CN109791813B - Conductive resin particles and use thereof - Google Patents

Conductive resin particles and use thereof Download PDF

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CN109791813B
CN109791813B CN201780060713.9A CN201780060713A CN109791813B CN 109791813 B CN109791813 B CN 109791813B CN 201780060713 A CN201780060713 A CN 201780060713A CN 109791813 B CN109791813 B CN 109791813B
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conductive resin
resin particles
conductive
particles
monomer
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CN109791813A (en
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田中浩平
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Sekisui Kasei Co Ltd
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Sekisui Plastics Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C08J3/126—Polymer particles coated by polymer, e.g. core shell structures
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/283—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing one or more carboxylic moiety in the chain, e.g. acetoacetoxyethyl(meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/285—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety
    • C08F220/286—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety and containing polyethylene oxide in the alcohol moiety, e.g. methoxy polyethylene glycol (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/124—Intrinsically conductive polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/285—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety
    • C08F220/288—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety and containing polypropylene-co-ethylene oxide in the alcohol moiety

Abstract

The present invention provides conductive resin particles having good electrical conductivity. The conductive resin particles have: a core particle formed from a polymer; and a shell which covers the core particle and is formed of a conductive polymer, wherein the conductive resin particle has a compressive strength of 0.1 to 30MPa when the conductive resin particle is deformed by compression by 10%.

Description

Conductive resin particles and use thereof
Technical Field
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 for applications for the purpose of exhibiting conductivity by causing conductive resin particles to adhere to each other, and to applications thereof (conductive resin composition, coating agent, thin film, and gap material).
Background
Known are: an electronic circuit board in which a conductive paste in which conductive particles are dispersed in a binder resin is interposed between electrodes, thereby improving the reliability of connection between the electrodes. Conductive particles made of metal such as gold, silver, or nickel have been used heretofore. However, such conductive particles are uneven in shape or have a higher specific gravity than the binder resin, and therefore, they settle in the conductive paste or are difficult to uniformly disperse once in the conductive paste, and thus, reliability is low.
Accordingly, there is disclosed a conductive particle powder comprising: a core particle formed of an organic particle; a conductive layer formed on a surface of the core particle; and a conductive polymer, wherein the conductive layer contains 1 or 2 or more conductive fillers selected from metals, metal oxides, and alloys (patent document 1).
Documents of the prior art
Patent document
Patent document 1: japanese patent No. 5630596
Disclosure of Invention
Problems to be solved by the invention
However, since the above-mentioned conductive particle powder has a hard conductive layer containing 1 or 2 or more conductive fillers selected from metals, metal oxides, or alloys, when the conductive resin particles are compressed and the conductive resin particles are bonded to each other, the adhesion between the conductive resin particles, the adhesion between a conductive member (for example, an electrode) to be electrically connected via the conductive resin particles and the conductive resin particles is low, and the contact area between the conductive resin particles and the contact area between the conductive member and the conductive resin particles are small, so that the resistance at the time of compression is high, and good conductivity cannot be obtained.
The present invention has been made in view of the above conventional problems, and an object thereof is to provide: conductive resin particles having good electrical conductivity, and a conductive resin composition, a coating agent, a thin film, and an interstitial material using the same.
Means for solving the problems
Therefore, the present inventors have conducted intensive studies to solve the above problems and, as a result, have found that: the present inventors have completed the present invention by finding that conductive resin particles having good electrical conductivity can be obtained by setting the compressive strength at 10% compressive deformation to 0.1 to 30MPa in conductive resin particles having core particles made of a polymer and shells made of a conductive polymer covering the core particles.
That is, in order to solve the above problem, the conductive resin particles of the present invention are characterized by comprising: a core particle formed from a polymer; and a shell which covers the core particle and is formed of a conductive polymer, wherein the conductive resin particle has a compressive strength of 0.1 to 30MPa when the conductive resin particle is deformed by compression by 10%.
According to the feature of the present invention, the core particle and the shell are both formed of a polymer, and the conductive resin particle is soft and largely deformed when compressed because the compressive strength at 10% compression deformation is 30MPa or less. Therefore, when the conductive resin particles are compressed and the conductive resin particles are bonded to each other, the bonding between the conductive resin particles and the bonding between the conductive member (for example, an electrode) to be electrically connected by the conductive resin particles and the conductive resin particles are 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 at the time of compression can be reduced, and good electrical conductivity can be obtained.
In order to solve the above problems, the conductive resin composition of the present invention includes: the conductive resin particles of the present invention, and a matrix resin.
The conductive resin composition having the above-described configuration contains the conductive resin particles of the present invention having good conductivity, and therefore, a molded article having excellent conductivity and antistatic properties can be obtained by molding the conductive resin composition having the above-described configuration.
In order to solve the above problems, the coating agent of the present invention is characterized by comprising the conductive resin particles of the present invention and a binder resin.
The coating agent of the above constitution contains the conductive resin particles of the present invention having good conductivity, and therefore, by applying the coating agent of the above constitution to a substrate, a product which can be suitably used as a conductive product (for example, a conductive film) or an antistatic product (for example, an antistatic film) can be obtained.
In order to solve the above problems, the film of the present invention is characterized by containing the conductive resin particles of the present invention.
The film having the above-described structure contains the conductive resin particles of the present invention having good conductivity, and therefore, can be suitably used as a conductive film or an antistatic film.
In order to solve the above problems, the gap material of the present invention is characterized by containing the conductive resin particles of the present invention.
The gap material having the above-described structure contains the conductive resin particles of the present invention having good conductivity, and therefore, has conductivity and exhibits an antistatic function.
ADVANTAGEOUS EFFECTS OF INVENTION
The present invention has an effect of providing conductive resin particles having good conductivity, and a conductive resin composition, a coating agent, a thin film, and an interstitial material using the same.
Detailed Description
The present invention will be described in detail below.
[ electroconductive resin particles ]
The conductive resin particle of the present invention has: a core particle formed from a polymer; and a shell which covers the core particle and is formed of a conductive polymer, wherein the conductive resin particle has a compressive strength of 0.1 to 30MPa when the conductive resin particle is deformed by compression by 10%.
The conductive resin particles have a compressive strength of 0.1 to 30MPa, preferably 0.1 to 17MPa, at 10% compressive deformation. The conductive resin particles having a compressive strength of less than 0.1MPa at a compressive deformation of 10% are inferior in mechanical strength and may be broken in use. When the conductive resin particles are compressed and the conductive resin particles are bonded to each other, the adhesion between the conductive resin particles and the adhesion between the conductive member (for example, an electrode) to be electrically connected to each other via the conductive resin particles are further improved, and the contact area between the conductive resin particles and the contact area between the conductive member and the conductive resin particles are further increased, whereby the resistance at the time of compression can be further reduced, and further excellent electrical conductivity can be obtained. In the present document, the "compressive strength at 10% compressive deformation" refers to the compressive strength at 10% compressive deformation (hereinafter referred to as "10% compressive strength") obtained by the measurement method described in the later-described example section.
The conductive resin particles preferably have a volume average particle diameter of 1 to 200 μm. The conductive resin particles have a volume average particle diameter of 1 μm or more, and thus, when used in a conductive paste or the like, the dispersibility in various solvents is improved, and good workability can be obtained. The conductive resin particles have a volume average particle diameter of 200 μm or less, and when the conductive resin particles are bonded to each other or when the conductive member is bonded to the conductive resin particles, the conductive resin particles are in good contact with each other, and a larger number of conductive paths can be obtained. In the present specification, the "volume average particle diameter" refers to a volume average particle diameter obtained by the measurement method described in the following example.
The coefficient of variation 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) contain a larger amount of conductive resin particles having a very small particle diameter (a particle diameter significantly smaller than the volume-average particle diameter) than conductive resin particles having the same composition and a volume-based particle diameter variation coefficient of 15% or less, and when the conductive resin particles are compressed and are caused to adhere to each other, a large amount of conductive resin particles having a very small particle diameter enter between the other conductive resin particles, thereby increasing the filling rate. Therefore, the adhesion between the conductive resin particles and the adhesion between the conductive member (for example, an electrode) to be electrically connected to the conductive resin particles and the conductive resin particles are 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 at the time of compression can be reduced, and further excellent conductivity can be obtained. In the present application, the term "coefficient of variation of volume-based particle diameter" as used herein refers to the coefficient of variation of volume-based particle diameter obtained by the measurement method described in the later-described example.
The recovery 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. The recovery rate of the conductive resin particles is 15% or more, and when the compressive stress is reduced after the conductive resin particles are compressed, the shape of the conductive resin particles is also recovered, and the adhesion between the conductive resin particles can be maintained. Therefore, good conductivity can be stably obtained. The recovery rate of the conductive resin particles is less than 30%, so that the shape of the compressed conductive resin particles is easily maintained, and as a result, good adhesion can be maintained.
The conductivity of the conductive resin particles of the present invention is preferably 5.0 × 10-3～5.0×10-1(S/cm), more preferably 9 × 10-3～1×10-1(S/cm), more preferably 1 × 10-2～5×10-2(S/cm). The conductivity of the conductive resin particles is not less than the lower limit of the above range, and thus conductive resin particles having good conductivity can be realized.
[ nuclear particles ]
The core particle may be a condensation polymer such as polyurethane or a silicone polymer, and is preferably formed of a polymer of a vinyl monomer. The vinyl monomer may be a compound having at least 1 ethylenically unsaturated group (vinyl group in a broad sense), and may be a monofunctional vinyl monomer having 1 ethylenically unsaturated group, or may be a polyfunctional vinyl monomer having 2 or more ethylenically unsaturated groups.
Examples of the monofunctional vinyl monomer include monofunctional (meth) acrylate monomers described in detail later; styrene monomers such as styrene, p-methylstyrene and α -methylstyrene; vinyl ester monomers such as vinyl acetate. Among them, a monofunctional (meth) acrylate monomer is preferable as the monofunctional vinyl-based monomer. In this specification, "(meth) acrylic acid" means acrylic acid and/or methacrylic acid, and "(meth) acrylate" means acrylate and/or methacrylate.
Examples of the polyfunctional vinyl monomer include: the following general formula (I)
CH2＝C(R1)-COO-(CH2CH2O)n-CO-C(R1)＝CH2···(I)
(in the formula, R1Is hydrogen or methyl, n is1 to 4. ) A monomer represented by the general formula (II)
CH2＝C(R2)-COO-(CH2CH2O)m-CO-C(R2)＝CH2···(II)
(in the formula, R2Is hydrogen or methyl, and m is an integer of 5 to 15. ) Polyfunctional (meth) acrylate monomers having 2 or more ethylenically unsaturated groups, such as 1, 3-butanediol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, glycerol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, phthalic acid diethylene glycol di (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified hydroxypivalate neopentyl glycol diacrylate, polyester acrylate, and urethane acrylate oligomer (described in detail in the following paragraph); aromatic divinyl monomers such as divinylbenzene, divinylnaphthalene, and derivatives thereof. Among them, the monomer represented by the above general formula (I), the monomer represented by the above general formula (II), and urethane acrylate are preferable. These vinyl monomers may be used alone or in combination of 2 or more.
The above core particle preferably contains: a polymer comprising a monomer mixture (vinyl monomer) of a monofunctional (meth) acrylate monomer and a monomer represented by the following general formula (I),
CH2＝C(R1)-COO-(CH2CH2O)n-CO-C(R1)＝CH2···(I)
(in the formula, R1Is hydrogen or methyl, and n is an integer of 1 to 4. ). The polymer is a polymer having a crosslinked structure, and therefore, restoration properties can be imparted to the core particle. Therefore, by including the polymer in the core particle, a conductive resin particle having a good recovery rate can be realized.
The monofunctional (meth) acrylate monomer is not particularly limited, and examples thereof include: acrylic esters such as methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, and 2-ethylhexyl acrylate; methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, isobornyl methacrylate, 2-hydroxyethyl methacrylate, 2-methoxyethyl methacrylate, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, diethylaminoethyl methacrylate, trifluoroethyl methacrylate, heptadecafluorodecyl methacrylate, methacrylic esters such as n-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, and (meth) acrylic esters having an epoxyalkyl group (described in detail in the following paragraph), and the like. These monofunctional (meth) acrylate monomers may be used either individually or in combination of 2 or more.
Among the monofunctional (meth) acrylate monomers, alkyl acrylates having 1 to 12 carbon atoms in the alkyl group are preferable, and alkyl acrylates having 1 to 8 carbon atoms in the alkyl group are more preferable. By using such an alkyl acrylate, the 10% compressive strength of the core particle can be reduced, and therefore, it is easy to realize a conductive resin particle having a 10% compressive strength of not more than the upper limit of the above range.
The content of the monofunctional (meth) acrylate monomer in the monomer mixture is preferably 70 to 99 parts by weight based on 100 parts by weight of the monomer mixture. By setting the content of the monofunctional (meth) acrylate monomer within the above range, conductive resin particles having a recovery ratio within the above range can be easily realized.
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. Among these monomers represented by the general formula (I), 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 amount added.
The content of the monomer represented by the general formula (I) in the monomer mixture is preferably 1 to 30 parts by weight based on 100 parts by weight of the monomer mixture. By setting the content of the monomer represented by the general formula (I) within the above range, conductive resin particles having a recovery ratio within the above range can be easily realized.
The polymer of the monomer mixture contained in the core particle is preferably a polymer of a monomer mixture further containing a monomer represented by the following general formula (II) in addition to the monofunctional (meth) acrylate monomer and the monomer represented by the general formula (I),
CH2＝C(R2)-COO-(CH2CH2O)m-CO-C(R2)＝CH2···(II)
(in the formula, R2Is hydrogen or methyl, and m is an integer of 5 to 15. ). As a result, a soft cross-linked structure can be introduced into the polymer contained in the core particle, and therefore, the 10% compressive strength of the conductive resin particle can be reduced, and the recovery rate of the conductive resin particle can be improved. Therefore, conductive resin particles having a compressive strength of 10% or less at the upper limit of the above range can be easily obtained, and conductive resin particles having a recovery ratio of at least the lower limit of the above range can be easily obtained.
Examples of the monomer represented by the general formula (II) include pentaethyleneglycol di (meth) acrylate, hexaethyleneglycol di (meth) acrylate, heptaethyleneglycol di (meth) acrylate, octaethyleneglycol di (meth) acrylate, nonaethyleneglycol di (meth) acrylate, decaethyleneglycol di (meth) acrylate, tetradecethyleneglycol di (meth) acrylate, pentadecaethyleneglycol di (meth) acrylate, and the like. Among the monomers represented by the general formula (II), when a monomer having m in the general formula (II) between nonaethylene glycol di (meth) acrylate (m ═ 9) and tetradecethylene glycol di (meth) acrylate (m ═ 14), that is, a monomer having m in the range of 9 to 14 in the general formula (II) is used, conductive resin particles having a compressive strength of 10% of the above range and conductive resin particles having a recovery ratio of the above range are easily realized.
The content of the monomer represented by the general formula (II) in the monomer mixture is preferably 1 to 20 parts by weight, more preferably 10 to 20 parts by weight, based on 100 parts by weight of the monomer mixture. When the content of the monomer represented by the general formula (II) is within the above range, conductive resin particles having a compressive strength of 10% of the above range can be easily obtained, and conductive resin particles having a recovery ratio within the above range can be easily obtained.
The monomer mixture may contain other monomers in addition to the above monomers. For example, the monomer mixture may contain another monofunctional vinyl monomer copolymerizable with the monofunctional (meth) acrylate monomer. Examples of the other monofunctional vinyl monomer copolymerizable with the monofunctional (meth) acrylate monomer include the styrene monomer and the vinyl ester monomer. These other monofunctional vinyl monomers may be used alone or in combination of 2 or more.
The monomer mixture may contain other polyfunctional vinyl monomers than those represented by the general formulae (I) and (II). Examples of the other polyfunctional vinyl monomer include the polyfunctional (meth) acrylate monomer and the aromatic divinyl monomer.
The vinyl monomer preferably includes a monomer having a hydrophilic group such as a carboxyl group or a hydroxyl group as a part thereof, and more preferably includes a (meth) acrylate having an alkylene oxide group. Thus, when the portion derived from the other component of the vinyl monomer in the core particle has high hydrophobicity, hydrophilicity may be imparted to the surface of the core particle. As a result, when the shell is formed by oxidative polymerization of the monomer in the dispersion in which the core particles are dispersed in the aqueous medium, the core particles can be easily dispersed in the aqueous medium as primary particles, and each core particle can be easily covered with the shell. Examples of such (meth) acrylate having an alkylene oxide group include compounds represented by the following general formulae.
Figure GDA0002011998190000091
In the above formula, R3Represents H or CH3，R4And R5Is different and represents a group selected from C2H4、C3H6、C4H8、C5H10Wherein p is 0 to 50, q is 0 to 50 (wherein p and q are not 0 at the same time), and R6Represents H or CH3。
In the monomer of the above general formula, when p is more than 50 and q is more than 50, polymerization stability may be lowered and composite particles may be generated. The preferable ranges of p and q are 0 to 30, and the more preferable ranges of p and q are 0 to 15.
As the (meth) acrylate having an alkylene oxide group, commercially available ones can be used. Examples of commercially available products include Brenmar (registered trademark) series manufactured by japan oil corporation. Further in the Brenmar (registered trade Mark) series, it is appropriate that Brenmar (registered trade Mark) 50PEP-300 (is R)3Is CH3、R4Is C2H5、R5Is C3H6Mixtures of p and q with p ═ 3.5 and q ═ 2.5, R6Is H), Brenmar (registered trademark) 70PEP-350B (is R)3Is CH3、R4Is C2H5、R5Is C3H6P and q are on average a mixture of p ═ 3.5 and q ═ 2.5, R6Is H), Brenmar (registered trademark) PP-1000 (is R)3Is CH3、R4Is C2H5、R5Is C3H6P is 0, q is on average 4-6, R6Is H), Brenmar (registered trademark) PME-400 (is R)3Is CH3、R4Is C2H5、R5Is C3H6P is on average 9, q is 0, R6Is CH3) And the like.
The amount of the (meth) acrylate having an alkylene oxide group used is preferably 40% by weight or less, more preferably 1 to 15% by weight, further preferably 2 to 10% by weight, and particularly preferably 3 to 7% by weight, based on the total amount of the vinyl monomers. When the amount of the (meth) acrylate having an alkylene oxide group used is not less than the lower limit of the above range, the core particles can be more easily dispersed as primary particles in an aqueous medium. When the amount of the (meth) acrylate having an alkylene oxide group used exceeds 40% by weight based on the total amount of the polymerizable vinyl monomers, the polymerization stability is lowered and the composite particles sometimes increase.
Further, the vinyl monomer preferably contains a urethane acrylate oligomer as a polyfunctional vinyl monomer together with a monofunctional vinyl monomer such as a (meth) acrylate monomer. Accordingly, the 10% compressive strength of the core particle can be reduced, and therefore, it is easy to realize a conductive resin particle having a 10% compressive strength of not more than the upper limit of the above range. The urethane acrylate oligomer preferably exhibits a glass transition temperature (Tg) (measured by viscoelasticity) of 0 to 30 ℃ when cured alone. When the Tg is less than 0 ℃, adhesiveness may sometimes occur in the core particle. When the Tg is 30 ℃ or lower, conductive resin particles having high recovery properties can be obtained. The Tg of the urethane acrylate oligomer when cured alone is more preferably 0 to 28 ℃, and still more preferably 0 to 25 ℃.
The urethane acrylate oligomer preferably exhibits a pencil hardness of H to HB when cured alone. When such a urethane acrylate oligomer is used, conductive resin particles having a higher recovery rate can be obtained.
Examples of commercially available products of the urethane acrylate oligomer include urethane acrylate oligomers of the New front (registered trademark) series such as "New front (registered trademark) RST-402" of the New front (registered trademark) RST series manufactured by first industrial pharmaceutical co, and "New front (registered trademark) RST-201", and UF series "UF-a 01P" manufactured by Kyoeisha Chemical co., ltd.
[ method for producing Nuclear particles ]
When the core particle of the present invention is formed of a polymer of a vinyl monomer, it can be obtained by polymerizing the vinyl monomer. As the polymerization method, a known method for obtaining resin particles, such as emulsion polymerization, dispersion polymerization, suspension polymerization, seed polymerization, or the like, can be used.
[ method of 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 (e.g., a lower alcohol having 5 or less carbon atoms).
The suspension polymerization may be carried out in the presence of a polymerization initiator as required. Examples of the polymerization initiator include oil-soluble peroxides such as benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, o-chlorobenzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxydicarbonate, cumene hydroperoxide, and t-butyl hydroperoxide; oil-soluble azo compounds such as 2,2 '-azobisisobutyronitrile and 2, 2' -azobis (2, 4-dimethylvaleronitrile). These polymerization initiators may be used alone or in combination of 2 or more. The amount of the polymerization initiator to be used is preferably about 0.1 to 1 part by weight based on 100 parts by weight of the vinyl monomer.
The suspension polymerization may be carried out in the presence of a dispersant and/or a surfactant, if necessary. Examples of the dispersant include inorganic salts which are hardly soluble in water, such as calcium phosphate and magnesium pyrophosphate; water-soluble polymers such as polyvinyl alcohol, methyl cellulose, and polyvinylpyrrolidone.
Examples of the surfactant include anionic surfactants such as sodium oleate, sodium lauryl sulfate, sodium dodecylbenzenesulfonate, alkylnaphthalenesulfonate, and alkylphosphate salts; nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene alkylamine, and glycerin fatty acid ester; amphoteric surfactants such as lauryl dimethyl amine oxide.
The above-mentioned dispersing agent and surfactant may be used singly or in combination of 2 or more. Among them, from the viewpoint of dispersion stability, it is preferable to use a dispersant of a sparingly water-soluble phosphate such as calcium phosphate or magnesium pyrophosphate in combination with an anionic surfactant such as alkyl sulfate or alkylbenzene sulfonate.
The amount of the dispersant is preferably 0.5 to 10 parts by weight per 100 parts by weight of the vinyl monomer, and the amount of the surfactant is preferably 0.01 to 0.2 parts by weight per 100 parts by weight of the aqueous medium.
In the suspension polymerization, the suspension polymerization can be initiated by preparing an oil phase containing the vinyl monomer and heating the aqueous phase in which the oil phase is dispersed while dispersing the prepared oil phase in an aqueous phase containing an aqueous medium. When a polymerization initiator is used, the polymerization initiator is mixed with the vinyl monomer to prepare an oil phase. In addition, when a dispersant and/or a surfactant is used, the dispersant and/or the surfactant is mixed with the aqueous medium to prepare an aqueous phase. The volume average particle diameter of the core particles can be suitably controlled by adjusting the mixing ratio of the oil phase and the aqueous phase, the amount of the dispersant and the surfactant, and the stirring and dispersing conditions.
Examples of the method for dispersing the oil phase in the aqueous phase include the following methods: a method in which an oil phase is directly added to an aqueous phase and the oil phase is dispersed in the aqueous phase in the form of droplets by using the stirring force of a propeller or the like; a method in which an oil phase is directly added to an aqueous phase and the oil phase is dispersed in the aqueous phase by using a homogenizer which is a high shear dispersing machine composed of a rotor and a stator; a method in which an oil phase is directly added to an aqueous phase and the oil phase is dispersed in the aqueous phase using an ultrasonic disperser or the like. A method in which, if an oil phase is directly added to an aqueous phase, the oil phase is dispersed in the form of droplets in the aqueous phase by collision of droplets of the mixture with each other or collision of the mixture with a machine wall using a high-pressure dispersing machine such as a microfluidizer, a Nanomizer (registered trademark); the MPG (microporous glass) porous membrane is preferably used because the particle size of the core particles can be more uniformly aligned by dispersing the oil phase into the aqueous phase by a method such as pressing the oil phase into the aqueous phase.
The polymerization temperature is preferably about 40 to 90 ℃. The time for maintaining the polymerization temperature is preferably about 0.1 to 10 hours. The polymerization reaction may be carried out in an inert gas atmosphere such as a nitrogen atmosphere which is inert to the reactants (oil phase) in the polymerization reaction system. When the boiling point of the vinyl monomer is near or below the polymerization temperature, suspension polymerization is preferably carried out in a closed or pressurized state using a pressure-resistant polymerization apparatus such as an autoclave so that the vinyl monomer does not volatilize.
After the polymerization reaction is completed, the dispersant is decomposed and removed with an acid or the like as desired, and the target core particles can be obtained by filtration, washing with water, dehydration, drying, pulverization, classification, or the like.
[ method for producing core particles by seed polymerization ]
In the method for producing core particles by seed polymerization, 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 (e.g., a lower alcohol having 5 or less carbon atoms).
In the aqueous medium, a surfactant is preferably contained. As the surfactant, an anionic surfactant, a cationic surfactant, a nonionic surfactant, and a zwitterionic surfactant may be used.
Examples of the anionic surfactant include fatty acid soaps such as sodium oleate and potassium castor oil soap, alkylsulfate salts such as sodium lauryl sulfate and ammonium lauryl sulfate, alkylbenzene sulfonate such as sodium dodecylbenzenesulfonate, dialkylsulfosuccinate salts such as alkylnaphthalenesulfonate, alkanesulfonate and sodium di (2-ethylhexyl) sulfosuccinate, alkenylsuccinate (dipotassium salt), alkyl phosphate salts, naphthalenesulfonic acid-formaldehyde condensates, polyoxyethylene alkylphenyl ether sulfate salts, polyoxyethylene lauryl ether sulfate salts such as polyoxyethylene lauryl ether sodium sulfate, and polyoxyethylene alkyl sulfate salts.
Examples of the cationic surfactant include alkylamine salts such as laurylamine acetate and stearylamine acetate, and quaternary ammonium salts such as lauryltrimethylammonium chloride.
Examples of the zwitterionic surfactant include lauryl dimethyl amine oxide, phosphate ester-based surfactants, and phosphite ester-based surfactants. The above surfactants may be used alone or in combination of 2 or more. Among the above surfactants, anionic surfactants are preferred from the viewpoint of dispersion stability at the time of polymerization.
The aqueous emulsion can be prepared by a known method. For example, an aqueous emulsion can be obtained by adding a vinyl monomer to an aqueous medium and dispersing the vinyl monomer in a fine emulsifier such as a homogenizer, an ultrasonic processor, or a Nanomizer. The vinyl monomer may contain a polymerization initiator as needed. The polymerization initiator may be mixed with the vinyl monomer in advance and then dispersed in the aqueous medium, or may be mixed with the vinyl monomer and the aqueous medium in which both are dispersed. When the particle diameter of the vinyl monomer droplets in the aqueous emulsion obtained is smaller than that of the seed particles, the vinyl monomer can be effectively absorbed by the seed particles, and therefore, the vinyl monomer is preferable.
The seed particles may be added directly to the aqueous emulsion or may be added in the form of a dispersion of seed particles in an aqueous dispersion medium. After the seed particles are added to the aqueous emulsion, the vinyl monomer is absorbed in the seed particles. The absorption is usually carried out by stirring the aqueous emulsion to which the seed particles are added at room temperature (about 20 ℃) for 1 to 12 hours. In addition, the absorption can be promoted by heating the aqueous emulsion to about 30 to 50 ℃.
The seed particles swell by absorbing the vinyl monomer. The mixing ratio of the vinyl monomer to the seed particle is preferably 5 to 150 parts by weight, more preferably 10 to 120 parts by weight, based on 1 part by weight of the seed particle. When the mixing ratio of the vinyl monomer to the seed particles is decreased, the increase in particle size due to polymerization is decreased, and the productivity may be decreased. When the mixing ratio of the vinyl monomer to the seed particles is increased, the vinyl monomer is not absorbed at all by the seed particles, and the vinyl monomer alone is suspension-polymerized in an aqueous medium to form abnormal particles in some cases. The completion of absorption was determined by confirming the enlargement of the particle size by observation with an optical microscope.
To the aqueous emulsion, a polymerization initiator may be added as needed. Examples of the polymerization initiator include organic peroxides such as benzoyl peroxide, lauroyl peroxide, o-chlorobenzoyl peroxide, o-methoxybenzoyl peroxide, 3,5, 5-trimethylhexanoyl peroxide, t-butylperoxy-2-ethylhexanoate, and di-t-butyl peroxide, azo compounds such as 2,2 ' -azobisisobutyronitrile, 1 ' -azobiscyclohexanecarbonitrile, and 2,2 ' -azobis (2, 4-dimethylvaleronitrile), and the like. The polymerization initiator is preferably used in an amount of 0.1 to 3 parts by weight based on 100 parts by weight of the vinyl monomer.
Next, the vinyl monomer absorbed in the seed particle is polymerized to obtain the core particle. The polymerization temperature is suitably selected depending on the type of the vinyl monomer and the type of the polymerization initiator. The polymerization temperature is preferably in the range of 25 to 110 ℃ and more preferably in the range of 50 to 100 ℃. The polymerization reaction is preferably carried out as follows: the monomer and the polymerization initiator are completely absorbed by the seed particles, and then the temperature is raised. After completion of the polymerization, the core particles are centrifuged as necessary to remove the aqueous medium, washed with water and a solvent, and then dried and separated.
In the polymerization step, a polymer dispersion stabilizer may be added to improve the dispersion stability of the core particles. Examples of the polymer dispersion stabilizer include polyvinyl alcohol, polycarboxylic acid, celluloses (hydroxyethyl cellulose, carboxymethyl cellulose, and the like), and polyvinylpyrrolidone. These polymer dispersion stabilizers may be used in combination with an inorganic water-soluble polymer compound such as sodium tripolyphosphate. Among them, polyvinyl alcohol and polyvinyl pyrrolidone are preferable as the polymer dispersion stabilizer. The amount of the polymeric dispersion stabilizer added is preferably 1 to 10 parts by weight based on 100 parts by weight of the vinyl monomer.
In order to suppress the generation of emulsified particles in the aqueous system, a water-soluble polymerization inhibitor such as nitrites, sulfites, hydroquinones, ascorbic acids, water-soluble vitamin B compounds, citric acid, or polyphenols may be used.
[ Shell ]
The shell is formed of a conductive polymer. The conductive polymer may be a polyaniline-based polymer, a polyisothianaphthene-based polymer, or the like, and is preferably a polymer of at least 1 monomer selected from the group consisting of nitrogen-containing heteroaromatic compounds and sulfur-containing heteroaromatic compounds, from the viewpoint of facilitating the formation of a more uniform shell and obtaining conductive resin particles having desired conductivity.
Examples of the nitrogen-containing heteroaromatic compounds include derivatives of pyrrole, indole, imidazole, pyridine, pyrimidine, pyrazine, and alkyl substituents thereof (for example, substituents derived from alkyl groups having 1 to 4 carbon atoms such as methyl, ethyl, propyl, and butyl), halogen substituents (for example, substituents derived from halogen groups such as fluoro, chloro, and bromo), and nitrile substituents. From the viewpoint of facilitating the formation of a more uniform shell and obtaining conductive resin particles having desired conductivity, a polymer of pyrrole and a pyrrole derivative is preferable as the nitrogen-containing heteroaromatic compound. The pyrrole derivative may be 3, 4-dimethylpyrrole.
As the sulfur-containing aromatic compound, thiophene and a thiophene derivative are preferable as the nitrogen-containing aromatic compound in terms of obtaining conductive resin particles having desired conductivity. Examples of the thiophene derivative include 3, 4-ethylenedioxythiophene, 3-methylthiophene, and 3-octylthiophene. These monomers may be used alone to form a homopolymer, or 2 or more of them may be used in combination to form a copolymer.
The thickness of the shell is preferably in the range of 30 to 300nm, more preferably in the range of 50 to 200 nm. When the thickness of the shell is within the above range, sufficient conductivity can be obtained. The width of the thickness of the shell is preferably 50% or less, more preferably 40% or less.
[ method of Forming Shell ]
When the conductive polymer constituting the shell is a polymer of at least 1 monomer (hereinafter, simply referred to as "monomer") selected from the group consisting of nitrogen-containing heteroaromatic compounds and sulfur-containing heteroaromatic compounds, the conductive resin particles can be produced by a method in which the core particles are covered with a polymer of the monomer. As a method for coating the polymer of the monomer on the core particle, the following method is preferable: the core particles are dispersed in an aqueous medium containing an oxidizing agent to form a dispersion (emulsion or suspension), and a monomer is added to the dispersion and stirred, thereby covering the surfaces of the core particles with a polymer of the monomer 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, more preferably 3 to 20 parts by weight, based on 100 parts by weight of the core particle. When the amount of the monomer added is 1 part by weight or more per 100 parts by weight of the core particle, the entire surface of the core particle is uniformly covered with the polymer of the monomer, and desired conductivity can be obtained. On the other hand, by making the addition amount of the monomer 30 parts by weight or less with respect to 100 parts by weight of the core particles, the monomer added is polymerized alone, and formation of substances other than the target conductive resin particles can be prevented.
(1) Oxidizing agent
Examples of the oxidizing agent include inorganic acids such as hydrochloric acid, sulfuric acid and chlorosulfonic acid, organic acids such as alkylbenzenesulfonic acid and alkylnaphthalenesulfonic acid, metal halides such as ferric chloride and aluminum chloride, halogen acids such as potassium perchlorate, peroxides such as potassium persulfate, ammonium persulfate, sodium persulfate and hydrogen peroxide. They may be used alone or in admixture thereof. As the oxidizing agent, alkali metal salts of inorganic peroxy acids are preferred. Specific examples of the alkali metal salt of an inorganic peroxy acid include potassium persulfate, sodium persulfate, and the like.
The amount of the oxidizing agent is preferably 0.5 to 2.0 molar equivalents based on the total amount of the monomers. By setting the amount of the oxidizing agent to 0.5 molar equivalent or more based on the total amount of the monomers, the entire surface of the core particle can be uniformly covered with the shell of the polymer containing the monomers, and desired conductivity can be obtained. On the other hand, when the amount of the oxidizing agent used is 2.0 molar equivalents or less relative to the total amount of the monomers, the added monomers are polymerized alone, and formation of substances other than the target conductive resin particles can be prevented.
The aqueous medium to which the oxidizing agent is added is not particularly limited as long as the monomer can be dissolved or dispersed, and water may be mentioned; or mixing water with alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, and tert-butanol; ethers such as diethyl ether, isopropyl ether, dibutyl ether, methyl cellosolve, and tetrahydrofuran; acetone, methyl ethyl ketone, diethyl ketone, etc.
(2) Aqueous medium
The aqueous medium to which the oxidizing agent is added preferably has a pH of 3 or more. When the pH is 3 or more, the entire surface of the core particle can be uniformly covered with the shell of the polymer containing the monomer, and desired conductivity can be obtained. For stable coverage, the pH is more preferably adjusted to a range of 3 to 10.
(3) Surface active agent
The aqueous medium may contain a surfactant. As the surfactant, an anionic surfactant, a cationic surfactant, a zwitterionic surfactant, and a nonionic surfactant may be used.
Examples of the anionic surfactant include fatty acid soaps such as sodium oleate and potassium castor oil soap, alkyl sulfate ester salts such as sodium lauryl sulfate and ammonium lauryl sulfate, alkyl benzene sulfonate salts such as sodium dodecylbenzenesulfonate, alkyl sulfonate salts, alkylnaphthalene sulfonate salts, alkane sulfonate salts, dialkyl sulfosuccinate salts, alkyl phosphate ester salts, naphthalene sulfonic acid formaldehyde condensates, polyoxyethylene alkylphenyl ether sulfate ester salts, and polyoxyethylene alkyl sulfate ester salts.
Examples of the nonionic surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, polyoxyethylene alkylamines, glycerin fatty acid esters, and oxyethylene-oxypropylene block polymers.
Examples of the cationic surfactant include alkylamine salts such as laurylamine acetate and stearylamine acetate, and quaternary ammonium salts such as lauryltrimethylammonium chloride.
Examples of the zwitterionic surfactant include lauryl dimethyl amine oxide, phosphate ester-based or phosphite ester-based surfactants, and the like. The above surfactants may be used alone or in combination of 2 or more. The amount of the surfactant added is preferably in the range of 0.0001 to 1 part by weight based on 100 parts by weight of the aqueous medium.
In addition, a polymer dispersion stabilizer may be added to the aqueous medium in addition to the surfactant. Examples of the polymer dispersion stabilizer include polyacrylic acid, a copolymer thereof, a neutralized product thereof, polymethacrylic acid, a copolymer thereof, a neutralized product thereof, polyvinylpyrrolidone, hydroxypropyl cellulose (HPC), and the like. The polymer dispersion stabilizer may be used in combination with the above surfactant.
(4) Oxidative polymerization
In the method for producing conductive resin particles by 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 and stirred to perform oxidative polymerization, thereby obtaining conductive resin particles in which the core particles are covered with a polymer of the monomer. The temperature of the oxidative polymerization is preferably in the range of-20 to 40 ℃ and the time of the 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 separated.
In the above description, as a method of coating the core particle with the polymer, a method of mixing the core particle and the oxidizing agent in an aqueous medium and oxidatively polymerizing the monomer has been described, but the method of coating the core particle with the polymer is not limited to this method. For example, the following method may be employed: a method of coating the core particle with a polymer by a dry method. As the dry method, for example, there can be used: a method using a ball mill, a method using a V-type mixer, a method using a high-speed flow dryer, a method using a mixing mill, a mechanical Fusion (Mechano Fusion) method, and the like.
[ use of conductive resin particles ]
The conductive resin particles of the present invention can be suitably used for applications for the purpose of exhibiting conductivity by bringing conductive resin particles into close contact with each other. The conductive resin particles of the present invention can be used as conductive particles used in a conductive paste (a substance in which conductive particles are dispersed in a binder resin) used for electrical connection in an electronic circuit board or the like, a conductive ink (a substance in which conductive particles are dispersed in a solution in which a binder resin is dissolved in a solvent) capable of forming a conductive film used for electrical connection in an electronic circuit board or the like at the time of coating and drying, a conductive elastic layer (a substance in which conductive particles are dispersed in an elastic body) of a conductive roller used in a transfer roller or the like, an anti-blocking agent, and the like.
[ conductive resin composition ]
The conductive resin composition of the present invention comprises 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.
As the aforementioned matrix resin, there can be used: 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, polyamideimide, polyethersulfone, polyimide, polyphenylene ether, polyphenylene sulfide, polystyrene, thermoplastic polyurethane elastomer, thermoplastic polyester elastomer, thermoplastic polyamide elastomer, polyvinyl chloride, polyvinylidene fluoride, ethylene tetrafluoroethylene copolymer (ETFE resin), tetrafluoroethylene perfluoroalkyl vinyl ether copolymer (PFA resin), polyether ketone, or the like. The type of the thermoplastic resin used as the matrix resin can be appropriately selected depending on the characteristics of the conductive resin composition to be used (mechanical strength, abrasion resistance, chemical resistance, heat resistance, moldability in molding the conductive resin composition to produce a molded article, and the like).
The conductive resin particles are preferably added in an amount of 1 to 200 parts by weight based on 100 parts by weight of the matrix resin.
In the conductive resin composition, other functional fillers may be added as appropriate depending on the functions required for the intended molded article. Examples of the functional filler include reinforcing fibers such as glass fibers and carbon fibers, flame retardants, delustering agents, heat stabilizers, light stabilizers, colorants, lubricants, and the like.
The conductive resin composition of the present invention can be formed into a molded article by mixing (kneading) the matrix resin, the conductive resin particles, and other functional fillers which are appropriately contained, and then molding the mixture into a desired shape by hot pressing. Alternatively, the conductive resin composition of the present invention can be formed into a molded article by extrusion molding, injection molding, or the like using pellets obtained by appropriately mixing (kneading) the matrix resin, the conductive resin particles, and other functional fillers in a heated state. Thus, a molded article having excellent conductivity and antistatic properties can be obtained.
[ coating agent ]
The coating agent of the present invention comprises the conductive resin particles of the present invention and a binder resin.
The binder resin is not particularly limited by those skilled in the art as long as it has the required properties such as transparency, dispersibility of the conductive resin particles, light resistance, moisture resistance, and heat resistance. Examples of the binder resin include (meth) acrylic resins; a (meth) acrylic acid-urethane resin; a urethane resin; a polyvinyl chloride resin; a polyvinylidene chloride resin; a melamine resin; a styrene resin; an alkyd-based resin; a phenolic resin; an epoxy resin; a polyester resin; silicone resins such as alkyl polysiloxane resins; modified silicone resins such as (meth) acrylic-silicone resins, silicone-alkyd resins, silicone-urethane resins, and silicone-polyester resins; and fluorine-based resins such as polyvinylidene fluoride and fluoroolefin vinyl ether polymers.
From the viewpoint of improving the durability of the coating agent, the binder resin is preferably a curable resin capable of forming a crosslinked structure by a crosslinking reaction. The curable resin can be cured under various curing conditions. The curable resin may be classified into an ionizing radiation curable resin such as an ultraviolet curable resin and an electron beam curable resin, a thermosetting resin, a warm-air curable resin, and the like, depending on the type of curing.
Examples of the thermosetting resin include a thermosetting urethane resin formed from an acrylic polyol and an isocyanate prepolymer, a phenol resin, a urea melamine resin, an epoxy resin, an unsaturated polyester resin, and a silicone resin.
Examples of the ionizing radiation curable resin include polyfunctional (meth) acrylate resins such as polyol polyfunctional (meth) acrylates; and polyfunctional urethane acrylate resins synthesized from diisocyanates, polyols, hydroxyl group-containing (meth) acrylates, and the like. The ionizing radiation curable resin is preferably a polyfunctional (meth) acrylate resin, and more preferably a polyol polyfunctional (meth) acrylate having 3 or more (meth) acryloyl groups in 1 molecule. Specific examples of the polyhydric alcohol polyfunctional (meth) acrylate having 3 or more (meth) acryloyl groups in 1 molecule include trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, 1,2, 4-cyclohexane tetra (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, and the like. Two or more of the above ionizing radiation curable resins may be used in combination.
As the ionizing radiation curable resin, in addition to the above, there can be used: polyether resins, polyester resins, epoxy resins, alkyd resins, spiroacetal resins, polybutadiene resins, polythiolpolyene resins, and the like having acrylate functional groups.
When an ultraviolet-curable resin is used as the ionizing radiation-curable resin, a photopolymerization initiator is added to the ultraviolet-curable resin to form a binder resin. The photopolymerization initiator may be any one, and preferably one corresponding to the ultraviolet-curable resin used.
Examples of the photopolymerization initiator include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, α -hydroxyalkylbenzophenones, α -aminoalkylbenzophenones, anthraquinones, thioxanthones, azo compounds, peroxides (described in Japanese patent application laid-open No. 2001-139663), 2, 3-dialkyldione compounds, disulfides, fluoroamine compounds, aromatic sulfonium compounds, onium salts, borate salts, active halogen compounds, and α -acyloxime esters.
Examples of the acetophenone include acetophenone, 2-diethoxyacetophenone, p-dimethylacetophenone, 1-hydroxydimethylphenyl ketone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-4-methylthio-2-morpholinopropiophenone, and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone. Examples of the benzoins include benzoin, benzoin benzoate, benzoin benzenesulfonate, benzoin tosylate, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether. Examples of the benzophenone compound include benzophenone, 2, 4-dichlorobenzophenone, 4-dichlorobenzophenone, and p-chlorobenzophenone. Examples of the phosphine oxides include 2,4, 6-trimethylbenzoyldiphenylphosphine oxide. Examples of the ketal include benzyl methyl ketals such as 2, 2-dimethoxy-1, 2-diphenylethan-1-one. Examples of the α -hydroxyalkylphenones include 1-hydroxycyclohexylphenylketone. Examples of the α -aminoalkylphenones include 2-methyl-1- [4- (methylthio) phenyl ] -2- (4-morpholinyl) -1-propanone.
Preferable examples of the commercially available photoradical polymerization initiator include "Irgacure (registered trademark) 651" (2, 2-dimethoxy-1, 2-diphenylethane-1-one) manufactured by ltd., product name "Irgacure (registered trademark) 184" manufactured by ltd., product name "Irgacure (registered trademark) 907" manufactured by BASF Japan co., product name "Irgacure (registered trademark) 907" (2-methyl-1- [4- (methylthio) phenyl ] -2- (4-morpholinyl) -1-propanone) manufactured by ltd., and the like.
The amount of the photopolymerization initiator is usually in the range of 0.5 to 20% by weight, preferably 1 to 5% by weight, based on 100% by weight of the binder resin.
As the binder resin, a thermoplastic resin may be used in addition to the curable resin. Examples of the thermoplastic resin include cellulose derivatives such as acetyl cellulose, nitrocellulose, acetyl butyl cellulose, ethyl cellulose, and methyl cellulose; vinyl resins such as homopolymers and copolymers of vinyl acetate, homopolymers and copolymers of vinyl chloride, and homopolymers and copolymers of vinylidene chloride; acetal resins such as polyvinyl formal and polyvinyl butyral; (meth) acrylic resins such as homopolymers and copolymers of acrylic acid esters and homopolymers and copolymers of methacrylic acid esters; a polystyrene resin; a polyamide resin; a linear polyester resin; polycarbonate resins, and the like.
The coating agent may further comprise water and/or an organic solvent. When the coating agent is applied to a substrate film, the organic solvent is not particularly limited as long as the organic solvent is contained in the coating agent and the coating agent can be easily applied to the substrate film. Examples of the organic solvent include aromatic solvents such as toluene and xylene; alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, 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; glycol ethers such as 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, and propylene glycol methyl ether; glycol ether esters such as 2-methoxyethyl acetate, 2-ethoxyethyl acetate (cellosolve acetate), 2-butoxyethyl acetate, and propylene glycol methyl ether acetate; chlorine-based solvents such as chloroform, dichloromethane, chloroform and dichloromethane; ether solvents such as tetrahydrofuran, diethyl ether, 1, 4-dioxane and 1, 3-dioxolane; amide solvents such as N-methylpyrrolidone, dimethylformamide, dimethylsulfoxide and dimethylacetamide. These organic solvents may be used in a mixture of 1 or 2 or more.
[ film ]
The film of the present invention contains the conductive resin particles of the present invention. The film of the present invention is formed by applying a coating agent containing conductive resin particles and a binder resin to a base film, for example. The film having such a structure can be suitably used as a conductive film or an antistatic film.
The substrate film is preferably transparent. Examples of the transparent substrate film include: films are formed from polymers such as polyester polymers such as polyethylene terephthalate (hereinafter abbreviated as "PET") and polyethylene naphthalate, cellulose polymers such as diacetylcellulose and Triacetylcellulose (TAC), and acrylic polymers such as polycarbonate polymers and polymethyl methacrylate. Further, as the transparent base film, there can be mentioned: films formed from polymers such as styrene polymers, e.g., polystyrene and acrylonitrile-styrene copolymers, olefin polymers, e.g., polyethylene, polypropylene, polyolefins having a cyclic and/or norbornene structure, ethylene-propylene copolymers, vinyl chloride polymers, and amide polymers, e.g., nylon and aromatic polyamides. Further, as the transparent base film, there can be mentioned: and films formed from polymers such as imide polymers, sulfone polymers, polyethersulfone polymers, polyether ether ketone polymers, polyphenylene sulfide polymers, vinyl alcohol polymers, vinylidene chloride polymers, vinyl butyral polymers, aryl ester polymers, polyoxymethylene polymers, epoxy polymers, and blends of the above polymers. The substrate film is particularly preferably a film having a low birefringence. Further, a film formed of these polymers and further provided with an easy-adhesion layer may be used as the base film. The easy-adhesion layer may be formed of a resin such as a (meth) acrylic resin, a copolyester resin, a polyurethane resin, a styrene-maleic acid graft polyester resin, or an acrylic acid graft polyester resin. In the present specification, "(meth) acrylic acid" means acrylic acid or methacrylic acid.
The thickness of the base film may be suitably determined, and is generally within a range of 10 to 500. mu.m, preferably within a range of 20 to 300. mu.m, and more preferably within a range of 30 to 200. mu.m, in terms of strength, workability such as handling, and thin layer properties.
In addition, additives may be added to the base film. Examples of the additives include an ultraviolet absorber, an infrared absorber, an antistatic agent, a refractive index adjuster, and a reinforcing agent.
Examples of the method for applying the coating agent to the base film include known coating methods such as bar coating, blade coating, spin coating, reverse coating, die coating, spray coating, roll coating, gravure coating, microgravure coating, lip coating, air knife coating, and dipping.
When the binder resin contained in the coating agent is an ionizing radiation curable resin, the ionizing radiation curable resin can be cured by drying the solvent as necessary after the coating agent is coated, and further irradiating the solvent with an active energy ray.
As the active energy ray, for example, there can be used: ultraviolet rays emitted from light sources such as xenon lamps, low-pressure mercury lamps, high-pressure mercury lamps, ultrahigh-pressure mercury lamps, metal halide lamps, carbon arc lamps, tungsten lamps, and the like; electron beams, alpha rays, beta rays, gamma rays and the like, which are extracted from electron beam accelerators of 20 to 2000KeV, such as Cockroft-Walton type, VandeGraaff type, resonance transformer type, insulation core conversion type, linear type, Dinamitron type, high frequency type and the like, are generally used.
The thickness of the layer (antiglare layer) in which the conductive resin particles are dispersed in the binder resin, which layer is formed by application (and curing) of the coating agent, is not particularly limited, and may be appropriately determined depending on the particle diameter of the conductive resin particles, and is preferably within a range of 1 to 10 μm, and more preferably within a range of 3 to 7 μm.
The film of the present invention is not limited to the above configuration, and the same molding resin composition as the coating agent containing the conductive resin particles and the binder resin may be molded into a film shape. The film having such a structure can be suitably used as a conductive film or an antistatic film.
[ interstitial material ]
The gap material of the present invention contains the conductive resin particles of the present invention. The gap material of the present invention can be used as a spacer for maintaining a gap distance, such as an in-plane spacer for a liquid crystal display element, a sealing portion spacer for a liquid crystal display element, a spacer for an EL (electroluminescence) display element, a spacer for a touch panel, and a gap maintaining material capable of uniformly maintaining a gap between various substrates such as ceramics and plastics. The gap material of the present invention contains the conductive resin particles of the present invention having good conductivity, and therefore, has conductivity and exerts an antistatic function.
When the gap material of the present invention has a uniform covering effect, the coefficient of variation of the volume-based particle diameter of the conductive resin particles is preferably 20% or less, and more preferably less than 10%.
Examples
The present invention will be described below with reference to examples and comparative examples, but the present invention is not limited thereto. First, the measurement methods of the volume average particle diameter, the coefficient of variation of the volume-based particle diameter, the 10% compressive strength, and the electrical conductivity of the conductive resin particles in the following examples and comparative examples will be described.
(method of measuring coefficient of variation between volume average particle diameter of conductive resin particles and volume-based particle diameter)
The coefficient of variation (CV value) between the volume average particle diameter of the conductive resin particles and the volume-based particle diameter was measured by the coulter method as follows.
Volume average particle diameter of conductive resin particles by Coulter MultisizerTM3 (measuring apparatus manufactured by Beckmann Kort Co., Ltd.). The measurement was carried out using a Multisizer manufactured by Beckmann Coulter LtdTM3 user manual corrected aperture.
The aperture used for the measurement is appropriately selected depending on the size of the conductive resin particles to be measured. Current (aperture Current) and Gain (Gain) are appropriately set depending on the size of the aperture selected. For example, when a diaphragm having a size of 50 μm is selected, the Current (diaphragm Current) is set to-800 and Gain is set to 4.
As the measurement sample, a dispersion obtained as follows was used: 0.1g of conductive resin particles was dispersed in 10ml of a 0.1% by weight nonionic surfactant aqueous solution using a Touch Mixer (manufactured by Yamatoscientific Inc., "Touch HMIXER MT-31") and an ULTRASONIC cleaner (manufactured by Velvoklya Corporation, "ULTRASONIC CLEANER VS-150") to form a dispersion. In the measurement, the conductive resin particles were gently stirred in a beaker to such an extent that the conductive resin particles did not enter the beaker, and the measurement was terminated at a time when 10 ten thousand conductive resin particles were measured. The volume average particle diameter of the conductive resin particles is an arithmetic average in a volume-based particle size distribution of 10 ten thousand particles.
The coefficient of variation of the volume-based particle diameter of the conductive resin particles is calculated by the following equation.
Coefficient of variation 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
(method of measuring 10% compressive Strength of electroconductive resin particles)
The 10% compressive strength (S10 strength) of the resin pellets was measured under the following measurement conditions using a micro compression tester "MCTM-200" manufactured by Shimadzu corporation.
Specifically, a dispersion liquid in which resin particles are dispersed in ethanol is applied to a steel sample stage that is mirror-finished, and dried to prepare a sample for measurement. Next, under an environment of room temperature of 20 ℃ and relative humidity of 65%, one independent fine resin particle (a state where no other resin particle exists at least in a range of 100 μm in diameter) was selected by an optical microscope of MCTM-200, and the diameter of the selected resin particle was measured under a particle size measuring cursor of the MCTM-200. At this time, resin particles in the range of ± 0.5 μm were selected from the volume average particle diameter confirmed by the measurement method based on the foregoing coulter method. Resin particles outside the range were not used for the determination of compressive strength. Next, the test indenter was lowered to the top of the selected resin pellet at a load speed described below, and a load was gradually applied to the resin pellet until the maximum load was 9.81mN, and the compressive strength was determined from the load at the time when the diameter of the resin pellet was displaced by 10% as measured above, according to the following equation. Each resin pellet was measured 6 times, data of the maximum value and the minimum value were removed, and the average of 4 data was defined as 10% compressive strength (S10 strength).
< calculation formula of compressive Strength >
Compressive strength (MPa) ═ 2.8 × load (N)/{ pi × (particle diameter (mm))2}
< measurement Condition of compressive Strength >
Test temperature: relative humidity at normal temperature (20 ℃) is 65 percent
An upper pressurizing pressure head: planar indenter (material: diamond) with diameter of 50 μm
A lower pressurizing plate: SKS flat plate
The test types are as follows: compression test (MODE1)
Test load: 9.81mN
Load speed: 0.732 mN/second
Displacement full scale; 20(μm)
(method of measuring the conductivity of conductive resin particles)
The conductivity of the conductive resin particles filled in the probe was measured by a powder resistance measuring system MCP-PD51 model (Mitsubishi Chemical analytical co., ltd.) by gradually applying a load from 0kN to 20kN every 4kN using a hydraulic pump, and by applying the conductive resin particles in a state of each load (0, 4kN, 8kN, 12kN, 16kN, and 20 kN). The highest value among the conductivities measured at the respective loads was taken as the conductivity of the conductive resin particles. The moisture content of the conductive resin particles was measured by karl fischer moisture measurement in advance, and it was confirmed that the moisture content was 1.0 wt% or less. As the 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 analysis co.
(example 1)
[ production of core particles ]
[ preparation of the 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 dispersant, and 0.04 part by weight of sodium lauryl sulfate as an anionic surfactant were put to prepare an aqueous phase.
[ 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, 15 parts by weight of methyl acrylate, 10 parts by weight of 2-ethylhexyl acrylate, and 5 parts by weight of poly (ethylene glycol-propylene glycol) monomethacrylate ("Brenmar (registered trademark) 50 PEP-300", manufactured by nippon oil co.), 10 parts by weight of ethylene glycol dimethacrylate ("Light Ester EG", manufactured by Kyoeisha Chemical co., ltd.) as a monomer represented by the above general formula (I), 0.2 parts by weight of 2, 2' -azobis (2, 4-dimethylvaleronitrile) as a polymerization initiator, and 0.15 parts by weight of benzoyl peroxide were put into the beaker and sufficiently stirred to prepare a mixture as an oil phase.
[ polymerization reaction ]
The prepared oil phase was added to the previously prepared aqueous phase, and the resulting mixture was stirred with a homogenizer (model p. PRIMIX corporation, desk top type, product name "homogenizer MARKII 2.5") at a stirring speed of 5000rpm for 10 minutes to disperse the oil phase in the aqueous phase, thereby obtaining a dispersion. The dispersion was put into a polymerization reactor equipped with a stirrer, a heating device and a thermometer, and stirred at 60 ℃ for 6 hours to perform suspension polymerization. Subsequently, the suspension (reaction solution) in the polymerization reactor was cooled to 30 ℃ and then hydrochloric acid was added to decompose magnesium pyrophosphate. The suspension was then filtered off with suction. The filtered residue was washed with ion-exchanged water and dehydrated to obtain an aqueous cake of core particles composed of a polymer of the target vinyl monomer.
[ production of conductive resin particles ]
[ polymerization reaction ]
In a beaker, 25 parts by weight of the obtained aqueous cake body of core particles was dispersed in 50 parts by weight of deionized water to obtain a core particle dispersion liquid. Subsequently, 20 parts by weight of potassium persulfate as an oxidizing agent was dissolved in 300 parts by weight of deionized water to prepare an aqueous potassium persulfate solution. The prepared core particle dispersion was mixed with the aqueous potassium persulfate solution, and stirred for 30 minutes. To the obtained mixed solution, 5 parts by weight of pyrrole as a nitrogen-containing aromatic compound was added, and the mixture was stirred at 25 ℃ for 5 hours to polymerize the pyrrole, thereby obtaining conductive resin particles (core-shell particles) in which the core particles were covered with a shell made of polypyrrole as a conductive polymer. The obtained conductive resin particles were as follows: the volume average particle diameter was 14.8 μm, the coefficient of variation of the volume-based particle diameter was 45%, and the 10% compressive strength was 1.4 MPa.
[ measurement of conductivity ]
The conductivity of the conductive resin particles obtained in the above-mentioned step was measured, and the result was 2.4 × 10-2S/cm。
(example 2)
[ production of core particles ]
An aqueous cake of the objective core particles was obtained in the same manner as in example 1 except that 79 parts by weight of n-butyl acrylate was used 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, 1 part by weight of ethylene glycol dimethacrylate (Light Ester EG manufactured by Kyoeisha Chemical co., ltd.) and 15 parts by weight of tetradecene glycol dimethacrylate (Light Ester 14EG manufactured by Kyoeisha Chemical co., ltd.) as a monomer represented by the above general formula (II) were used instead of 10 parts by weight of ethylene glycol dimethacrylate, the amount of benzoyl peroxide was changed to 0.3 part by weight, and the stirring conditions for dispersing the oil phase in the aqueous phase were changed to "3500 rpm and 5 minutes at the stirring speed".
[ production of conductive resin particles ]
The target conductive resin particles were obtained in the same manner as in example 1 except that the aqueous cake of core particles obtained in the above-described step was used instead of the core particles of example 1 and the amount of deionized water used in obtaining the core particle dispersion was changed to 25 parts by weight. The obtained conductive resin particles were as follows: the volume average particle diameter was 15.4 μm, the coefficient of variation of the volume-based particle diameter was 39%, and the 10% compressive strength was 2.3 MPa.
[ measurement of conductivity ]
The conductivity of the conductive resin particles obtained in the above-mentioned step was measured, and the result was 2.8 × 10-2S/cm。
(example 3)
[ production of core particles ]
An aqueous cake of the objective core particles was obtained in the same manner as in example 1.
[ production of conductive resin particles ]
Conductive resin particles in which core particles were covered with a shell made of poly (3, 4-ethylenedioxythiophene) which is a conductive polymer were obtained in the same manner as in example 1, except that 3, 4-ethylenedioxythiophene was used instead of pyrrole and the stirring time during polymerization was changed to 24 hours. The obtained conductive resin particles were as follows: the volume average particle size was 16.2 μm, the coefficient of variation of the volume-based particle size was 46%, and the 10% compressive strength was 2.5 MPa.
[ measurement of conductivity ]
The conductivity of the conductive resin particles obtained in the above-mentioned step was measured, and the result was 1.8 × 10-2S/cm。
(example 4)
[ production of core particles ]
[ soap-free polymerization ]
In a beaker, 15 parts by weight of methyl methacrylate as a monofunctional (meth) acrylate monomer was mixed with 0.2 part by weight of n-octyl mercaptan as a molecular weight modifier to prepare an oil phase.
In a beaker different from the above, 0.1 part by weight of potassium persulfate as a polymerization initiator was dissolved in 80 parts by weight of ion-exchanged water to prepare an aqueous potassium persulfate solution, and the oil phase was mixed with the aqueous potassium persulfate solution to carry out soap-free polymerization at 55 ℃ for 12 hours. Thereby, a dispersion liquid containing seed particles made of polymethyl methacrylate was obtained. The volume average particle diameter of the resulting seed particles was 0.51. mu.m.
[ seed polymerization ]
Subsequently, in a new beaker, 70 parts by weight of n-butyl acrylate, 5 parts by weight of methyl acrylate, 5 parts by weight of 2-ethylhexyl acrylate, and 5 parts by weight of poly (ethylene glycol-propylene glycol) monomethacrylate ("Brenmar (registered trademark) 50 PEP-300", manufactured by nippon oil co., ltd.), 10 parts by weight of ethylene glycol dimethacrylate, which is a monomer represented by the above general formula (I), and 0.01 part by weight of 2, 2' -azobis (2-methylbutyronitrile), which is a polymerization initiator, were mixed. In the obtained mixture, 0.08 part by weight of sodium bis (2-ethylhexyl) sulfosuccinate as an anionic surfactant was dissolved in 80 parts by weight of ion-exchanged water as an aqueous medium to obtain an aqueous solution, and the obtained aqueous solution was mixed and treated with a homogenizer (product of PRIMIX, desk top, product name "homogenizer MARKII 2.5") at a stirring speed of 8000rpm for 10 minutes to obtain an emulsion.
40 parts by weight of the dispersion containing seed particles obtained by soap-free polymerization was added to the emulsion while stirring. After stirring for 3 hours, 240 parts by weight of ion-exchanged water in which 0.03 part by weight of polyvinyl alcohol as a polymer dispersion stabilizer was dissolved was added, and polymerization was carried out while stirring at 60 ℃ for 6 hours, and after the obtained polymer emulsion was dehydrated by suction filtration, the residue was washed with ion-exchanged water, thereby obtaining a water-containing filter cake body having a core particle with a sharp particle size distribution. The volume average particle diameter of the obtained core particles was 1.2. mu.m.
[ production of conductive resin particles ]
The target conductive resin particles were obtained in the same manner as in example 1 except that the aqueous cake of core particles obtained in the above-described step was used in place of the core particles of example 1, and the amount of deionized water used in obtaining a core particle dispersion by dispersing the core particles was changed to 25 parts by weight. The obtained conductive resin particles were as follows: the volume average particle diameter was 1.3 μm, the coefficient of variation of the volume-based particle diameter was 9%, and the 10% compressive strength was 1.4 MPa.
[ measurement of conductivity ]
The conductivity of the conductive resin particles obtained in the above-mentioned step was measured, and the result was 1.5 × 10-2S/cm。
(example 5)
[ production of core particles ]
An aqueous cake of the objective core particles was obtained in the same manner as in example 1, except that the amount of sodium lauryl sulfate used was changed to 0.005 parts by weight, and the stirring speed for dispersing the oil phase in the aqueous phase was changed to 200rpm for 10 minutes without using a homogenizer.
[ production of conductive resin particles ]
The target conductive resin particles were obtained in the same manner as in example 1, except that the aqueous cake of core particles obtained in the above-described step was used instead of the core particles of example 1. The obtained conductive resin particles were as follows: the volume average particle diameter was 198 μm, the coefficient of variation of the volume-based particle diameter was 49%, and the 10% compressive strength was 1.7 MPa.
[ measurement of conductivity ]
The conductivity of the conductive resin particles obtained in the above-mentioned step was measured, and the result was 2.0 × 10-2S/cm。
(example 6)
[ production of core particles ]
An aqueous cake of the objective core particle was obtained in the same manner as in example 1 except that 45 parts by weight of n-butyl acrylate was used 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, and 50 parts by weight of urethane acrylate oligomer (product name "New front (registered trademark) RST-402", manufactured by first industrial pharmaceutical co., ltd.) was used instead of 10 parts by weight of ethylene glycol dimethacrylate.
[ production of conductive resin particles ]
The target conductive resin particles were obtained in the same manner as in example 1 except that the aqueous cake of core particles obtained in the above-described step was used instead of the core particles of example 1 and the amount of deionized water used in obtaining a core particle dispersion by dispersing the core particles was changed to 25 parts by weight. The obtained conductive resin particles were as follows: the volume average particle diameter was 16.2 μm, the coefficient of variation of the volume-based particle diameter was 44%, and the 10% compressive strength was 1.2 MPa.
[ measurement of conductivity ]
The conductivity of the conductive resin particles obtained in the above-mentioned step was measured, and the result was 2.6 × 10-2S/cm。
(example 7)
[ production of core particles ]
An aqueous cake of the objective core particles was obtained in the same manner as in example 1.
[ production of conductive resin particles ]
The target conductive resin particles were obtained in the same manner as in example 3, except that the core particles obtained in the above-described step were used in place of the core particles of example 3, and the amount of deionized water used in obtaining a core particle dispersion by dispersing the core particles was changed to 50 parts by weight. The obtained conductive resin particles were as follows: the volume average particle diameter was 16.5 μm, the coefficient of variation of the volume-based particle diameter was 42%, and the 10% compressive strength was 1.2 MPa.
[ measurement of conductivity ]
The conductivity of the conductive resin particles obtained in the above-mentioned step was measured, and the result was 2.9 × 10-2S/cm。
Comparative example 1
[ production of core particles ]
Core particles were obtained in the same manner as in example 1 except that 95 parts by weight of methyl methacrylate was used instead of 60 parts by weight of n-butyl acrylate, 15 parts by weight of methyl acrylate, 10 parts by weight of 2-ethylhexyl acrylate, and 5 parts by weight of poly (ethylene glycol-propylene glycol) monomethacrylate as monofunctional (meth) acrylate monomers, and the amount of ethylene glycol dimethacrylate used was changed to 5 parts by weight.
[ production 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 instead of 50 parts by weight of deionized water as a dispersion medium used in obtaining the core particle dispersion liquid. The 10% compressive strength of the obtained conductive resin particles was 34.3 MPa.
[ measurement of conductivity ]
The conductivity of the conductive resin particles obtained in the above-mentioned step was measured, and the result was 2.2 × 10-3S/cm。
Comparative example 2
Conductive resin particles were obtained in the same manner as in comparative 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 10% compressive strength of the obtained conductive resin particles was 36.4 MPa.
[ measurement of conductivity ]
The conductivity of the conductive resin particles obtained in the above-mentioned step was measured, and the result was 2.2 × 10-3S/cm。
Comparative example 3
[ production of core particles ]
In the seed polymerization, core particles were obtained in the same manner as in example 4 except that 70 parts by weight of methyl methacrylate was used instead of 70 parts by weight of n-butyl acrylate, 5 parts by weight of methyl acrylate, 5 parts by weight of 2-ethylhexyl acrylate, and 5 parts by weight of poly (ethylene glycol-propylene glycol) monomethacrylate ("Brenmar (registered trademark) 50 PEP-300", manufactured by nippon oil co. The volume average particle diameter of the obtained core particles was 1.1. mu.m.
[ production of conductive resin particles ]
The objective conductive resin particles were obtained in the same manner as in example 4, except that the core particles obtained in the above-described steps were used instead of the core particles of example 4. The obtained conductive resin particles were as follows: the volume average particle diameter was 1.2 μm, the coefficient of variation of the volume-based particle diameter was 9%, and the 10% compressive strength was 36.1 MPa.
[ measurement of conductivity ]
The conductivity of the conductive resin particles obtained in the above-mentioned step was measured, and the result was 3.5 × 10-3S/cm。
Table 1 summarizes the volume average particle diameter, the coefficient of variation in volume-based particle diameter, the 10% compressive strength, and the electrical conductivity of the conductive resin particles obtained in examples 1 to 7 and comparative examples 1 to 3, and the composition of the monomer mixture used for producing the core particles (the composition of the monomer mixture used for seed polymerization in example 4 and comparative example 3) and the kind of the monomer used for forming the shell. In table 1, n-butyl acrylate is abbreviated as "BA", methyl acrylate is abbreviated as "MA", 2-ethylhexyl acrylate is abbreviated as "2 EHA", methyl methacrylate is abbreviated as "MMA", poly (ethylene glycol-propylene glycol) monomethacrylate "Brenmar (registered trademark) 50 PEP-300" is abbreviated as "50 PEP-300", ethylene glycol dimethacrylate is abbreviated as "EGDMA", tetradecethylene glycol dimethacrylate is abbreviated as "14 EG", and urethane acrylate "New front (registered trademark) RST-402" is abbreviated as "RST-402", respectively.
[ Table 1]
Figure GDA0002011998190000341
As described above, the conductive resin particles of examples 1 to 7 had 10% compressive strength of 0.1 to 30MPa (1.2 to 2.5MPa), and thus had electrical conductivity (2.2 to 3.5 × 10) comparable to that of the conductive resin particles of comparative examples 1 to 3 where 10% compressive strength exceeded 30MPa (34.3 to 36.4MPa)-3S/cm) has an excellent conductivity (1.5 to 2.9 × 10-2S/cm)。
(example 8)
In a binder solution in which 10 parts by weight of an acrylic resin (product name "Dianal (registered trademark) BR-106", manufactured by Mitsubishi Chemical Corporation) as a binder resin was dissolved in 50 parts by weight of toluene as an organic solvent, 10 parts by weight of the conductive resin particles obtained in example 1 were blended and uniformly dispersed to prepare a coating agent.
The coating agent was applied to a PET film having a thickness of 100 μm as a base film by using a 30 μm applicator to form a coating film. The film was left to stand in a high-temperature bath at 70 ℃ for 2 hours to dry the coating film on the PET film, thereby obtaining a film having conductivity.
The present invention may be embodied in other specific forms without departing from its spirit or essential characteristics. Therefore, the above embodiments are merely examples in all respects and are not to be construed as limiting. The scope of the invention is indicated by the appended claims, and is not limited by the text of the description. Further, all changes and modifications that fall within the scope of the claims are to be embraced within their scope.
In addition, the present application claims priority based on Japanese application No. 2016-. The entire contents of which are hereby incorporated by reference into the present application.

Claims (11)

1. An electroconductive resin particle characterized by comprising:
a core particle formed from a polymer; and the combination of (a) and (b),
a shell which covers the core particle and is formed of a conductive polymer,
the conductive resin particles have a compressive strength of 0.1 to 30MPa when the conductive resin particles are deformed by compression by 10%,
the coefficient of variation of the volume-based particle diameter is 9% or 10% or more,
the method for calculating the coefficient of variation of the volume-based particle diameter:
the coefficient of variation of the volume-based particle size is (standard deviation of volume-based particle size distribution ÷ volume average particle size) × 100.
2. The electroconductive resin particle according to claim 1,
the polymer contains: a polymer comprising a monomer mixture of a monofunctional (meth) acrylate monomer and a monomer represented by the following general formula (I),
CH2＝C(R1)-COO-(CH2CH2O)n-CO-C(R1)＝CH2…(I)
in the formula, R1Is hydrogen or methyl, and n is an integer of 1 to 4.
3. The electroconductive resin particle according to claim 2,
the monomer mixture further comprises a monomer represented by the following general formula (II),
CH2＝C(R2)-COO-(CH2CH2O)m-CO-C(R2)＝CH2…(II)
in the formula, R2Is hydrogen or methyl, and m is an integer of 5 to 15.
4. The electroconductive resin particle according to any one of claims 1 to 3,
the conductive polymer is a polymer of at least 1 monomer selected from the group consisting of nitrogen-containing heteroaromatic compounds and sulfur-containing heteroaromatic compounds.
5. The electroconductive resin particle according to any one of claims 1 to 3,
has a volume average particle diameter of 1 to 200 μm.
6. The electroconductive resin particle according to any one of claims 1 to 3,
the coefficient of variation of the volume-based particle diameter is 10% or more.
7. The electroconductive resin particle according to any one of claims 1 to 3, wherein the width of the thickness of the shell is 50% or less.
8. An electrically conductive resin composition, comprising: the conductive resin particle according to any one of claims 1 to 7; and, a matrix resin.
9. A coating agent, characterized by comprising: the conductive resin particle according to any one of claims 1 to 7; and, a binder resin.
10. A film comprising the conductive resin particles according to any one of claims 1 to 7.
11. An interstitial material comprising the conductive resin particles according to any one of claims 1 to 7.
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