WO2018061374A1 - Conductive resin particles and use of same - Google Patents
Conductive resin particles and use of same Download PDFInfo
- 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
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- conductive resin
- resin particles
- particles
- conductive
- weight
- Prior art date
Links
Classifications
-
- 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.
Abstract
Description
〔導電性樹脂粒子〕
本発明の導電性樹脂粒子は、重合体からなるコア粒子と、前記コア粒子を被覆する導電性高分子からなるシェルとを有する導電性樹脂粒子であって、10%圧縮変形時の圧縮強度が0.1~30MPaである。 Hereinafter, the present invention will be described in detail.
[Conductive resin particles]
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.
上記コア粒子は、ポリウレタン、シリコーン系重合体等の縮合重合体であってもよいが、ビニル系単量体の重合体からなることが好ましい。上記ビニル系単量体は、少なくとも1個のエチレン性不飽和基(広義のビニル基)を有する化合物であればよく、1個のエチレン性不飽和基を有する単官能ビニル系単量体であってもよく、2個以上のエチレン性不飽和基を有する多官能ビニル系単量体であってもよい。 [Core particles]
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.
本発明のコア粒子は、ビニル系単量体の重合体からなる場合、ビニル系単量体を重合させることにより得ることができる。重合方法としては、乳化重合、分散重合、懸濁重合、シード重合など、樹脂粒子を得るための公知の方法を用いることができる。 [Method for producing core particles]
When 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. As 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.
上記懸濁重合は、水性媒体中でビニル系単量体を重合させる方法である。上記水性媒体としては、水、及び、水と水溶性有機溶媒(例えば、炭素数5以下の低級アルコール)との混合物が挙げられる。 [Method for producing core particles by suspension polymerization]
The suspension polymerization is a method of polymerizing a vinyl monomer in an aqueous medium. Examples of 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).
シード重合法によるコア粒子の製造方法では、まず、ビニル系単量体と水性媒体とから構成される水性乳化液に種粒子を添加する。水性媒体としては、水、水と水溶性溶媒(例えば、炭素数5以下の低級アルコール)との混合媒体が挙げられる。 [Method of producing core particles by seed polymerization]
In the method for producing core particles by the seed polymerization method, first, seed particles are added to an aqueous emulsion composed of a vinyl monomer and an aqueous medium. Examples of 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).
上記シェルは、導電性高分子からなる。上記導電性高分子は、ポリアニリン系重合体やポリイソチアナフテン系重合体等であってもよいが、より均一なシェルが形成されやすいこと、および所望の導電性を有する導電性樹脂粒子が得られることから、含窒素複素芳香族化合物及び含硫黄複素芳香族化合物からなる群より選ばれる少なくとも1種の単量体の重合体であることが好ましい。 〔shell〕
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.
上記導電性樹脂粒子は、そのシェルを構成する導電性高分子が、含窒素複素芳香族化合物及び含硫黄複素芳香族化合物からなる群より選ばれる少なくとも1種の単量体(以下、単に「単量体」と称する)の重合体である場合、上記コア粒子に上記単量体の重合体を被覆する方法により製造できる。上記コア粒子に上記単量体の重合体を被覆する方法としては、酸化剤を含む水性媒体中に上記コア粒子を分散させて分散液(乳化液または懸濁液)とし、該分散液に単量体を添加し攪拌して、酸化重合により上記コア粒子の表面に上記単量体の重合体を被覆させる方法が好ましい。 [Method of forming shell]
In the conductive resin particles, 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”). In the case of 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.
上記酸化剤としては、塩酸、硫酸、クロロスルホン酸のような無機酸、アルキルベンゼンスルホン酸、アルキルナフタレンスルホン酸のような有機酸、塩化第二鉄、塩化アルミニウムのような金属ハロゲン化物、過塩素酸カリウムのようなハロゲン酸、過硫酸カリウム、過硫酸アンモニウム、過硫酸ナトリウム、過酸化水素のような過酸化物等が挙げられる。これらは単独または混合して使用してもよい。酸化剤としては、無機過酸のアルカリ金属塩が好ましい。無機過酸のアルカリ金属塩としては、具体的には、過硫酸カリウム、過硫酸ナトリウム等が挙げられる。 (1) Oxidizing agent 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. As the oxidizing agent, 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.
上記酸化剤が添加された水性媒体は、3以上のpHを有することが好ましい。pHが3以上であれば、コア粒子の表面全体が均一に単量体の重合体を含むシェルで覆われ、所望の導電性を得ることが可能となる。安定に被覆するには、pHを3~10の範囲に調整することがより好ましい。 (2) Aqueous medium 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.
上記水性媒体には、界面活性剤を添加してもよい。界面活性剤としては、アニオン性界面活性剤、カチオン性界面活性剤、両性イオン性界面活性剤、ノニオン性界面活性剤をいずれも使用できる。 (3) Surfactant A surfactant may be added to the aqueous medium. As the surfactant, any of an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant can be used.
上述した酸化重合を用いた導電性樹脂粒子の製造方法では、酸化剤を含む水性媒体中に上記コア粒子を分散させて分散液とし、該分散液に単量体を添加し、攪拌して酸化重合することにより、コア粒子が上記単量体の重合体で被覆された導電性樹脂粒子を得る。酸化重合の温度は-20~40℃の範囲であることが好ましく、酸化重合の時間は、0.5~10時間の範囲であることが好ましい。 (4) Oxidative polymerization In the above-described method for producing conductive resin particles using oxidative polymerization, 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. By conducting oxidative polymerization with stirring, 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.
本発明の導電性樹脂粒子は、導電性樹脂粒子同士を密着させて導電性を発現することを目的とした用途において好適に使用することができる。本発明の導電性樹脂粒子は、電子回路基板等における電気接続のための導電性ペースト(バインダー樹脂中に導電性粒子が分散されているもの)、塗布及び乾燥されたときに電子回路基板等における電気接続のための導電性膜を形成できる導電性インク(バインダー樹脂を溶剤に溶解させた溶液中に導電性粒子が分散されているもの)、転写ローラ等に利用される導電性ローラの導電性弾性体層(弾性体中に導電性粒子が分散されているもの)、アンチブロッキング剤等に使用される導電性粒子として使用できる。 [Use of conductive resin particles]
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.
本発明の導電性樹脂組成物は、本発明の導電性樹脂粒子とマトリックス樹脂とを含んでいる。本発明の導電性樹脂組成物は、本発明の導電性樹脂粒子をマトリックス樹脂に混合することで製造できる。 [Conductive resin composition]
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.
本発明のコーティング剤は、本発明の導電性樹脂粒子とバインダー樹脂とを含んでいる。 〔Coating agent〕
The coating agent of the present invention contains the conductive resin particles of the present invention and a binder resin.
本発明のフィルムは、本発明の導電性樹脂粒子を含んでいる。本発明のフィルムは、例えば、導電性樹脂粒子とバインダー樹脂とを含むコーティング剤を基材フィルム上に塗工してなる構成である。この構成のフィルムは、導電性フィルム又は帯電防止フィルムとして好適に使用できる。 〔the film〕
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.
本発明のギャップ材は、本発明の導電性樹脂粒子を含んでいる。本発明のギャップ材は、液晶表示素子用面内スペーサー、液晶表示素子用シール部スペーサー、EL(エレクトロルミネッセンス)表示素子用スペーサー、タッチパネル用スペーサー、セラミックやプラスチック等の各種基板間の隙間を均一に保持し得る隙間保持材等の隙間距離保持用スペーサーとして用いられる。本発明のギャップ材は、良好な導電率を有する本発明の導電性樹脂粒子を含むため、導電性を有し、帯電防止機能を発揮する。 [Gap material]
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.
導電性樹脂粒子の体積平均粒子径及び体積基準の粒子径の変動係数(CV値)の測定は、以下のようにしてコールター法により行った。 (Measuring method of coefficient of variation of volume average particle diameter and volume-based particle diameter of conductive resin particles)
The 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.
導電性樹脂粒子の体積基準の粒子径の変動係数
=(導電性樹脂粒子の体積基準の粒度分布の標準偏差
÷導電性樹脂粒子の体積平均粒子径)×100 The coefficient of variation of the volume-based particle diameter of the conductive resin particles is calculated by the following formula.
Variation coefficient of volume-based particle diameter of conductive resin particles = (standard deviation of volume-based particle size distribution of conductive resin particles / volume average particle diameter of conductive resin particles) × 100
樹脂粒子の10%圧縮強度(S10強度)は、株式会社島津製作所製の微小圧縮試験機「MCTM-200」を用いて、下記測定条件にて測定した。 (Method for measuring 10% compressive strength of conductive resin 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.
圧縮強度(MPa)=2.8×荷重(N)/{π×(粒子径(mm))2}
<圧縮強度の測定条件>
試験温度:常温(20℃)相対湿度65%
上部加圧圧子:直径50μmの平面圧子(材質:ダイヤモンド)
下部加圧板:SKS平板
試験種類:圧縮試験(MODE1)
試験荷重:9.81mN
負荷速度:0.732mN/sec
変位フルスケール;20(μm) <Calculation formula of compressive strength>
Compressive strength (MPa) = 2.8 × load (N) / {π × (particle diameter (mm)) 2 }
<Measurement conditions of compressive strength>
Test temperature: Normal temperature (20 ° C) Relative humidity 65%
Upper pressure indenter: Flat indenter with a diameter of 50 μm (material: diamond)
Lower pressure plate: SKS flat plate Test type: Compression test (MODE1)
Test load: 9.81 mN
Load speed: 0.732 mN / sec
Displacement full scale: 20 (μm)
「粉体抵抗測定システム MCP-PD51型」(株式会社三菱化学アナリテック製)にて、プローブに充填した導電性樹脂粒子に対し、油圧ポンプにて0~20kNまで4kN刻みで荷重をかけていき、それぞれの荷重(0、4kN、8kN、12kN、16kN、及び20kN)をかけた状態の導電性樹脂粒子について、導電率の測定を行った。各荷重で測定して得られた導電率のうちで最も高い数値を、その導電性樹脂粒子の導電率とした。導電性樹脂粒子については、事前に、カールフィッシャー水分測定により含有水分量を測定し、含有水分量が1.0重量%以下であることを確認した。「粉体抵抗測定システム MCP-PD51型」で使用する抵抗率計としては、低抵抗率計「ロレスタ(登録商標)-GX MCP-T700」(株式会社三菱化学アナリテック製)を用いた。 (Measurement method of conductivity of conductive resin particles)
With "Powder Resistance Measurement System MCP-PD51 Type" (Mitsubishi Chemical Analytech Co., Ltd.), 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. For 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. As a resistivity meter used in the “powder resistance measurement system MCP-PD51 type”, a low resistivity meter “Loresta (registered trademark) -GX MCP-T700” (manufactured by Mitsubishi Chemical Analytech Co., Ltd.) was used.
[コア粒子の製造]
〔水相の調製〕
ビーカーに、水性媒体としての脱イオン水200重量部と、分散剤としてのピロリン酸マグネシウム10重量部と、アニオン性界面活性剤としてのラウリル硫酸ナトリウム0.04重量部とを投入し、水相を調製した。 Example 1
[Manufacture of core particles]
(Preparation of aqueous phase)
In a beaker, 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. Prepared.
水相の調製に用いたビーカーとは別のビーカーに、単官能(メタ)アクリル酸エステル単量体としてのアクリル酸n-ブチル60重量部、アクリル酸メチル15重量部、アクリル酸2-エチルヘキシル10重量部、及びポリ(エチレングリコール-プロピレングリコール)モノメタクリレート(日油株式会社製の「ブレンマー(登録商標)50PEP-300」)5重量部と、上記一般式(I)で示される単量体としてのエチレングリコールジメタクリレート(共栄社化学株式会社製の「ライトエステルEG」)10重量部と、重合開始剤としての2,2’-アゾビス(2,4-ジメチルバレロニトリル)0.2重量部及び過酸化ベンゾイル0.15重量部を投入し、十分に攪拌して、油相となる混合物を調製した。 (Preparation of oil phase)
In a beaker other than the beaker used for the preparation of the aqueous phase, 60 parts by weight of n-butyl acrylate as a monofunctional (meth) acrylate monomer, 15 parts by weight of methyl acrylate, 2-ethylhexyl acrylate 10 Parts by weight, 5 parts by weight of poly (ethylene glycol-propylene glycol) monomethacrylate (“Blemmer (registered trademark) 50PEP-300” manufactured by NOF Corporation), and a monomer represented by the above general formula (I) 10 parts by weight of ethylene glycol dimethacrylate (“Eye ester EG” manufactured by Kyoeisha Chemical Co., Ltd.), 0.2 part by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator, and excess 0.15 part by weight of benzoyl oxide was added and sufficiently stirred to prepare a mixture that became an oil phase.
調製された油相を先に調製した水相に加え、ホモミクサー(プライミクス株式会社製、、卓上型、製品名「ホモミクサーMARKII 2.5型」)を用い、攪拌速度5000rpmで10分間攪拌して、油相を水相中に分散させ、分散液を得た。この分散液を、攪拌機、加熱装置、及び温度計を備えた重合反応器に投入し、60℃で6時間攪拌することにより、懸濁重合反応させた。次いで、重合反応器内の懸濁液(反応液)を30℃まで冷却させた後、塩酸を加えて、ピロリン酸マグネシウムを分解させた。次いで、懸濁液を吸引ろ過した。ろ過の残渣をイオン交換水により洗浄、脱水して、目的とするビニル系単量体の重合体からなるコア粒子の含水ケーキ体を得た。 (Polymerization reaction)
Add the prepared oil phase to the previously prepared aqueous phase, and use a homomixer (manufactured by PRIMIX Co., Ltd., desktop type, product name “Homomixer MARK II 2.5 type”) and stir at a stirring speed of 5000 rpm for 10 minutes. The oil phase was dispersed in the aqueous phase to obtain a dispersion. This dispersion was put into a polymerization reactor equipped with a stirrer, a heating device, and a thermometer, and stirred at 60 ° C. for 6 hours to cause a suspension polymerization reaction. Next, after the suspension (reaction solution) in the polymerization reactor was cooled to 30 ° C., hydrochloric acid was added to decompose magnesium pyrophosphate. The suspension was then filtered with suction. The filtration residue was washed with ion-exchanged water and dehydrated to obtain a water-containing cake of core particles made of a target vinyl monomer polymer.
[重合反応]
ビーカーに、得られたコア粒子の含水ケーキ体25重量部を脱イオン水50重量部に分散させ、コア粒子分散液を得た。次に、酸化剤としての過硫酸カリウム20重量部を脱イオン水300重量部に溶解させて過硫酸カリウム水溶液を調製した。上記過硫酸カリウム水溶液に、先に調製したコア粒子分散液を混合し、30分間攪拌する。得られた混合液に、含窒素芳香族化合物としてのピロール5重量部を添加し、25℃で5時間攪拌してピロールを重合させることにより、目的とする、導電性高分子としてのポリピロールからなるシェルでコア粒子が被覆された導電性樹脂粒子(コアシェル粒子)を得た。得られた導電性樹脂粒子は、体積平均粒子径が14.8μmであり、体積基準の粒子径の変動係数が45%であり、10%圧縮強度が1.4MPaであった。 [Manufacture of conductive resin particles]
[Polymerization reaction]
In a beaker, 25 parts by weight of the obtained core particle hydrous cake was dispersed in 50 parts by weight of deionized water to obtain a core particle dispersion. Next, 20 parts by weight of potassium persulfate as an oxidizing agent was dissolved in 300 parts by weight of deionized water to prepare a potassium persulfate aqueous solution. The core particle dispersion prepared above is mixed with the aqueous potassium persulfate solution and stirred for 30 minutes. It consists of 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 μm, a volume-based particle diameter variation coefficient of 45%, and a 10% compressive strength of 1.4 MPa.
先の工程で得られた導電性樹脂粒子の導電率を測定したところ、2.4×10-2S/cmであった。 [Conductivity measurement]
The conductivity of the conductive resin particles obtained in the previous step was measured and found to be 2.4 × 10 −2 S / cm.
[コア粒子の製造]
アクリル酸n-ブチル60重量部、アクリル酸メチル15重量部、及びアクリル酸2-エチルヘキシル10重量部に代えて、アクリル酸n-ブチル79重量部を使用し、エチレングリコールジメタクリレート10重量部に代えて、エチレングリコールジメタクリレート(共栄社化学株式会社製の「ライトエステルEG」)1重量部及び上記一般式(II)で示される単量体としてのテトラデカエチレングリコールジメタクリレート(共栄社化学株式会社製の「ライトエステル14EG」)15重量部を使用し、過酸化ベンゾイルの使用量を0.3重量部に変更し、油相を水相中に分散させる際の撹拌条件を「攪拌速度3500rpmで5分間」に変更したこと以外は、実施例1と同様にして目的のコア粒子の含水ケーキ体を得た。 (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. 1 part by weight of ethylene glycol dimethacrylate (“Kyoeisha Chemical Co., Ltd.“ Light Ester EG ”) and tetradecaethylene glycol dimethacrylate (manufactured by Kyoeisha Chemical Co., Ltd.) as a monomer represented by the above general formula (II) “Light Ester 14EG”) was used at 15 parts by weight, the amount of benzoyl peroxide used was changed to 0.3 parts by weight, and the stirring conditions for dispersing the oil phase in the aqueous phase were “stirring speed 3500 rpm for 5 minutes. A water-containing cake body of the target core particles was obtained in the same manner as in Example 1 except that it was changed to "".
先の工程で得られたコア粒子の含水ケーキ体を実施例1のコア粒子に代えて使用し、コア粒子分散液を得る際に使用する脱イオン水の量を25重量部に変更したこと以外は、実施例1と同様にして目的の導電性樹脂粒子を得た。得られた導電性樹脂粒子は、体積平均粒子径が15.4μmであり、体積基準の粒子径の変動係数が39%であり、10%圧縮強度が2.3MPaであった。 [Manufacture of conductive resin particles]
Except that the hydrous cake of core particles obtained in the previous step was used in place of the core particles of Example 1, and the amount of deionized water used when obtaining the core particle dispersion was changed to 25 parts by weight. Obtained the target conductive resin particles in the same manner as in Example 1. The obtained conductive resin particles had a volume average particle diameter of 15.4 μm, a coefficient of variation of the volume-based particle diameter of 39%, and a 10% compressive strength of 2.3 MPa.
先の工程で得られた導電性樹脂粒子の導電率を測定したところ、2.8×10-2S/cmであった。 [Conductivity measurement]
The conductivity of the conductive resin particles obtained in the previous step was measured and found to be 2.8 × 10 −2 S / cm.
[コア粒子の製造]
実施例1と同様にして、目的のコア粒子の含水ケーキ体を得た。 (Example 3)
[Manufacture of core particles]
In the same manner as in Example 1, a desired water-containing cake of core particles was obtained.
ピロールに代えて3,4-エチレンジオキシチオフェンを使用し、重合時の撹拌時間を24時間に変更したこと以外は、実施例1と同様にして、目的とする、導電性高分子としてのポリ(3,4-エチレンジオキシチオフェン)からなるシェルでコア粒子が被覆された導電性樹脂粒子を得た。得られた導電性樹脂粒子は、体積平均粒子径が16.2μmであり、体積基準の粒子径の変動係数が46%であり、10%圧縮強度は2.5MPaであった。 [Manufacture of conductive resin particles]
In the same manner as in Example 1, except that 3,4-ethylenedioxythiophene was used in place of pyrrole and the stirring time during polymerization was changed to 24 hours, the target polypolymer as a conductive polymer was used. Conductive resin particles having core particles coated with a shell made of (3,4-ethylenedioxythiophene) were obtained. The obtained conductive resin particles had a volume average particle diameter of 16.2 μm, a volume-based particle diameter variation coefficient of 46%, and a 10% compressive strength of 2.5 MPa.
先の工程で得られた導電性樹脂粒子の導電率を測定したところ、1.8×10-2S/cmであった。 [Conductivity measurement]
When the conductivity of the conductive resin particles obtained in the previous step was measured, it was 1.8 × 10 −2 S / cm.
[コア粒子の製造]
〔ソープフリー重合〕
ビーカー内にて、単官能(メタ)アクリル酸エステル単量体としてのメチルメタクリレート15重量部に、分子量調整剤としてのn-オクチルメルカプタン0.2重量部を混合して油相を作製した。 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.
次に、新たなビーカーに、単官能(メタ)アクリル酸エステル単量体としてのアクリル酸n-ブチル70重量部、アクリル酸メチル5重量部、アクリル酸2-エチルヘキシル5重量部、及びポリ(エチレングリコール-プロピレングリコール)モノメタクリレート(日油株式会社製の「ブレンマー(登録商標)50PEP-300」)5重量部と、上記一般式(I)で示される単量体としてのエチレングリコールジメタクリレート10重量部と、重合開始剤としての2,2’-アゾビス(2-メチルブチロニトリル)0.01重量部とを混合した。得られた混合物に、水性媒体としてのイオン交換水80重量部にアニオン性界面活性剤としてのジ(2-エチルヘキシル)スルホコハク酸ナトリウム0.08重量部を溶解させて得られた水溶液を混合し、ホモミクサー(プライミクス株式会社製、卓上型、製品名「ホモミクサーMARKII 2.5型」)により撹拌速度8000rpmで10分間処理することで、乳化液を得た。 [Seed polymerization]
Next, in a new beaker, 70 parts by weight of n-butyl acrylate as a monofunctional (meth) acrylate monomer, 5 parts by weight of methyl acrylate, 5 parts by weight of 2-ethylhexyl acrylate, and poly (ethylene 5 parts by weight of glycol-propylene glycol) monomethacrylate (“Blemmer (registered trademark) 50PEP-300” manufactured by NOF Corporation) and 10 parts by weight of ethylene glycol dimethacrylate as the monomer represented by the above general formula (I) Part and 0.01 part by weight of 2,2′-azobis (2-methylbutyronitrile) as a polymerization initiator were mixed. 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.
先の工程で得られたコア粒子の含水ケーキ体を実施例1のコア粒子に代えて使用し、コア粒子を分散させてコア粒子分散液を得る際に使用する脱イオン水の量を25重量部に変更したこと以外は、実施例1と同様にして目的の導電性樹脂粒子を得た。得られた導電性樹脂粒子は、体積平均粒子径が1.3μmであり、体積基準の粒子径の変動係数が9%であり、10%圧縮強度が1.4MPaであった。 [Manufacture of conductive resin particles]
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 μm, a volume-based particle diameter variation coefficient of 9%, and a 10% compressive strength of 1.4 MPa.
先の工程で得られた導電性樹脂粒子の導電率を測定したところ、1.5×10-2S/cmであった。 [Conductivity measurement]
When the conductivity of the conductive resin particles obtained in the previous step was measured, it was 1.5 × 10 −2 S / cm.
[コア粒子の製造]
ラウリル硫酸ナトリウムの使用量を0.005重量部に変更し、油相を水相中に分散させる際の撹拌を、ホモミクサーを用いることなく攪拌速度200rpmで10分間行うように変更したこと以外は、実施例1と同様にして目的のコア粒子の含水ケーキ体を得た。 (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.
先の工程で得られたコア粒子の含水ケーキ体を実施例1のコア粒子に代えて使用したこと以外は、実施例1と同様にして目的の導電性樹脂粒子を得た。得られた導電性樹脂粒子は、体積平均粒子径が198μmであり、体積基準の粒子径の変動係数が49%であり、10%圧縮強度が1.7MPaであった。 [Manufacture of conductive resin particles]
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 μm, a volume-based particle diameter variation coefficient of 49%, and a 10% compressive strength of 1.7 MPa.
先の工程で得られた導電性樹脂粒子の導電率を測定したところ、2.0×10-2S/cmであった。 [Conductivity measurement]
The conductivity of the conductive resin particles obtained in the previous step was measured and found to be 2.0 × 10 −2 S / cm.
[コア粒子の製造]
アクリル酸n-ブチル60重量部、アクリル酸メチル15重量部、及びアクリル酸2-エチルヘキシル10重量部に代えて、アクリル酸n-ブチル45重量部を使用し、エチレングリコールジメタクリレート10重量部に代えて、ウレタンアクリレートオリゴマー(製品名「ニューフロンティア(登録商標)RST-402」、第一工業製薬株式会社製)50重量部を使用したこと以外は、実施例1と同様にして目的のコア粒子の含水ケーキ体を得た。 (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. In the same manner as in Example 1 except that 50 parts by weight of urethane acrylate oligomer (product name “New Frontier (registered trademark) RST-402”, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was used, A water-containing cake body was obtained.
先の工程で得られたコア粒子の含水ケーキ体を実施例1のコア粒子に代えて使用し、コア粒子を分散させてコア粒子分散液を得る際に使用する脱イオン水の量を25重量部に変更したこと以外は、実施例1と同様にして目的の導電性樹脂粒子を得た。得られた導電性樹脂粒子は、体積平均粒子径が16.2μmであり、体積基準の粒子径の変動係数が44%であり、10%圧縮強度が1.2MPaであった。 [Manufacture of conductive resin particles]
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 μm, a volume-based particle diameter variation coefficient of 44%, and a 10% compressive strength of 1.2 MPa.
先の工程で得られた導電性樹脂粒子の導電率を測定したところ、2.6×10-2S/cmであった。 [Conductivity measurement]
The conductivity of the conductive resin particles obtained in the previous step was measured and found to be 2.6 × 10 −2 S / cm.
[コア粒子の製造]
実施例1と同様にして、目的のコア粒子の含水ケーキ体を得た。 (Example 7)
[Manufacture of core particles]
In the same manner as in Example 1, a desired water-containing cake of core particles was obtained.
先の工程で得られたコア粒子を実施例3のコア粒子に代えて使用し、コア粒子を分散させてコア粒子分散液を得る際に使用する脱イオン水の量を50重量部に変更したこと以外は、実施例3と同様にして目的の導電性樹脂粒子を得た。得られた導電性樹脂粒子は、体積平均粒子径が16.5μmであり、体積基準の粒子径の変動係数が42%であり、10%圧縮強度が1.2MPaであった。 [Manufacture of conductive resin particles]
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 μm, a volume-based particle diameter variation coefficient of 42%, and a 10% compressive strength of 1.2 MPa.
先の工程で得られた導電性樹脂粒子の導電率を測定したところ、2.9×10-2S/cmであった。 [Conductivity measurement]
The conductivity of the conductive resin particles obtained in the previous step was measured and found to be 2.9 × 10 −2 S / cm.
[コア粒子の製造]
単官能(メタ)アクリル酸エステル単量体として、アクリル酸n-ブチル60重量部、アクリル酸メチル15重量部、アクリル酸2-エチルヘキシル10重量部、及びポリ(エチレングリコール-プロピレングリコール)モノメタクリレート5重量部に代えて、メタクリル酸メチル95重量部を使用し、エチレングリコールジメタクリレートの使用量を5重量部に変更したこと以外は、実施例1と同様にしてコア粒子を得た。 (Comparative Example 1)
[Manufacture of core particles]
As monofunctional (meth) acrylate monomers, 60 parts by weight of n-butyl acrylate, 15 parts by weight of methyl acrylate, 10 parts by weight of 2-ethylhexyl acrylate, and poly (ethylene glycol-propylene glycol) monomethacrylate 5 Instead of parts by weight, core particles were obtained in the same manner as in Example 1 except that 95 parts by weight of methyl methacrylate was used and the amount of ethylene glycol dimethacrylate was changed to 5 parts by weight.
コア粒子分散液を得る際に使用する分散媒として脱イオン水50重量部に代えてイソプロピルアルコール25重量部を使用したこと以外は、実施例1と同様にして導電性樹脂粒子を得た。得られた導電性樹脂粒子の10%圧縮強度は34.3MPaであった。 [Manufacture of conductive resin particles]
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.
先の工程で得られた導電性樹脂粒子の導電率を測定したところ、2.2×10-3S/cmであった。 [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.
ピロールに代えて3,4-エチレンジオキシチオフェンを使用し、重合時の撹拌時間を24時間に変更したこと以外は、比較例1と同様にして導電性樹脂粒子を得た。得られた導電性樹脂粒子の10%圧縮強度は36.4MPaであった。
[導電率測定]
先の工程で得られた導電性樹脂粒子の導電率を測定したところ、2.2×10-3S/cmであった。 (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.
[コア粒子の製造]
シード重合において、アクリル酸n-ブチル70重量部、アクリル酸メチル5重量部、アクリル酸2-エチルヘキシル5重量部、及びポリ(エチレングリコール-プロピレングリコール)モノメタクリレート(日油株式会社製の「ブレンマー(登録商標)50PEP-300」)5重量部に代えて、メタクリル酸メチル70重量部を使用し、エチレングリコールジメタクリレートの使用量を30重量部に変更したこと以外は、実施例4と同様にしてコア粒子を得た。得られたコア粒子の体積平均粒子径は1.1μmであった。 (Comparative Example 3)
[Manufacture of core particles]
In the seed polymerization, 70 parts by weight of n-butyl acrylate, 5 parts by weight of methyl acrylate, 5 parts by weight of 2-ethylhexyl acrylate, and poly (ethylene glycol-propylene glycol) monomethacrylate (“Blemmer” manufactured by NOF Corporation) (Registered Trademark) 50PEP-300 ") Instead of 5 parts by weight, 70 parts by weight of methyl methacrylate was used, and the amount of ethylene glycol dimethacrylate was changed to 30 parts by weight. Core particles were obtained. The volume average particle diameter of the obtained core particles was 1.1 μm.
先の工程で得られたコア粒子を実施例4のコア粒子に代えて使用したこと以外は、実施例4と同様にして目的の導電性樹脂粒子を得た。得られた導電性樹脂粒子は、体積平均粒子径が1.2μmであり、体積基準の粒子径の変動係数が9%であり、10%圧縮強度が36.1MPaであった。 [Manufacture of conductive resin particles]
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 μm, a volume-based particle diameter variation coefficient of 9%, and a 10% compressive strength of 36.1 MPa.
先の工程で得られた導電性樹脂粒子の導電率を測定したところ、3.5×10-3S/cmであった。 [Conductivity measurement]
When the conductivity of the conductive resin particles obtained in the previous step was measured, it was 3.5 × 10 −3 S / cm.
バインダー樹脂としてのアクリル系樹脂(三菱ケミカル株式会社製、商品名「ダイヤナール(登録商標)BR-106」)10重量部を、有機溶剤としてのトルエン50重量部に溶解したバインダー溶液に、実施例1にて得られた導電性樹脂粒子を10重量部配合して、均一に分散させてコーティング剤を調製した。 (Example 8)
Examples 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.
Claims (10)
- 重合体からなるコア粒子と、
前記コア粒子を被覆する導電性高分子からなるシェルとを有する導電性樹脂粒子であって、
10%圧縮変形時の圧縮強度が0.1~30MPaであることを特徴とする導電性樹脂粒子。 Polymer core particles,
Conductive resin particles having a shell made of a conductive polymer covering the core particles,
Conductive resin particles characterized by having a compressive strength at 10% compressive deformation of 0.1 to 30 MPa. - 請求項1に記載の導電性樹脂粒子であって、
前記重合体が、単官能(メタ)アクリル酸エステル単量体と、
下記一般式(I)
The polymer is a monofunctional (meth) acrylic acid ester monomer;
The following general formula (I)
- 請求項2に記載の導電性樹脂粒子であって、
前記単量体混合物が、下記一般式(II)
The monomer mixture is represented by the following general formula (II)
- 請求項1~3のいずれか1項に記載の導電性樹脂粒子であって、
前記導電性高分子が、含窒素複素芳香族化合物及び含硫黄複素芳香族化合物からなる群より選ばれる少なくとも1種の単量体の重合体であることを特徴とする導電性樹脂粒子。 The conductive resin particle according to any one of claims 1 to 3,
Conductive resin particles, wherein the conductive polymer is a polymer of at least one monomer selected from the group consisting of a nitrogen-containing heteroaromatic compound and a sulfur-containing heteroaromatic compound. - 請求項1~4のいずれか1項に記載の導電性樹脂粒子であって、
1~200μmの体積平均粒子径を有することを特徴とする導電性樹脂粒子。 The conductive resin particle according to any one of claims 1 to 4, wherein
Conductive resin particles having a volume average particle diameter of 1 to 200 μm. - 請求項1~5のいずれか1項に記載の導電性樹脂粒子であって、
体積基準の粒子径の変動係数が10%以上であることを特徴とする導電性樹脂粒子。 The conductive resin particle according to any one of claims 1 to 5,
Conductive resin particles having a volume-based particle diameter variation coefficient of 10% or more. - 請求項1~6のいずれか1項に記載の導電性樹脂粒子と、マトリックス樹脂とを含むことを特徴とする導電性樹脂組成物。 A conductive resin composition comprising the conductive resin particles according to any one of claims 1 to 6 and a matrix resin.
- 請求項1~6のいずれか1項に記載の導電性樹脂粒子と、バインダー樹脂とを含むことを特徴とするコーティング剤。 A coating agent comprising the conductive resin particles according to any one of claims 1 to 6 and a binder resin.
- 請求項1~6のいずれか1項に記載の導電性樹脂粒子を含むことを特徴とするフィルム。 A film comprising the conductive resin particles according to any one of claims 1 to 6.
- 請求項1~6のいずれか1項に記載の導電性樹脂粒子を含むことを特徴とするギャップ材。 A gap material comprising the conductive resin particles according to any one of claims 1 to 6.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2018541923A JP6722766B2 (en) | 2016-09-30 | 2017-06-30 | Conductive resin particles and uses thereof |
CN201780060713.9A CN109791813B (en) | 2016-09-30 | 2017-06-30 | Conductive resin particles and use thereof |
KR1020197004208A KR102248989B1 (en) | 2016-09-30 | 2017-06-30 | Conductive resin particles and their uses |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2016194260 | 2016-09-30 | ||
JP2016-194260 | 2016-09-30 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2018061374A1 true WO2018061374A1 (en) | 2018-04-05 |
Family
ID=61763201
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2017/024195 WO2018061374A1 (en) | 2016-09-30 | 2017-06-30 | Conductive resin particles and use of same |
Country Status (4)
Country | Link |
---|---|
JP (1) | JP6722766B2 (en) |
KR (1) | KR102248989B1 (en) |
CN (1) | CN109791813B (en) |
WO (1) | WO2018061374A1 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2020064833A (en) * | 2018-10-19 | 2020-04-23 | 株式会社日本触媒 | Base particles for conductive particles and use thereof |
JP2021005514A (en) * | 2019-06-27 | 2021-01-14 | 東洋インキScホールディングス株式会社 | Conductive particle, dispersion and method for producing the same |
FR3100250A1 (en) * | 2019-09-04 | 2021-03-05 | Université de Pau et des Pays de l’Adour | Electrically conductive nanocomposite particles having a polyalkylacrylate core and a conductive polymer shell |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000268634A (en) * | 1999-03-15 | 2000-09-29 | Canon Inc | Conductive expansion particle and manufacture thereof |
JP2002367433A (en) * | 2001-06-08 | 2002-12-20 | Fujitsu Ltd | Conductive polymer particulate and method of manufacture |
JP2004241132A (en) * | 2003-02-03 | 2004-08-26 | Aica Kogyo Co Ltd | Conductive particulate, conductive resin emulsion and its manufacturing method as well as conductive paint composition and conductive sheet member |
WO2013046374A1 (en) * | 2011-09-28 | 2013-04-04 | 積水化成品工業株式会社 | Resin particles, method for producing resin particles, and use of resin particles |
WO2014017658A1 (en) * | 2012-07-24 | 2014-01-30 | 株式会社ダイセル | Conductive fiber-coated particle, curable composition and cured article derived from curable composition |
WO2014050653A1 (en) * | 2012-09-28 | 2014-04-03 | 古河電気工業株式会社 | Collector, electrode structure, nonaqueous electrolyte battery, conductive filler, and electricity storage component |
WO2014163059A1 (en) * | 2013-04-01 | 2014-10-09 | スリーボンドファインケミカル株式会社 | Electrically conductive coating material, and adherend using same |
JP2015155532A (en) * | 2014-01-14 | 2015-08-27 | 積水化学工業株式会社 | Base particle, conductive particle, conductive material and connection structure |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5433799A (en) | 1977-07-29 | 1979-03-12 | Sankyo Denki Co Ltd | Device of receiving and discharging article of automatic vending machine |
JP4962706B2 (en) * | 2006-09-29 | 2012-06-27 | 日本化学工業株式会社 | Conductive particles and method for producing the same |
JP4793456B2 (en) * | 2009-02-20 | 2011-10-12 | トヨタ自動車株式会社 | Thermally conductive insulating resin molding |
WO2012042918A1 (en) * | 2010-09-28 | 2012-04-05 | 積水化成品工業株式会社 | Coloring resin particles, and production method and uses therefor |
KR101655944B1 (en) * | 2011-03-31 | 2016-09-08 | 세키스이가세이힝코교가부시키가이샤 | Colored resin particle, method for producing same, and use thereof |
WO2014115468A1 (en) * | 2013-01-24 | 2014-07-31 | 積水化学工業株式会社 | Base material particle, conductive particle, conductive material, and connection structure |
CN105493201B (en) * | 2014-02-24 | 2018-12-07 | 积水化学工业株式会社 | The manufacturing method of conductive paste, connection structural bodies and connection structural bodies |
WO2016043265A1 (en) * | 2014-09-18 | 2016-03-24 | 積水化学工業株式会社 | Electrically conductive paste, joined structure, and method for manufacturing joined structure |
JP6514615B2 (en) * | 2014-09-18 | 2019-05-15 | 積水化学工業株式会社 | Method of manufacturing connection structure |
-
2017
- 2017-06-30 CN CN201780060713.9A patent/CN109791813B/en active Active
- 2017-06-30 JP JP2018541923A patent/JP6722766B2/en active Active
- 2017-06-30 KR KR1020197004208A patent/KR102248989B1/en active IP Right Grant
- 2017-06-30 WO PCT/JP2017/024195 patent/WO2018061374A1/en active Application Filing
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000268634A (en) * | 1999-03-15 | 2000-09-29 | Canon Inc | Conductive expansion particle and manufacture thereof |
JP2002367433A (en) * | 2001-06-08 | 2002-12-20 | Fujitsu Ltd | Conductive polymer particulate and method of manufacture |
JP2004241132A (en) * | 2003-02-03 | 2004-08-26 | Aica Kogyo Co Ltd | Conductive particulate, conductive resin emulsion and its manufacturing method as well as conductive paint composition and conductive sheet member |
WO2013046374A1 (en) * | 2011-09-28 | 2013-04-04 | 積水化成品工業株式会社 | Resin particles, method for producing resin particles, and use of resin particles |
WO2014017658A1 (en) * | 2012-07-24 | 2014-01-30 | 株式会社ダイセル | Conductive fiber-coated particle, curable composition and cured article derived from curable composition |
WO2014050653A1 (en) * | 2012-09-28 | 2014-04-03 | 古河電気工業株式会社 | Collector, electrode structure, nonaqueous electrolyte battery, conductive filler, and electricity storage component |
WO2014163059A1 (en) * | 2013-04-01 | 2014-10-09 | スリーボンドファインケミカル株式会社 | Electrically conductive coating material, and adherend using same |
JP2015155532A (en) * | 2014-01-14 | 2015-08-27 | 積水化学工業株式会社 | Base particle, conductive particle, conductive material and connection structure |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2020064833A (en) * | 2018-10-19 | 2020-04-23 | 株式会社日本触媒 | Base particles for conductive particles and use thereof |
JP7220548B2 (en) | 2018-10-19 | 2023-02-10 | 株式会社日本触媒 | Substrate particles for conductive particles and use thereof |
JP2021005514A (en) * | 2019-06-27 | 2021-01-14 | 東洋インキScホールディングス株式会社 | Conductive particle, dispersion and method for producing the same |
JP7408930B2 (en) | 2019-06-27 | 2024-01-09 | 東洋インキScホールディングス株式会社 | Conductive particles, dispersion and manufacturing method thereof |
FR3100250A1 (en) * | 2019-09-04 | 2021-03-05 | Université de Pau et des Pays de l’Adour | Electrically conductive nanocomposite particles having a polyalkylacrylate core and a conductive polymer shell |
WO2021043820A1 (en) * | 2019-09-04 | 2021-03-11 | Université De Pau Et Des Pays De L'adour | Electrically conductive nanocomposite particles having an alkyl polyacrylate core and a conductive polymer shell |
Also Published As
Publication number | Publication date |
---|---|
JP6722766B2 (en) | 2020-07-15 |
KR102248989B1 (en) | 2021-05-06 |
CN109791813B (en) | 2020-08-14 |
CN109791813A (en) | 2019-05-21 |
KR20190029656A (en) | 2019-03-20 |
JPWO2018061374A1 (en) | 2019-08-29 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5316000B2 (en) | Conductive polymer / dopant organic solvent dispersion and composition containing the dispersion | |
JP6722766B2 (en) | Conductive resin particles and uses thereof | |
JP4947759B2 (en) | Carbon nanotube-containing curable composition and composite having the cured coating film | |
KR20100088155A (en) | Method for producing carbon nanotube-containing conductor | |
US10913806B2 (en) | (Meth)acrylic conductive material | |
US20220056178A1 (en) | Hollow fine particle production method and hollow fine particles | |
KR20180097461A (en) | Transparent conductive film, transparent conductive laminate, three-dimensional shape display and resin composition | |
JP6176431B2 (en) | Active energy ray-curable coating composition and coating agent | |
KR102112598B1 (en) | Antistatic photho-curable resin composition, antistactic plastic sheet prepared by using this and manufacturing method for the sames | |
JP2008056765A (en) | Carbon nanotube-containing structure and its manufacturing method | |
JP2009286939A (en) | Nano-material-containing composition, nano-material-containing porous material, method for producing the same, layered product, and method for producing the same | |
JP2015004007A (en) | Resin particle solvent dispersion and application thereof | |
KR101029734B1 (en) | The method of preparing electroconductive polymer composite containing oxyfluorinated grahene | |
JP2012247681A (en) | Laminate for antireflection and manufacturing method thereof, and curable composition | |
JP2011031591A (en) | Nano-material-containing molded article, and method for manufacturing the same | |
CN109790391B (en) | Curable resin composition for forming easily peelable film and method for producing same | |
JP6188517B2 (en) | COMPOSITE PARTICLE, PROCESS FOR PRODUCING THE SAME, AND FILM | |
KR102033930B1 (en) | Antistatic photho-curable resin composition, antistactic plastic sheet and manufacturing method of antistactic plastic sheet | |
JP5516685B2 (en) | Conductive composition, conductive film using the same, and laminate having the conductive film | |
WO2022210893A1 (en) | Resin fine particles, coating softener, matting agent for paint, stress relaxation agent for curable resin, light diffusing agent, light diffusing resin composition, and resin composition | |
JP7379782B2 (en) | Resin fine particles and their manufacturing method | |
KR101170962B1 (en) | Manufacturing Method of Monodispersed Cross-Linked Particle Using 1 Step Process | |
JP2015193748A (en) | Light curable resin film | |
JP2024044239A (en) | Hollow resin particles and method for producing hollow resin particles | |
WO2022181349A1 (en) | Fine resin particles and composition containing fine resin particles |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 17855333 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 20197004208 Country of ref document: KR Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 2018541923 Country of ref document: JP Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 17855333 Country of ref document: EP Kind code of ref document: A1 |