • the beaker is gently stirred to the extent that bubbles do not enter, and the measurement is terminated when 100,000 conductive resin particles are measured.
  • the volume average particle diameter of the conductive resin particles is an arithmetic average in a volume-based particle size distribution of 100,000 particles.
  • the 10% compressive strength (S10 strength) of the resin particles was measured under the following measurement conditions using a micro compression tester “MCTM-200” manufactured by Shimadzu Corporation.
  • a dispersion liquid in which resin particles are dispersed in ethanol was applied to a mirror-finished steel sample table and dried to prepare a measurement sample.
  • single independent fine resin particles at least 100 ⁇ m in diameter and no other resin particles exist
  • the diameter of the resin particles was measured with a particle size measurement cursor of MCTM-200.
  • the resin particles selected within the range of ⁇ 0.5 ⁇ m from the volume average particle diameter confirmed by the measurement method by the Coulter method described above were selected. Resin particles outside that range are not used for the measurement of compressive strength.
  • the compressive strength was determined by the following formula. Six measurements were performed on each resin particle, and the average value of the four data excluding the maximum value and minimum value data was defined as 10% compressive strength (S10 strength).
  • the conductive resin particles filled in the probe are loaded in increments of 4kN from 0 to 20kN with a hydraulic pump.
  • the conductivity of the conductive resin particles in a state where each load (0, 4 kN, 8 kN, 12 kN, 16 kN, and 20 kN) was applied was measured.
  • the highest numerical value among the electrical conductivity obtained by measuring with each load was defined as the electrical conductivity of the conductive resin particles.
  • the moisture content was measured in advance by Karl Fischer moisture measurement, and it was confirmed that the moisture content was 1.0% by weight or less.
  • Example 1 [Manufacture of core particles] (Preparation of aqueous phase)
  • aqueous medium 200 parts by weight of deionized water as an aqueous medium, 10 parts by weight of magnesium pyrophosphate as a dispersing agent, and 0.04 part by weight of sodium lauryl sulfate as an anionic surfactant are added, and an aqueous phase is added.
  • the target polypyrrole As a conductive polymer by adding 5 parts by weight of pyrrole as a nitrogen-containing aromatic compound to the obtained mixed liquid and polymerizing pyrrole by stirring at 25 ° C. for 5 hours.
  • Conductive resin particles core-shell particles in which the core particles were coated with the shell were obtained.
  • the obtained conductive resin particles had a volume average particle diameter of 14.8 ⁇ m, a volume-based particle diameter variation coefficient of 45%, and a 10% compressive strength of 1.4 MPa.
  • Example 2 (Manufacture of core particles] Instead of 60 parts by weight of n-butyl acrylate, 15 parts by weight of methyl acrylate, and 10 parts by weight of 2-ethylhexyl acrylate, 79 parts by weight of n-butyl acrylate is used and replaced by 10 parts by weight of ethylene glycol dimethacrylate.
  • Example 3 Manufacture of core particles
  • a desired water-containing cake of core particles was obtained.
  • Example 4 [Manufacture of core particles] [Soap-free polymerization] In a beaker, 15 parts by weight of methyl methacrylate as a monofunctional (meth) acrylic acid ester monomer was mixed with 0.2 parts by weight of n-octyl mercaptan as a molecular weight modifier to prepare an oil phase.
  • An aqueous solution obtained by dissolving 0.08 parts by weight of sodium di (2-ethylhexyl) sulfosuccinate as an anionic surfactant in 80 parts by weight of ion-exchanged water as an aqueous medium was mixed with the obtained mixture,
  • An emulsion was obtained by treating with a homomixer (Primix Co., Ltd., desktop type, product name “Homomixer MARK II 2.5 type”) at a stirring speed of 8000 rpm for 10 minutes.
  • a homomixer Principal Co., Ltd., desktop type, product name “Homomixer MARK II 2.5 type
  • the water-containing cake of core particles obtained in the previous step is used in place of the core particles of Example 1, and the amount of deionized water used to obtain a core particle dispersion by dispersing the core particles is 25 wt. Except having changed into the part, it carried out similarly to Example 1, and obtained the target conductive resin particle.
  • the obtained conductive resin particles had a volume average particle diameter of 1.3 ⁇ m, a volume-based particle diameter variation coefficient of 9%, and a 10% compressive strength of 1.4 MPa.
  • Example 5 [Manufacture of core particles] The amount of sodium lauryl sulfate used was changed to 0.005 parts by weight, and the stirring when dispersing the oil phase in the aqueous phase was changed to be performed at a stirring speed of 200 rpm for 10 minutes without using a homomixer. In the same manner as in Example 1, a desired water-containing cake of core particles was obtained.
  • the target conductive resin particles were obtained in the same manner as in Example 1, except that the hydrous cake of core particles obtained in the previous step was used instead of the core particles in Example 1.
  • the obtained conductive resin particles had a volume average particle diameter of 198 ⁇ m, a volume-based particle diameter variation coefficient of 49%, and a 10% compressive strength of 1.7 MPa.
  • Example 6 [Manufacture of core particles] Instead of 60 parts by weight of n-butyl acrylate, 15 parts by weight of methyl acrylate, and 10 parts by weight of 2-ethylhexyl acrylate, 45 parts by weight of n-butyl acrylate is used and replaced by 10 parts by weight of ethylene glycol dimethacrylate.
  • urethane acrylate oligomer product name “New Frontier (registered trademark) RST-402”, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
  • the water-containing cake of core particles obtained in the previous step is used in place of the core particles of Example 1, and the amount of deionized water used to obtain a core particle dispersion by dispersing the core particles is 25 wt. Except having changed into the part, it carried out similarly to Example 1, and obtained the target conductive resin particle.
  • the obtained conductive resin particles had a volume average particle diameter of 16.2 ⁇ m, a volume-based particle diameter variation coefficient of 44%, and a 10% compressive strength of 1.2 MPa.
  • Example 7 Manufacture of core particles
  • a desired water-containing cake of core particles was obtained.
  • the core particles obtained in the previous step were used in place of the core particles of Example 3, and the amount of deionized water used to obtain the core particle dispersion by dispersing the core particles was changed to 50 parts by weight. Except for this, the same conductive resin particles as in Example 3 were obtained.
  • the obtained conductive resin particles had a volume average particle diameter of 16.5 ⁇ m, a volume-based particle diameter variation coefficient of 42%, and a 10% compressive strength of 1.2 MPa.
  • Conductive resin particles were obtained in the same manner as in Example 1 except that 25 parts by weight of isopropyl alcohol was used in place of 50 parts by weight of deionized water as a dispersion medium used when obtaining the core particle dispersion.
  • the 10% compressive strength of the obtained conductive resin particles was 34.3 MPa.
  • Comparative Example 2 Conductive resin particles were obtained in the same manner as in Comparative Example 1, except that 3,4-ethylenedioxythiophene was used instead of pyrrole, and the stirring time during polymerization was changed to 24 hours. The 10% compressive strength of the obtained conductive resin particles was 36.4 MPa. [Conductivity measurement] The conductivity of the conductive resin particles obtained in the previous step was measured and found to be 2.2 ⁇ 10 ⁇ 3 S / cm.
  • the target conductive resin particles were obtained in the same manner as in Example 4 except that the core particles obtained in the previous step were used instead of the core particles in Example 4.
  • the obtained conductive resin particles had a volume average particle diameter of 1.2 ⁇ m, a volume-based particle diameter variation coefficient of 9%, and a 10% compressive strength of 36.1 MPa.
  • the volume average particle diameter, the coefficient of variation of the volume-based particle diameter, the 10% compressive strength, and the conductivity of the conductive resin particles obtained in Examples 1 to 7 and Comparative Examples 1 to 3 are used for the production of the core particles.
  • Table 1 summarizes the composition of the monomer mixture (composition of the monomer mixture used in seed polymerization in Example 4 and Comparative Example 3) and the type of monomer used to form the shell.
  • n-butyl acrylate is “BA”
  • methyl acrylate is “MA”
  • 2-ethylhexyl acrylate is “2EHA”
  • methyl methacrylate is “MMA”
  • Monomethacrylate “Blemmer (registered trademark) 50 PEP-300”) “50 PEP-300”
  • tetradecaethylene glycol dimethacrylate 14EG
  • urethane acrylate New Frontier (registered trademark)” “RST-402” is abbreviated as “RST-402”.
  • the conductive resin particles of Examples 1 to 7 have a 10% compressive strength of 0.1 to 30 MPa (1.2 to 2.5 MPa), so that the 10% compressive strength exceeds 30 MPa (34 Compared to the conductivity (2.2 to 3.5 ⁇ 10 ⁇ 3 S / cm) of the conductive resin particles of Comparative Examples 1 to 3 which is .3 to 36.4 MPa), the conductivity (1. 5 to 2.9 ⁇ 10 ⁇ 2 S / cm).
  • Example 8 A binder solution in which 10 parts by weight of an acrylic resin as a binder resin (trade name “Dianal (registered trademark) BR-106” manufactured by Mitsubishi Chemical Corporation) was dissolved in 50 parts by weight of toluene as an organic solvent was used. 10 parts by weight of the conductive resin particles obtained in 1 were blended and dispersed uniformly to prepare a coating agent.
  • an acrylic resin as a binder resin trade name “Dianal (registered trademark) BR-106” manufactured by Mitsubishi Chemical Corporation
  • This coating agent was applied on a PET film having a thickness of 100 ⁇ m as a base film using a 30 ⁇ m applicator to form a coating film.
  • the film which has electroconductivity was obtained by leaving still in a 70 degreeC high temperature tank for 2 hours, and drying the coating film on PET film.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Physics & Mathematics (AREA)
  • Graft Or Block Polymers (AREA)
  • Paints Or Removers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Non-Insulated Conductors (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
  • Conductive Materials (AREA)

Abstract

L'invention concerne des particules de résine conductrice ayant une bonne conductivité électrique. Chacune des particules de résine conductrice présente : une particule de cœur qui est formée d'un polymère ; et une enveloppe qui recouvre la particule de cœur et est formée d'un polymère conducteur. Les particules de résine conductrice ont une résistance à la compression à 10 % de déformation par compression de 0,1 à 30 MPa.
PCT/JP2017/024195 2016-09-30 2017-06-30 Particules de résine conductrice et utilisation desdites particules WO2018061374A1 (fr)

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JP2021005514A (ja) * 2019-06-27 2021-01-14 東洋インキＳｃホールディングス株式会社 導電性粒子、分散体及びその製造方法
FR3100250A1 (fr) * 2019-09-04 2021-03-05 Université de Pau et des Pays de l’Adour Particules nanocomposites électriquement conductrices possédant un cœur de polyacrylate d’alkyle et une écorce de polymère conducteur

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