KR102248989B1 - Conductive resin particles and their uses - Google Patents

Abstract

It provides electroconductive resin particles having good electrical conductivity. The conductive resin particles are conductive resin particles having a core particle made of a polymer and a shell made of a conductive polymer covering the core particles, and have a compressive strength of 0.1 to 30 MPa at 10% compression deformation.

Description

Conductive resin particles and their uses

The present invention relates to conductive resin particles and uses thereof. More specifically, the present invention relates to conductive resin particles that can be preferably used in applications for the purpose of expressing conductivity by bringing conductive resin particles in close contact with each other, and uses thereof (conductive resin composition, coating agent, film, and gap material). will be.

An electronic circuit board is known in which the connection reliability between electrodes is improved by interposing a conductive paste in which conductive particles are dispersed in a binder resin between electrodes. Until now, electroconductive particles made of metals such as gold, silver, and nickel have been used for such electroconductive particles. However, since these electroconductive particles have a non-uniform shape or have a higher specific gravity than a binder resin, it is difficult to settle in the electroconductive paste or uniformly primary disperse in the electroconductive paste, and thus lack reliability.

Thus, as a conductive particle powder further containing a core particle composed of organic particles, a conductive layer formed on the surface of the core particle, and a conductive polymer, the conductive layer is one selected from metals, metal oxides, or alloys. Alternatively, electroconductive particle powder comprising two or more types of electroconductive fillers is disclosed (Patent Document 1).

Japanese Patent No. 5630596

However, since the electroconductive particle powder has a solid conductive layer made of one or more conductive fillers selected from metals, metal oxides, or alloys, when the conductive resin particles are compressed and the conductive resin particles are in close contact with each other. , The adhesion between the conductive resin particles or the adhesion between the conductive member (for example, electrode) and the conductive resin particles to be electrically connected by the conductive resin particles is low, and the contact area between the conductive resin particles or the contact area between the conductive resin particles or the conductive member and the conductive resin particles Since the contact area of is small, resistance during compression is high, and good electrical conductivity is not 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 a good conductivity, and a conductive resin composition, a coating agent, a film, and a gap material using the same.

Accordingly, as a result of intensive examination by the present inventors so as to solve the above problems, in the conductive resin particles having a core particle made of a polymer and a shell made of a conductive polymer covering the core particle, the compressive strength at 10% compression deformation By setting the value to 0.1 to 30 MPa, it was found that electroconductive resin particles having a good conductivity were obtained, and the present invention was completed.

That is, in order to solve the above problems, the conductive resin particles of the present invention are conductive resin particles having a core particle made of a polymer and a shell made of a conductive polymer covering the core particles, and have a compressive strength at 10% compression deformation. It is characterized in that it is 0.1 to 30 MPa.

According to the configuration of the present invention, since both the core particles and the shell are made of a polymer, and the compressive strength at 10% compression deformation is 30 MPa or less, the conductive resin particles are flexible and deform greatly during compression. For this reason, when the conductive resin particles are compressed and the conductive resin particles are in close contact with each other, the adhesion between the conductive resin particles and the conductive member (e.g., electrode) to be electrically connected by the conductive resin particles and the adhesion between the conductive resin particles This improves, and since the contact area between the conductive resin particles and the contact area between the conductive member and the conductive resin particles becomes large, resistance during compression can be lowered, and good conductivity can be obtained.

In order to solve the said subject, the electroconductive resin composition of this invention is characterized by containing the electroconductive resin particle of this invention, and a matrix resin.

Since the conductive resin composition of the above-described configuration contains the conductive resin particles of the present invention having a good conductivity, 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 said subject, the coating agent of this invention is characterized by containing the electroconductive resin particle of this invention and a binder resin.

Since the coating agent of the above configuration contains the conductive resin particles of the present invention having a good conductivity, by applying the coating agent of the above configuration on a substrate, a conductive product (for example, a conductive film) or an antistatic product (for example, , An antistatic film) that can be preferably used as a product can be obtained.

In order to solve the said subject, the film of this invention is characterized by containing the electroconductive resin particle of this invention.

Since the film of the said structure contains the electroconductive resin particle of this invention which has favorable electric conductivity, it can be used suitably as a electroconductive film or an antistatic film.

In order to solve the said subject, the gap material of this invention is characterized by containing the electroconductive resin particle of this invention.

Since the gap material of the above-described configuration contains the conductive resin particles of the present invention having a good conductivity, it has conductivity and exhibits an antistatic function.

The present invention exhibits an effect of being able to provide conductive resin particles having good electrical conductivity and conductive resin compositions, coating agents, films, and gap materials using the same.

Hereinafter, the present invention will be described in detail.

[Conductive resin particles]

The conductive resin particles of the present invention are conductive resin particles having a core particle made of a polymer and a shell made of a conductive polymer covering the core particles, and have a compressive strength of 0.1 to 30 MPa at 10% compression deformation.

The compressive strength at the time of 10% compression deformation of the conductive resin particles is 0.1 to 30 MPa, but is preferably 0.1 to 17 MPa. Electroconductive resin particles having a compressive strength of less than 0.1 MPa at the time of 10% compression deformation have poor mechanical strength and may be destroyed when used. A conductive resin particle having a compressive strength of 17 MPa or less at the time of 10% compression deformation is a conductive member that is intended to be electrically connected by the adhesion between the conductive resin particles and the conductive resin particles when the conductive resin particles are compressed and the conductive resin particles are brought into close contact with each other ( For example, the adhesion between the electrode) and the conductive resin particles is further improved, and the contact area between the conductive resin particles or the contact area between the conductive member and the conductive resin particles is further increased. Conductivity can be obtained. On the other hand, in the document of this application, "compressive strength at 10% compressive deformation" is the compressive strength at 10% compressive deformation obtained by the measurement method described in the section of Examples to be described later (hereinafter, “10% compressive strength”). It shall mean).

It is preferable that the said electroconductive resin particle has a volume average particle diameter of 1 -200 micrometers. When the conductive resin particles have a volume average particle diameter of 1 µm or more, dispersibility in various solvents is improved when used in a conductive paste or the like, and good handling properties can be obtained. Since the conductive resin particles have a volume average particle diameter of 200 μm or less, when the conductive resin particles are brought into close contact with each other, or when the conductive member and the conductive resin particles are brought into close contact with each other, the contact between them is improved, and more conductive paths Can be obtained. In addition, in the document of this application, the "volume average particle diameter" shall mean a volume average particle diameter obtained by the measurement method described in the section of Examples to be described later.

The coefficient of variation of the particle diameter based on the volume of the conductive resin particles is preferably 10% or more, and more preferably in the range of 20% to 50%. Electroconductive resin particles having a volume-based particle diameter variation coefficient of 10% or more (especially 20% or more) have the same composition and a volume-based particle diameter variation coefficient of 15% or less compared to a fine particle diameter ( Since it contains a large number of conductive resin particles having a significantly smaller particle diameter compared to the volume average particle diameter), when the conductive resin particles are compressed and the conductive resin particles are brought into close contact with each other, the conductive resin particles having a large number of fine particle diameters have other conductivity. It enters between the resin particles and improves the filling rate. For this reason, the adhesion between the conductive resin particles and the adhesion between the conductive member (for example, electrode) and the conductive resin particles to be electrically connected by the conductive resin particles are improved, and the contact area between the conductive resin particles and the conductive member Since the contact area of the conductive resin particles increases, the resistance during compression can be lowered, so that more excellent conductivity can be obtained. In the meantime, in the document of the present application, "the coefficient of variation of the particle diameter on a volume basis" shall mean the coefficient of variation of the particle diameter on a volume basis obtained by the measurement method described in the section of Examples to be described later.

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 still more preferably 15% or more and 20% or less. When the restoration rate of the electroconductive resin particles is 15% or more, even when the compressive stress decreases after the electroconductive resin particles are compressed, the shape of the electroconductive resin particles is restored and the adhesion between the electroconductive resin particles can be maintained. Therefore, it is possible to stably obtain a good electrical conductivity. When the recovery rate of the electroconductive resin particles is less than 30%, it becomes easy to maintain the shape after compressing the electroconductive resin particles, and as a result, good adhesion can be maintained.

The conductivity of the conductive resin particles of the present invention ^{is preferably 5.0 × 10 -3 to 5.0 × 10 -1} (S/cm), more preferably 9 × 10 ^{-3 to} 1 × 10 ^-1 (S/cm). It is preferable, and it is more preferable that it is ^{1×10 -2} -5×10 ^{-2 (S/cm).} When the conductivity of the conductive resin particles is equal to or greater than the lower limit of the above range, conductive resin particles having good conductivity can be realized.

[Core particle]

The core particles may be condensed polymers such as polyurethane and silicone polymers, but it is preferably made of a polymer of vinyl monomers. The vinyl-based monomer may be a compound having at least one ethylenically unsaturated group (broad meaning vinyl group), and may be a monofunctional vinyl-based monomer having one ethylenically unsaturated group, and has two or more ethylenically unsaturated groups. It may be a functional vinyl-based monomer.

As the monofunctional vinyl-based monomer, for example, the monofunctional (meth)acrylic acid ester monomer described in the later stage; Styrene-based monomers such as styrene, p-methylstyrene, and α-methylstyrene; And vinyl ester monomers such as vinyl acetate. Among these, a monofunctional (meth)acrylic acid ester monomer is preferable as a monofunctional vinyl-based monomer. On the other hand, in the document of this application, "(meth)acrylic acid" means acrylic acid and/or methacrylic acid, and "(meth)acrylate" means acrylate and/or methacrylate.

As the polyfunctional vinyl-based monomer, the following formula (I)

(Wherein, R ₁ is hydrogen or a methyl group, n is an integer of 1 to 4) a monomer represented by the formula (II), the following formula (II)

(In the formula, R ₂ is hydrogen or a methyl group, m is an integer of 5 to 15) Monomer represented by, 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate , 1,6-hexanediol di(meth)acrylate, glycerin di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, diethylene glycol di(meth)acrylate phthalate Two such as acrylate, caprolactone-modified dipentaerythritol hexa (meth)acrylate, caprolactone-modified hydroxypivalic acid ester neopentyl glycol diacrylate, polyester acrylate, urethane acrylate oligomer (described in detail later) Polyfunctional (meth)acrylic acid ester monomers having the above ethylenically unsaturated groups; And aromatic divinyl monomers such as divinylbenzene, divinylnaphthalene, and derivatives thereof. Among these, the monomer represented by the formula (I), the monomer represented by the formula (II), and the urethane acrylate are preferred. These vinylic monomers can be used individually or in combination of two or more, respectively.

The core particles are monofunctional (meth)acrylic acid ester monomer, and the following formula (I)

(In the formula, R ₁ is hydrogen or a methyl group, and n is an integer of 1 to 4) It is preferable to contain a polymer of a monomer mixture (vinyl monomer) containing a monomer represented by. Since this polymer is a polymer having a crosslinked structure, resilience can be imparted to the core particles. Therefore, by containing this polymer in the said core particle|grains, electroconductive resin particle|grains which have a favorable recovery rate can be realized.

The monofunctional (meth)acrylic acid ester monomer is not particularly limited, and examples thereof include acrylic acid 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-methoxy methacrylate Ethyl, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, diethylaminoethyl methacrylate, trifluoroethyl methacrylate, heptadecafluorodecyl methacrylate, n-butyl methacrylate, methacrylic acid Methacrylic acid esters such as acid t-butyl and 2-ethylhexyl methacrylate, (meth)acrylic acid esters having an alkylene oxide group (described in detail later), and the like can all be used. These monofunctional (meth)acrylic acid ester monomers can be used alone or in combination of two or more.

Among the monofunctional (meth)acrylic acid ester monomers, alkyl acrylate having 1 to 12 carbon atoms in the alkyl group is preferred, and alkyl acrylate having 1 to 8 carbon atoms in the alkyl group is more preferred. By using such an alkyl acrylate, since the 10% compressive strength of the core particles can be lowered, it becomes easy to realize conductive resin particles having a 10% compressive strength equal to or less than the upper limit of the above-described range.

Further, the content of the monofunctional (meth)acrylic acid ester 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)acrylic acid ester monomer within the above range, it becomes easy to realize conductive resin particles having a recovery rate in the above range.

As a monomer represented by the above formula (I), for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) ) Acrylate, etc. are mentioned. Among the monomers represented by the formula (I), ethylene glycol di (meth) acrylate is particularly preferred, and when ethylene glycol di (meth) acrylate is used as the monomer represented by the formula (I), the conductive resin is more effectively It is possible to improve the solvent resistance of the particles.

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 making the content of the monomer represented by the general formula (I) within the above range, it becomes easy to realize conductive resin particles having a recovery rate in the above range.

In addition to the monofunctional (meth)acrylic acid ester monomer and the monomer represented by the general formula (I), the polymer of the monomer mixture contained in the core particle is the following general formula (II)

(In the formula, R ₂ is hydrogen or a methyl group, and m is an integer of 5 to 15) It is preferably a polymer of a monomer mixture further containing a monomer represented. Thereby, since a flexible crosslinked structure can be introduced into the polymer contained in the core particles, the 10% compressive strength of the conductive resin particles can be lowered, and the recovery rate of the conductive resin particles can be improved. Therefore, it becomes easy to realize electroconductive resin particles having a compressive strength of 10% or less of the upper limit of the above-described range, and furthermore, it becomes easy to realize electroconductive resin particles having a recovery rate equal to or greater than the lower limit of the aforementioned range.

As a monomer represented by the above formula (II), for example, pentaethylene glycol di (meth) acrylate, hexaethylene glycol di (meth) acrylate, hepta ethylene glycol di (meth) acrylate, octaethylene glycol di ( Meth) acrylate, nona ethylene glycol di (meth) acrylate, deca ethylene glycol di (meth) acrylate, tetradeca ethylene glycol di (meth) acrylate, penta deca ethylene glycol di (meth) acrylate, and the like. have. Among the monomers represented by the formula (II), m in the formula (II) is between nonaethylene glycol di (meth) acrylate (m = 9) and tetradecaethylene glycol di (meth) acrylate (m = 14). When a monomer, that is, a monomer in which m in the formula (II) is in the range of 9 to 14, it becomes easy to realize conductive resin particles having a compressive strength of 10% in the above-described range, and the recovery rate in the above-described range is improved. It becomes easy to realize the electroconductive resin particle which has.

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. By making the content of the monomer represented by the general formula (II) within the above range, it becomes easy to realize conductive resin particles having 10% compressive strength in the above range, and also, it is easy to realize conductive resin particles having a recovery rate in the above range. Lose.

On the other hand, the monomer mixture may contain other monomers other than the above-described monomers. For example, the monomer mixture may contain a monofunctional (meth)acrylic acid ester monomer and another monofunctional vinyl-based monomer copolymerizable. Other monofunctional vinyl monomers that can be copolymerized with the monofunctional (meth)acrylic acid ester monomer include, for example, the styrene monomers described above, the vinyl ester monomers described above, and the like. These other monofunctional vinyl-based monomers can be used alone or in combination of two or more.

Further, the monomer mixture may contain polyfunctional vinyl monomers other than those represented by the general formulas (I) and (II). As other polyfunctional vinyl-based monomers, the polyfunctional (meth)acrylic acid ester-based monomers described above, the aromatic divinyl-based monomers described above, and the like may be mentioned, for example.

Further, the vinyl-based monomer preferably contains a monomer having a hydrophilic group such as a carboxyl group and a hydroxy group as a part thereof, and more preferably contains a (meth)acrylic acid ester having an alkylene oxide group. Thereby, even in the case where the hydrophobicity of the part derived from another component of the vinyl-based monomer in the core particle is high, hydrophilicity can be imparted to the surface of the core particle. As a result, in the case of forming a shell by oxidation polymerization of a monomer in a dispersion in which the core particles are dispersed in an aqueous medium, the core particles can be easily dispersed in the primary particles in the aqueous medium, and individual cores can be easily The particles can be coated with a shell. Examples of the (meth)acrylic acid ester having an alkylene oxide group include compounds represented by the following formula.

In the above formula, R ₃ represents H or CH ₃ , R ₄ and R ₅ differently represent an alkylene group selected from _{C 2} H ₄ , C ₃ H ₆ , C ₄ H ₈ , C ₅ H _{10, and p} Is 0 to 50, q is 0 to 50 (however, p and q do not become 0 at the same time), and R ₆ represents H or CH ₃ .

On the other hand, in the monomer of the above formula, when p is greater than 50 and q is greater than 50, polymerization stability is lowered, and coalescence particles may be generated. Preferred ranges of p and q are 0 to 30, and more preferred ranges of p and q are 0 to 15.

As the (meth)acrylic acid ester having an alkylene oxide group, a commercial item can be used. As a commercial item, the Nichiyu Co., Ltd. BLEMMER (registered trademark) series is mentioned, for example. In addition, among the Blemmer (registered trademark) series, Blemmer (registered trademark) 50PEP-300 (R ₃ is CH ₃ , R ₄ is C ₂ H ₅ , R ₅ is C ₃ H ₆ , p and q are averaged p =3.5 and a mixture of q=2.5, R ₆ is H), Blemmer (registered trademark) 70PEP-350B (R ₃ is CH ₃ , R ₄ is C ₂ H ₅ , R ₅ is C ₃ H ₆ , p and q is a mixture of p=3.5 and q=2.5 on average, R ₆ is H), Blemmer (registered trademark) PP-1000 (R ₃ is CH ₃ , R ₄ is C ₂ H ₅ , R ₅ is C ₃ H ₆ , p is 0, q is a mixture of 4-6 on average, R ₆ is H), Blemmer (registered trademark) PME-400 (R ₃ is CH ₃ , R ₄ is C ₂ H ₅ , R ₅ is C ₃ H ₆ , p is a mixture of 9 on average, q is 0, R ₆ is CH ₃ ) and the like are suitable.

The amount of the (meth)acrylic acid ester having an alkylene oxide group is preferably 40% by weight or less, more preferably 1 to 15% by weight, and still more preferably 2 to 10% by weight with respect to the total amount of the vinyl-based monomer. And it is particularly preferably 3 to 7% by weight. By setting the amount of the (meth)acrylic acid ester having an alkylene oxide group to be more than the lower limit of the above range, it becomes easier to disperse the core particles in the primary particles in the aqueous medium. When the amount of the (meth)acrylic acid ester having an alkylene oxide group exceeds 40% by weight with respect to the total amount of the polymerizable vinyl-based monomer, polymerization stability decreases and the number of coalesced particles may increase.

In addition, it is preferable that the vinyl monomer contains a urethane acrylate oligomer as a polyfunctional vinyl monomer together with a monofunctional vinyl monomer such as a (meth)acrylic acid ester monomer. Thereby, since the 10% compressive strength of the core particles can be lowered, it becomes easy to realize the conductive resin particles having a 10% compressive strength equal to or less than the upper limit of the above-described range. The urethane acrylate oligomer, when cured alone, preferably exhibits a glass transition temperature (Tg) (measured from viscoelasticity) of 0 to 30°C. When Tg is less than 0°C, there are cases where adhesiveness appears on the core particles. When Tg is 30°C or less, conductive resin particles having high resilience can be obtained. The Tg shown when the urethane acrylate oligomer is cured alone is more preferably 0 to 28°C, and still more preferably 0 to 25°C.

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.

Commercially available products of the urethane acrylate oligomer include, for example, ``New Frontier (registered trademark) RST-402'' and ``New Frontier (registered trademark) RST'' of the New Frontier (registered trademark) RST series manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd. New Frontier (registered trademark) series urethane acrylate oligomers such as "201" and the like, and the UF series "UF-A01P" manufactured by Kyoeisha Chemical Co., Ltd. are mentioned.

[Method of manufacturing core particles]

When the core particle of the present invention is made of a polymer of a vinyl-based monomer, it can be obtained by polymerizing a vinyl-based monomer. As the polymerization method, known methods for obtaining resin particles, such as emulsion polymerization, dispersion polymerization, suspension polymerization, and seed polymerization, can be used.

[Method for producing core particles by suspension polymerization]

The suspension polymerization is a method of polymerizing a vinyl-based monomer in an aqueous medium. Examples of the aqueous medium include water and a mixture of water and a water-soluble organic solvent (eg, a lower alcohol having 5 or less carbon atoms).

If necessary, the suspension polymerization may be performed in the presence of a polymerization initiator. As a polymerization initiator, for example, benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, benzoyl orthochloroperoxide, methyl ethyl ketone peroxide, diisopropyl peroxy dicarbonate, cumene hydroperoxide, t-butyl hydroperoxide Oil-soluble peroxides such as; Oil-soluble azo compounds, such as 2,2'-azobisisobutyronitrile, and 2,2'-azobis (2,4-dimethylvaleronitrile), are mentioned. These polymerization initiators can be used individually or in combination of two or more, respectively. On the other hand, the amount of the polymerization initiator used is sufficient to be about 0.1 to 1 part by weight based on 100 parts by weight of the vinyl monomer.

Further, the suspension polymerization may be performed in the presence of a dispersant and/or a surfactant, if necessary. Examples of the dispersant include poorly water-soluble inorganic salts such as calcium phosphate and magnesium pyrophosphate; And water-soluble polymers such as polyvinyl alcohol, methylcellulose, and polyvinylpyrrolidone.

Further, examples of the surfactant include anionic surfactants such as sodium oleate, sodium lauryl sulfate, sodium dodecylbenzenesulfonate, alkyl naphthalene sulfonate, and alkyl phosphate ester salt; Nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxysorbitan fatty acid ester, polyoxyethylene alkylamine, and glycerin fatty acid ester; Amphoteric surfactants, such as lauryl dimethylamine oxide, etc. are mentioned.

The above dispersant and surfactant may be used alone or in combination of two or more. Among them, from the viewpoint of dispersion stability, it is preferable to use a dispersant of a poorly water-soluble phosphate such as calcium phosphate and magnesium pyrophosphate, and an anionic surfactant such as an alkyl sulfate or an alkylbenzene sulfonate in combination.

The amount of the dispersant is preferably 0.5 to 10 parts by weight based on 100 parts by weight of the vinyl-based monomer, and the amount of surfactant is preferably 0.01 to 0.2 parts by weight based on 100 parts by weight of the aqueous medium.

The suspension polymerization can be initiated by preparing an oil phase containing the vinyl-based monomer, dispersing the prepared oil phase in an aqueous phase containing an aqueous medium, and heating the aqueous phase in which the oil phase is dispersed. On the other hand, when a polymerization initiator is used, an oil phase is prepared by mixing a polymerization initiator with the vinyl-based monomer. In addition, when using a dispersant and/or a surfactant, an aqueous medium is prepared by mixing a dispersant and/or a surfactant in an aqueous medium. On the other hand, the volume average particle diameter of the core particles can be appropriately controlled by adjusting the mixing ratio of the oil phase and the aqueous phase, the amount of the dispersant, and the amount of surfactant, and the stirring conditions and the dispersion conditions.

As a method of dispersing the oil phase in the water phase, for example, a method of directly adding the oil phase into the water phase and dispersing the oil phase as droplets in the water phase by a stirring force such as a propeller blade; A method of dispersing the oil phase in the water phase using a homomixer, which is a dispersing machine that uses a high shear force composed of a rotor and a stirrer by directly adding the oil phase to the water phase; Various methods, such as a method of directly adding the oil phase in the water phase and dispersing the oil phase in the water phase using an ultrasonic disperser or the like, are mentioned. Among these, an oil phase is directly added to the aqueous phase, a high-pressure type disperser such as a microfluidizer or a nanomizer (registered trademark) is used, and the collision between droplets of the mixture or the collision of the mixture against the base wall is used, and the oil phase A method of dispersing in an aqueous phase as droplets; Dispersing the oil phase through a porous MPG (microporous glass) membrane into an aqueous phase or the like is preferable because the particle diameter of the core particles can be made more uniform.

In addition, the polymerization temperature is preferably about 40 to 90°C. And the time to maintain this polymerization temperature is preferably about 0.1 to 10 hours. On the other hand, the polymerization reaction may be performed in an inert gas atmosphere that is inert to the reactant (oil phase) in the polymerization reaction system, such as a nitrogen atmosphere. In addition, when the boiling point of the vinyl-based monomer is near the polymerization temperature or below the polymerization temperature, it is preferable to perform suspension polymerization under airtight or under pressure using an internal pressure polymerization equipment such as an autoclave so that the vinyl-based monomer does not volatilize.

Then, after completion of the polymerization reaction, depending on the purpose, the dispersant is decomposed and removed with an acid or the like, followed by filtration, water washing, dehydration, drying, pulverization, classification, etc., whereby the target core particles can be obtained.

[Method for producing core particles by seed polymerization]

In the method for producing core particles according to the seed polymerization method, first, seed particles are added to an aqueous emulsion composed of a vinyl-based monomer and an aqueous medium. Examples of the aqueous medium include water and a mixed medium of water and a water-soluble solvent (for example, a lower alcohol having 5 or less carbon atoms).

It is preferable that a surfactant is contained in an aqueous medium. As the surfactant, any of anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric ionic surfactants can be used.

Examples of the anionic surfactant include fatty acid soaps such as sodium oleate and castor oil potassium soap, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, and alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate. , Alkyl naphthalene sulfonate, alkanesulfonate, dialkyl sulfosuccinate such as sodium di(2-ethylhexyl) sulfosuccinate, alkenyl sulfonic acid salt (dipotassium salt), alkyl phosphate ester salt, naphthalene sulfonic acid formalin condensate, poly And polyoxyethylene alkyl ether sulfates such as oxyethylene alkylphenyl ether sulfate, sodium polyoxyethylene lauryl ether 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 amphoteric ionic surfactant include lauryl dimethylamine oxide and a phosphoric acid ester or phosphorous acid ester surfactant. These surfactants may be used alone or in combination of two or more. Among the above surfactants, anionic surfactants are preferred from the viewpoint of dispersion stability during polymerization.

An aqueous emulsion can be produced by a known method. For example, an aqueous emulsion can be obtained by adding a vinyl-based monomer to an aqueous medium and dispersing it with a fine emulsifier such as a homogenizer, an ultrasonic treatment device, or a nanomizer. The vinyl-based monomer may contain a polymerization initiator as necessary. The polymerization initiator may be mixed with a vinyl-based monomer in advance, and then dispersed in an aqueous medium, or those obtained by dispersing both separately in an aqueous medium may be mixed. The particle diameter of the droplets of the vinyl-based monomer in the obtained aqueous emulsion is preferably smaller than that of the seed particles, since the vinyl-based monomer is efficiently absorbed by the seed particles.

The seed particles may be added directly to the aqueous emulsion, or may be added in a form in which the seed particles are dispersed in an aqueous dispersion medium. After addition of the seed particles to the aqueous emulsion, the vinyl monomer is absorbed into the seed particles. This absorption can usually be performed by stirring the aqueous emulsion after the seed particles are added at room temperature (about 20° C.) for 1 to 12 hours. Further, the water absorption may be promoted by heating the aqueous emulsion to about 30 to 50°C.

The seed particles swell by absorbing the vinyl-based monomer. The mixing ratio of the vinyl-based monomer and the seed particle is preferably in the range of 5 to 150 parts by weight, and more preferably in the range of 10 to 120 parts by weight per 1 part by weight of the seed particle. When the mixing ratio of the vinyl-based monomer to the seed particles decreases, the increase in the particle diameter due to polymerization decreases, and thus the productivity may decrease. When the mixing ratio of the vinyl-based monomer to the seed particles increases, the vinyl-based monomer is not completely absorbed by the seed particles, and abnormal particles may be produced by independent suspension polymerization in an aqueous medium. On the other hand, the end of absorption can be determined by confirming the enlargement of the particle diameter by observation of an optical microscope.

To the aqueous emulsion, a polymerization initiator can be added as needed. As a polymerization initiator, for example, benzoyl peroxide, lauroyl peroxide, orthochloro benzoyl peroxide, orthomethoxy benzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, t-butylperoxy-2-ethylhexa Organic peroxides such as noate and di-t-butyl peroxide, 2,2'-azobisisobutyronitrile, 1,1'-azobiscyclohexanecarbonitrile, 2,2'-azobis (2,4 -Azo compounds, such as dimethylvaleronitrile), etc. are mentioned. It is preferable to use the polymerization initiator in the range of 0.1 to 3 parts by weight based on 100 parts by weight of the vinyl-based monomer.

Next, the core particles are obtained by polymerizing the vinyl-based monomer absorbed by the seed particles. The polymerization temperature is appropriately selected depending on the type of the vinyl-based monomer and the polymerization initiator. The polymerization temperature is preferably in the range of 25 to 110°C, and more preferably in the range of 50 to 100°C. It is preferable to perform the polymerization reaction by heating up after the monomer and the polymerization initiator are completely absorbed by the seed particles. After completion of polymerization, if necessary, the core particles are centrifuged to remove the aqueous medium, washed with water and a solvent, dried and isolated.

In the polymerization step, in order to improve the dispersion stability of the core particles, a polymer dispersion stabilizer may be added. As the polymer dispersion stabilizer, for example, polyvinyl alcohol, polycarboxylic acid, cellulose (hydroxyethyl cellulose, carboxymethyl cellulose, etc.), polyvinylpyrrolidone, and the like can be used. Further, these polymer dispersion stabilizers and inorganic water-soluble polymer compounds such as sodium tripolyphosphate can also be used in combination. Among these, polyvinyl alcohol and polyvinylpyrrolidone are preferable as polymer dispersion stabilizers. The amount of the polymer dispersion stabilizer added is preferably 1 to 10 parts by weight based on 100 parts by weight of the vinyl-based monomer.

Further, in order to suppress the generation of emulsified particles in an aqueous system, water-soluble polymerization inhibitors such as nitrites, sulfites, hydroquinones, ascorbic acids, water-soluble vitamins B, citric acid, and polyphenols may be used.

[Shell]

The shell is made of a conductive polymer. The conductive polymer may be a polyaniline-based polymer or a polyisothianapthene-based polymer, but since a more uniform shell is easily formed and conductive resin particles having a desired conductivity are obtained, a nitrogen-containing heteroaromatic compound and a sulfur-containing heteroaromatic It is preferably a polymer of at least one monomer selected from the group consisting of compounds.

Examples of the nitrogen-containing heteroaromatic compound include pyrrole, indole, imidazole, pyridine, pyrimidine, pyrazine, and their alkyl substituents (e.g., methyl, ethyl, propyl, butyl, etc. A substituent), a halogen substituent (for example, a substituent with a halogen group such as a fluoro group, a chloro group, and a bromo group), and derivatives such as a nitrile substituent. From the point where a more uniform shell is easily formed and conductive resin particles having a desired conductivity are obtained, a polymer of a pyrrole and a pyrrole derivative is preferable as a nitrogen-containing heteroaromatic compound. As a pyrrole derivative, 3,4-dimethylpyrrole is mentioned.

As the sulfur-containing aromatic compound, a thiophene and a thiophene derivative are preferable as the nitrogen-containing aromatic compound from the viewpoint of obtaining conductive resin particles having desired conductivity. As a thiophene derivative, 3,4-ethylenedioxythiophene, 3-methylthiophene, 3-octylthiophene, etc. are mentioned. These monomers may be used alone to form a homopolymer, or two or more types may be used in combination to form a copolymer.

The thickness of the shell is preferably in the range of 30 to 300 nm, more preferably in the range of 50 to 200 nm. When the thickness of the shell is within the above range, it becomes possible to obtain sufficient conductivity. The variation in the thickness of the shell is preferably 50% or less, and more preferably 40% or less.

[How to form a shell]

When the conductive resin particles constituting the shell is a polymer of at least one monomer selected from the group consisting of a nitrogen-containing heteroaromatic compound and a sulfur-containing heteroaromatic compound (hereinafter, simply referred to as a ``monomer''), It can be produced by a method of coating the polymer of the monomer on the core particles. As a method of coating the polymer of the monomer on the core particles, the core particles are dispersed in an aqueous medium containing an oxidizing agent to obtain a dispersion (emulsion or suspension), and a monomer is added to the dispersion and stirred to undergo oxidation polymerization. Thus, a method of coating the polymer of the monomer on the surface of the core particle is preferable.

The amount of the monomer to be added may be set according to the desired conductivity, and is preferably in the range of 1 to 30 parts by weight, and more preferably 3 to 20 parts by weight, based on 100 parts by weight of the core particles. The amount of the monomer added is 1 part by weight or more with respect to 100 parts by weight of the core particles, and the entire surface of the core particles is uniformly coated with the polymer of the monomer, so that desired conductivity can be obtained. On the other hand, by setting the addition amount of the monomer to 30 parts by weight or less based on 100 parts by weight of the core particles, it is possible to prevent the addition of the monomers from being independently polymerized and other than the target conductive resin particles.

(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, alkylnaphthalenesulfonic acid, metal halides such as ferric chloride and aluminum chloride, halogen acids such as potassium perchlorate, potassium persulfate, And peroxides such as ammonium persulfate, sodium persulfate, and hydrogen peroxide. These may be used alone or in combination. As the oxidizing agent, an alkali metal salt of an inorganic peracid is preferable. Specific examples of the alkali metal salt of the inorganic persulfate include potassium persulfate and sodium persulfate.

The amount of the oxidizing agent used 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 be 0.5 molar equivalent or more with respect to the total amount of the monomer, the entire surface of the core particles is uniformly coated with a shell containing the polymer of the monomer, so that desired conductivity can be obtained. On the other hand, by setting the amount of the oxidizing agent to be 2.0 molar equivalents or less with respect to the total amount of the monomers, it is possible to prevent the added monomers from being independently polymerized and other than the target conductive resin particles.

The aqueous medium to which the oxidizing agent is added is not particularly limited as long as it is capable of dissolving or dispersing a monomer, but water or alcohols such as water and methanol, ethanol, n-propanol, isopropanol, n-butanol and t-butanol; Ethers such as diethyl ether, isopropyl ether, butyl ether, methyl cellosolve, and tetrahydrofuran; Mixed media with ketone types, such as acetone, methyl ethyl ketone, and diethyl ketone, are mentioned.

(2) aqueous medium

It is preferable that the aqueous medium to which the oxidizing agent is added has a pH of 3 or more. When the pH is 3 or more, the entire surface of the core particles is uniformly covered with a shell containing a polymer of a monomer, so that desired conductivity can be obtained. In order to stably coat, it is more preferable to adjust the pH in the range of 3 to 10.

(3) surfactant

A surfactant may be added to the aqueous medium. As surfactants, anionic surfactants, cationic surfactants, amphoteric ionic surfactants, and nonionic surfactants can all be used.

Examples of the anionic surfactant include fatty acid soaps such as sodium oleate and castor oil potassium soap, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, and alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate. , Alkyl sulfonate, alkyl naphthalene sulfonate, alkanesulfonate, dialkyl sulfosuccinate, alkyl phosphate ester salt, naphthalene sulfonic acid formalin condensate, polyoxyethylene alkylphenyl ether sulfate, polyoxyethylene alkyl sulfate salt Can be lifted.

As the nonionic surfactant, for example, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxysorbitan fatty acid ester, polyoxyethylene alkylamine, glycerin Fatty acid ester, oxyethylene-oxypropylene block polymer, etc. are mentioned.

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 amphoteric surfactants include lauryl dimethylamine oxide, phosphoric acid ester or phosphorous acid ester surfactants, and the like. These surfactants may be used alone or in combination of two or more. The amount of 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 a surfactant. As a polymer dispersion stabilizer, for example, polyacrylic acid, its copolymer and its neutralization and polymethacrylic acid, its copolymer and its neutralization, polyvinylpyrrolidone, hydroxypropyl cellulose (HPC), etc. Can be mentioned. The polymer dispersion stabilizer may be used in combination with the above-described surfactant.

(4) Oxidative polymerization

In the above-described method for producing conductive resin particles using oxidation polymerization, the core particles are dispersed in an aqueous medium containing an oxidizing agent to form a dispersion, a monomer is added to the dispersion, and agitated to perform oxidative polymerization, so that the core particles are converted to the monomer. To obtain the conductive resin particles coated with the polymer of. The temperature for oxidation polymerization is preferably in the range of -20 to 40°C, and the time for oxidation polymerization is preferably in the range of 0.5 to 10 hours.

On the other hand, the emulsion in which the conductive resin particles are dispersed is centrifuged if necessary to remove the aqueous medium, washed with water and a solvent, and then dried and isolated.

In the above description, as a method of coating a polymer on the core particles, a method of oxidizing polymerization of the monomer by mixing with a monomer in an aqueous medium containing the core particles and an oxidizing agent has been described, but the method of coating the polymer on the core particles is this method. Not limited. For example, a method of coating a polymer on the core particles using a dry method may also be employed. As the dry method, for example, 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 hybridizer, a mechano fusion method, and the like can be used.

[Use of conductive resin particles]

The electroconductive resin particle of this invention can be used suitably in an application aimed at expressing electroconductivity by making electroconductive resin particle adhere closely. The conductive resin particles of the present invention form a conductive paste for electrical connection on an electronic circuit board, etc. (conductive particles are dispersed in a binder resin), and when applied and dried, a conductive film for electrical connection on an electronic circuit board, etc. is formed. Conductive ink (conductive particles are dispersed in a solution in which a binder resin is dissolved in a solvent), a conductive elastomer layer of a conductive roller used for transfer rollers (conductive particles are dispersed in the elastomer), anti-blocking agent It can be used as electroconductive particle used for etc.

[Conductive resin composition]

The conductive resin composition of the present invention contains the conductive resin particles of the present invention and a matrix resin. The conductive resin composition of the present invention can be produced by mixing the conductive resin particles of the present invention with a matrix resin.

As the matrix resin, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polyamide 6, polyamide 66, polyamide 12, ABS resin (acrylonitrile-butadiene-styrene copolymer resin), AS resin (acrylo Nitrile-styrene copolymer resin), polyethylene, polypropylene, polyacetal, polyamideimide, polyethersulfone, polyimide, polyphenylene oxide, polyphenylene sulfide, polystyrene, thermoplastic polyurethane elastomer, thermoplastic polyester elastomer, thermoplastic poly 1 of thermoplastic resins such as amide elastomer, polyvinyl chloride, polyvinylidene fluoride, ethylene tetrafluoroethylene copolymer (ETFE resin), tetrafluoroethylene perfluoroalkyl vinyl ether copolymer (PFA resin), and polyether ketone It is possible to use species or a mixture of two or more. The type of thermoplastic resin used as the matrix resin depends on the properties of the target conductive resin composition (mechanical strength, abrasion resistance, chemical resistance, heat resistance, moldability when forming a molded article by molding the conductive resin composition, etc.). It is selected appropriately.

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.

Other functional fillers may be appropriately added to the conductive resin composition according to the function required for the molded article of interest. Examples of the functional filler include reinforcing fibers such as glass fibers and carbon fibers, flame retardants, mat 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, conductive resin particles, and other appropriately contained functional fillers and molding them into a required shape by hot pressing. Alternatively, in the conductive resin composition of the present invention, the matrix resin, conductive resin particles, and other appropriately contained functional fillers are suitably mixed (kneaded) in a heated state, molded into pellets, and then extrusion-molded using the pellets or It can be made into a molded article by injection molding or the like. Thereby, a molded article excellent in conductivity and antistatic properties can be obtained.

[Coating agent]

The coating agent of the present invention contains the conductive resin particles of the present invention and a binder resin.

The binder resin is not particularly limited as long as it is used in the field according to required properties such as transparency, dispersibility of conductive resin particles, light resistance, moisture resistance, and heat resistance. Examples of the binder resin include (meth)acrylic resin; (Meth)acrylic-urethane resin; Urethane resin; Polyvinyl chloride resin; Polyvinylidene chloride resin; Melamine resin; Styrene resin; Alkyd resin; Phenolic resin; Epoxy resin; Polyester resin; Silicone resins such as alkyl polysiloxane resins; Modified silicone resins such as (meth)acrylic-silicone resin, silicone-alkyd resin, silicone-urethane resin, and silicone-polyester resin; 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 is classified into an ionizing radiation curable resin such as an ultraviolet curable resin and an electron beam curable resin, a thermosetting resin, and a warm curable resin, depending on the type of curing.

Examples of the thermosetting resin include a thermosetting urethane resin composed of 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 polyhydric alcohol polyfunctional (meth)acrylate; And a polyfunctional urethane acrylate resin synthesized from a diisocyanate, a polyhydric alcohol, and a (meth)acrylic acid ester having a hydroxy group. As the ionizing radiation curable resin, a polyfunctional (meth)acrylate resin is preferable, and a polyhydric alcohol polyfunctional (meth)acrylate having three or more (meth)acryloyl groups in one molecule is more preferable. As a polyhydric alcohol polyfunctional (meth)acrylate having three or more (meth)acryloyl groups in one molecule, specifically, trimethylolpropane tri(meth)acrylate, trimethylolethantri(meth)acrylate, 1,2,4-cyclohexanetetra(meth)acrylate, pentaglycerol triacrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol triacrylate, dipentaerythritol penta Acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol triacrylate, tripentaerythritol hexaacrylate, and the like. The ionizing radiation curable resin may be used in combination of two or more.

In addition to these, as the ionizing radiation curable resin, polyether resins, polyester resins, epoxy resins, alkyd resins, spiroacetal resins, polybutadiene resins, polythiolpolyene resins and the like can be used in addition to these.

When an ultraviolet curable resin is used among the ionizing radiation curable resins, a photopolymerization initiator is added to the ultraviolet curable resin to obtain a binder resin. Any of the photopolymerization initiators may be used, but it is preferable to use those in the ultraviolet curable resin to be used.

Examples of the photopolymerization initiator include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, α-hydroxyalkylphenones, α-aminoalkylphenones, anthraquinones, thioxanthones, azo compounds, Peroxides (described in Japanese Patent Laid-Open No. 2001-139663, etc.), 2,3-dialkyldione compounds, disulfide compounds, fluoroamine compounds, aromatic sulfoniums, onium salts, borate salts, active halogen compounds, α-acyloxime ester, etc. are mentioned.

Examples of the acetophenones include acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, 1-hydroxydimethylphenylketone, 1-hydroxycyclohexylphenylketone, and 2-methyl- 4-methylthio-2-morpholinopropiophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone, and the like. Examples of the benzoin include benzoin, benzoin benzoate, benzoin benzene sulfonic acid ester, benzoin toluene sulfonic acid ester, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and the like. . Examples of the benzophenones include benzophenone, 2,4-dichlorobenzophenone, 4,4-dichlorobenzophenone, and p-chlorobenzophenone. Examples of the phosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide. Examples of the ketals 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.

As a commercially available photo-radical polymerization initiator, BASF Japan Co., Ltd. product name "Irgacure (registered trademark) 651" (2,2-dimethoxy-1,2-diphenylethan-1-one), BASF Japan Co., Ltd. make "Irgacure (registered trademark) 184" of "Irgacure (registered trademark) 184" manufactured by BASF Japan Co., Ltd. "Irgacure (registered trademark) 907" (2-methyl-1-[4-(methylthio)phenyl]-2-(4) -Morpholinyl)-1-propanone) etc. are mentioned as a preferable example.

The amount of the photopolymerization initiator used is usually in the range of 0.5 to 20% by weight, and preferably in the range of 1 to 5% by weight, based on 100% by weight of the binder resin.

In addition to the curable resin, a thermoplastic resin may be used as the binder resin. Examples of the thermoplastic resin include cellulose derivatives such as acetyl cellulose, nitro cellulose, acetyl butyl cellulose, ethyl cellulose, and methyl cellulose; Vinyl resins such as vinyl acetate homopolymers and copolymers, vinyl chloride homopolymers and copolymers, and vinylidene chloride homopolymers and copolymers; 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; Polystyrene resin; Polyamide resin; Linear polyester resin; And polycarbonate resin.

The coating agent may further contain water and/or an organic solvent. When the coating agent is applied to the base film, the organic solvent is not particularly limited as long as it becomes easy to apply the coating agent to the base film by including it in the coating agent. Examples of the organic solvent include aromatic solvents such as toluene and xylene; Alcohol solvents such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, and propylene glycol monomethyl ether; Ester solvents such as ethyl acetate and butyl acetate; Ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone; 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 solvents such as chloroform, dichloromethane, trichloromethane, and methylene chloride; Ether solvents such as tetrahydrofuran, diethyl ether, 1,4-dioxane, and 1,3-dioxolane; An amide solvent, such as N-methylpyrrolidone, dimethylformamide, dimethyl sulfoxide, and dimethylacetamide, can be used. These organic solvents may be used alone or in combination of two or more.

[film]

The film of this invention contains the electroconductive resin particle of this invention. The film of the present invention has, for example, a configuration obtained by applying a coating agent containing conductive resin particles and a binder resin on a base film. A film of this configuration can be preferably used as a conductive film or an antistatic film.

It is preferable that the said base film is transparent. Examples of the transparent base film include polyester polymers such as polyethylene terephthalate (hereinafter abbreviated as "PET"), polyethylene naphthalate, and cellulose polymers such as diacetyl cellulose and triacetyl cellulose (TAC). And films made of polymers such as acrylic polymers such as polycarbonate polymers and polymethyl methacrylate. In addition, as a transparent base film, styrene polymers such as polystyrene, acrylonitrile-styrene copolymers, polyethylene, polypropylene, polyolefins having a cyclic to norbornene structure, olefin-based polymers such as ethylene-propylene copolymers, and chlorinated Films made of polymers such as vinyl-based polymers and amide-based polymers such as nylon and aromatic polyamides are also mentioned. In addition, as a transparent base film, imide polymer, sulfone polymer, polyether sulfone polymer, polyether ether ketone polymer, polyphenyl sulfide polymer, vinyl alcohol polymer, vinylidene chloride polymer, vinyl butyral polymer , Arylate-based polymers, polyoxymethylene-based polymers, epoxy-based polymers, and films made of polymers such as blends of the polymers. As the base film, one having a particularly low birefringence index is preferably used. Further, a film in which an easily adhesive layer is further formed on a film made of these polymers can also be used as the base film. The easily adhesive layer may be formed of a resin such as a (meth)acrylic resin, a copolymerized polyester resin, a polyurethane resin, a styrene-maleic acid graft polyester resin, and an acrylic graft polyester resin. In addition, in this specification, "(meth)acryl" shall mean acrylic or methacrylic.

The thickness of the base film can be appropriately determined, but generally, it is in the range of 10 to 500 µm, preferably in the range of 20 to 300 µm, from the viewpoints of strength, workability such as handling, and thin layer properties, It is more preferable that it is in the range of 30-200 micrometers.

Moreover, you may add an additive to the said base film. Examples of the additives include ultraviolet absorbers, infrared absorbers, antistatic agents, refractive index adjusters, and enhancers.

As a method of coating the coating agent on the base film, bar coating, blade coating, spin coating, reverse coating, die coating, spray coating, roll coating, gravure coating, micro gravure coating, lip coating, air knife coating, dipping method Known coating methods such as are mentioned.

When the binder resin contained in the coating agent is an ionizing radiation curable resin, after the coating agent is applied, the solvent is dried as necessary, and the ionizing radiation curable resin is further irradiated with active energy rays to cure the ionizing radiation curable resin.

Examples of the active energy ray include ultraviolet rays emitted from light sources such as xenon lamps, low pressure mercury lamps, high pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, carbon arc lamps, and tungsten lamps; Usually 20 to 2000KeV Cockcroft Walton type, Van Degraf type, resonance transformer type, insulation core transformer type, linear type, dynamitron type, high frequency type, etc.Electron rays, α-rays, β-rays, γ-rays, etc., taken out from electron beam accelerators You can use

The thickness of the layer (glare layer) in which conductive resin particles are dispersed in the binder resin formed by the coating (and curing) of the coating agent is not particularly limited, and is appropriately determined by the particle diameter of the conductive resin particles, but 1 to It is preferably in the range of 10 µm, and more preferably in the range of 3 to 7 µm.

On the other hand, the film of the present invention is not limited to the above-described configuration, and the same molding resin composition as the coating agent containing conductive resin particles and a binder resin may be formed into a film shape. A film of this configuration can be preferably used as a conductive film or an antistatic film.

[Gap material]

The gap material of the present invention contains the conductive resin particles of the present invention. The gap material of the present invention provides a uniform gap between various substrates, such as an in-plane spacer for a liquid crystal display element, a seal part spacer for a liquid crystal display element, a spacer for an EL (electroluminescence) display element, a spacer for a touch panel, and various substrates such as ceramics or plastics. It is used as a spacer for maintaining an inter-pole distance such as a retainable inter-pole holding material. Since the gap material of the present invention contains the conductive resin particles of the present invention having a good conductivity, it has conductivity and exhibits an antistatic function.

When the gap material of the present invention obtains a uniform gap effect, the coefficient of variation of the particle diameter based on the volume of the conductive resin particles is preferably 20% or less, and more preferably less than 10%.

Example

Hereinafter, the present invention will be described with reference to Examples and Comparative Examples, but the present invention is not limited thereto. First, the volume average particle diameter of the electroconductive resin particles in the following Examples and Comparative Examples, the coefficient of variation of the particle diameter based on the volume, the 10% compressive strength, and the measuring method of the electrical conductivity are described.

(Measurement method of the volume average particle diameter of the conductive resin particles and the coefficient of variation of the volume-based particle diameter)

The measurement of the volume average particle diameter of the electroconductive resin particles and the coefficient of variation (CV value) of the volume-based particle diameter were performed by the Coulter method as follows.

The volume average particle diameter of the electroconductive resin particles is measured by Coulter Multisizer ^™ 3 (a measuring apparatus manufactured by Beckman Coulter Co., Ltd.). It is assumed that the measurement is performed using an aperture calibrated according to ^{the Multisizer TM 3 User's Manual issued by Beckman Coulter.}

On the other hand, the aperture used for 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 according to the size of the selected aperture. For example, when an aperture having a size of 50 µm is selected, the Current (aperture current) is set to -800 and the Gain (gain) is set to 4.

As a sample for measurement, 0.1 g of conductive resin particles are contained in 10 ml of a 0.1 wt% nonionic surfactant aqueous solution, a touch mixer (manufactured by Yamato Scientific Co., Ltd., ``TOUCHMIXER MT-31'') and an ultrasonic cleaner (manufactured by Belvo Clear, ``ULTRASONIC CLEANER'' VS-150") and used as a dispersion. During the measurement, the beaker is slowly stirred so that no air bubbles enter, and the measurement is terminated when 100,000 conductive resin particles are measured. The volume average particle diameter of the electroconductive resin particles is an arithmetic average in the particle size distribution based on the volume of 100,000 particles.

The coefficient of variation of the particle diameter based on the volume of the conductive resin particles is calculated by the following equation.

Coefficient of variation of the particle diameter based on the volume of the conductive resin particles

=(Standard deviation of particle size distribution based on volume of conductive resin particles

÷ Volume average particle diameter of conductive resin particles) × 100

(Measurement method of 10% compressive strength of conductive resin particles)

The 10% compressive strength (S10 strength) of the resin particles was measured under the following measurement conditions using a micro compression tester "MCTM-200" manufactured by Shimadzu Corporation.

Specifically, a dispersion in which resin particles were dispersed in ethanol was applied to a mirror-finished steel sample stand and dried to prepare a sample for measurement. Then, under an environment of room temperature of 20°C and relative humidity of 65%, one independent fine resin particle (a state in which no other resin particles exist within the range of at least 100 μm in diameter) is selected and selected with an optical microscope of MCTM-200. The diameter of one resin particle was measured with the particle diameter measurement cursor of MCTM-200. At this time, as the resin particles, resin particles within the range of ±0.5 µm from the volume average particle diameter determined by the measurement method according to the Coulter method described above were selected. Resin particles outside the range are not used for the measurement of compressive strength. Next, by lowering the test indenter at the apex of the selected resin particles at the following load speed, a load is gradually applied to the resin particles up to a maximum load of 9.81 mN, and the load at the time when the diameter of the previously measured resin particles is displaced by 10%. From, the compressive strength was determined by the following equation. Each resin particle was measured six times, and the average value of the four data excluding the data of the maximum value and the minimum value was taken as 10% compressive strength (S10 strength).

<Calculation formula of compressive strength>

Compressive strength (MPa) = 2.8 × load (N)/｛π × (particle diameter (mm)) ² ｝

<Measurement conditions for compressive strength>

Test temperature: room temperature (20℃) relative humidity 65%

Upper pressure indenter: flat indenter with a diameter of 50 μm (material: diamond)

Lower platen: SKS flat plate

Test type: Compression test (MODE1)

Test load: 9.81mN

Load speed: 0.732mN/sec

Displacement full scale: 20(㎛)

(Measurement method of conductivity of conductive resin particles)

With ``Powder Resistance Measurement System Model MCP-PD51'' (manufactured by Mitsubishi Chemical Analytech Co., Ltd.), each load (0, 4kN, 8kN, 12kN, 16kN, and 20kN) were added to the conductive resin particles, and the conductivity was measured. Among the electrical conductivity obtained by measuring each load, the highest numerical value was taken as the electrical conductivity of the conductive resin particles. About the electroconductive resin particle, the amount of water contained was measured by Karl Fischer water measurement beforehand, and it confirmed that the contained water amount was 1.0 weight% or less. As a resistivity meter used in the "powder resistance measurement system MCP-PD51 type", a low resistivity meter "Loresta (registered trademark)-GX MCP-T700" (manufactured by Mitsubishi Chemical Analytech Co., Ltd.) is used.

(Example 1)

[Production of Core Particles]

[Preparation of awards]

200 parts by weight of deionized water as an aqueous medium, 10 parts by weight of magnesium pyrophosphate as a dispersant, and 0.04 parts by weight of sodium lauryl sulfate as an anionic surfactant were added to a beaker to prepare an aqueous phase.

[Paid preparation]

In a beaker different from the beaker used for the preparation of the aqueous phase, as monofunctional (meth)acrylic acid ester monomer, 60 parts by weight of n-butyl acrylate, 15 parts by weight of methyl acrylate, 10 parts by weight of 2-ethylhexyl acrylate, and poly(ethylene glycol-propylene glycol) ) Monomethacrylate ("Blemmer (registered trademark) 50PEP-300" manufactured by Nichiyu Corporation) 5 parts by weight, and ethylene glycol dimethacrylate as a monomer represented by the above formula (I) (manufactured by Kyoeisha Chemicals Co., Ltd.) ``Light ester EG'') 10 parts by weight, 0.2 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 0.15 parts by weight of benzoyl peroxide were added as polymerization initiators, and sufficiently stirred to obtain an oil phase. The resulting mixture was prepared.

[polymerization]

The prepared oil phase was added to the previously prepared aqueous phase, and stirred for 10 minutes at a stirring speed of 5000 rpm using a homomixer (manufactured by Primix Co., Ltd., table type, product name ``Homo Mixer MARKII 2.5 type''), and the oil phase was dispersed in the aqueous phase, and the dispersion liquid Got it. This dispersion was put into a polymerization reactor equipped with a stirrer, a heating device, and a thermometer, and stirred at 60° C. for 6 hours to carry out a suspension polymerization reaction. Subsequently, after cooling the suspension (reaction liquid) in the polymerization reactor to 30° C., hydrochloric acid was added to decompose magnesium pyrophosphate. Then, the suspension was suction filtered. The residue of the filtration was washed with ion-exchanged water and dehydrated to obtain a hydrous cake of core particles made of a polymer of the desired vinyl-based monomer.

[Preparation of conductive resin particles]

[polymerization]

25 parts by weight of the hydrous cake body of the obtained core particles was dispersed in 50 parts by weight of deionized water to obtain a core particle dispersion. Next, as an oxidizing agent, 20 parts by weight of potassium persulfate was dissolved in 300 parts by weight of deionized water to prepare an aqueous potassium persulfate solution. The above-prepared core particle dispersion was mixed with the aqueous potassium persulfate solution, followed by stirring for 30 minutes. To the obtained mixture, 5 parts by weight of pyrrole as a nitrogen-containing aromatic compound is added and stirred at 25° C. for 5 hours to polymerize pyrrole. ). The obtained electroconductive resin particles had a volume average particle diameter of 14.8 µm, a coefficient of variation of a volume-based particle diameter of 45%, and a 10% compressive strength of 1.4 MPa.

[Conductivity measurement]

As a result of measuring the conductivity of the conductive resin particles obtained in the previous step, it was 2.4×10 ^-2 S/cm.

(Example 2)

[Production of Core Particles]

Instead of 60 parts by weight of n-butyl acrylate, 15 parts by weight of methyl acrylate and 10 parts by weight of 2-ethylhexyl acrylate, 79 parts by weight of n-butyl acrylate is used, and instead of 10 parts by weight of ethylene glycol dimethacrylate, ethylene glycol di 1 part by weight of methacrylate ("Light Ester EG" manufactured by Kyoeisha Chemical Co., Ltd.) and tetradecaethylene glycol dimethacrylate as a monomer represented by the above formula (II) ("Light ester 14EG" manufactured by Kyoeisha Chemical Co., Ltd.) '') 15 parts by weight, the same as in Example 1, except that the amount of benzoyl peroxide was changed to 0.3 parts by weight, and the stirring conditions for dispersing the oil phase in the aqueous phase were changed to ``stirring speed of 3500 rpm for 5 minutes''. Thus, a water-containing cake body of the target core particles was obtained.

[Preparation of conductive resin particles]

The same as in Example 1, except that the hydrated cake body of the core particles obtained in the previous step was used instead of the core particles of Example 1, and the amount of deionized water used to obtain the core particle dispersion was changed to 25 parts by weight. Thus, the objective electroconductive resin particle was obtained. The obtained electroconductive resin particles had a volume average particle diameter of 15.4 µm, a coefficient of variation of a volume-based particle diameter of 39%, and a 10% compressive strength of 2.3 MPa.

[Conductivity measurement]

As a result of measuring the conductivity of the conductive resin particles obtained in the previous step, it was 2.8 × 10 ^-2 S/cm.

(Example 3)

[Production of Core Particles]

In the same manner as in Example 1, a water-containing cake body of the target core particles was obtained.

[Preparation of conductive resin particles]

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, poly(3,4-ethylenedioc) was used as the target conductive polymer. Cyclofen) to obtain conductive resin particles coated with core particles with a shell. The obtained electroconductive resin particles had a volume average particle diameter of 16.2 µm, a coefficient of variation of a volume-based particle diameter of 46%, and a 10% compressive strength of 2.5 MPa.

[Conductivity measurement]

As a result of measuring the conductivity of the conductive resin particles obtained in the previous step, it was 1.8 × 10 ^-2 S/cm.

(Example 4)

[Production of Core Particles]

[Soap-free polymerization]

In a beaker, an oil phase was prepared by mixing 15 parts by weight of methyl methacrylate as a monofunctional (meth)acrylic acid ester monomer and 0.2 parts by weight of n-octyl mercaptan as a molecular weight modifier.

In a beaker different from the above, an aqueous potassium persulfate solution was prepared by dissolving 0.1 parts by weight of potassium persulfate as a polymerization initiator in 80 parts by weight of ion-exchanged water, and the oil phase was mixed with the aqueous potassium persulfate solution at 55° C. for 12 hours. Soap-free polymerization was performed. Thereby, a dispersion containing seed particles made of polymethyl methacrylate was obtained. The volume average particle diameter of the obtained seed particles was 0.51 µm.

[Seed polymerization]

Next, in a new beaker, as monofunctional (meth)acrylic acid ester monomer, 70 parts by weight of n-butyl acrylate, 5 parts by weight of methyl acrylate, 5 parts by weight of 2-ethylhexyl acrylate, and poly(ethylene glycol-propylene glycol) monomethacrylate ("Blemmer (registered trademark) 50PEP-300" manufactured by Nichiyu Corporation) 5 parts by weight, 10 parts by weight of ethylene glycol dimethacrylate as a monomer represented by the above formula (I), and 2,2' as a polymerization initiator -0.01 parts by weight of azobis (2-methylbutyronitrile) were mixed. To the obtained mixture, an aqueous solution obtained by dissolving 0.08 parts by weight of sodium di(2-ethylhexyl)sulfosuccinate as an anionic surfactant in 80 parts by weight of ion-exchanged water as an aqueous medium was mixed, and a homomixer (manufactured by Primix Co., Ltd., a tabletop type) , An emulsion was obtained by treating for 10 minutes at a stirring speed of 8000 rpm with the product name "Homomixer MARKII 2.5 type").

To this emulsion, 40 parts by weight of a dispersion containing seed particles obtained by the soap-free polymerization is added while stirring. After stirring for 3 hours, 240 parts by weight of ion-exchanged water in which 0.03 parts by weight of polyvinyl alcohol was dissolved as a polymer dispersion stabilizer was added, and the polymer emulsion obtained by polymerization with stirring at 60° C. for 6 hours was dehydrated by suction filtration, and then added to ion-exchanged water. By washing the residue, a hydrous cake body of core particles having a sharp particle size distribution was obtained. The volume average particle diameter of the obtained core particles was 1.2 µm.

[Preparation of conductive resin particles]

Except for changing the amount of deionized water used to obtain the core particle dispersion liquid by dispersing the core particles, using the hydrated cake body of the core particles obtained in the previous step in place of the core particles of Example 1 It carried out similarly to Example 1, and obtained the objective electroconductive resin particle. The obtained electroconductive resin particles had a volume average particle diameter of 1.3 µm, a coefficient of variation of the particle diameter based on a volume of 9%, and a 10% compressive strength of 1.4 MPa.

[Conductivity measurement]

As a result of measuring the conductivity of the conductive resin particles obtained in the previous step, it was 1.5 × 10 ^-2 S/cm.

(Example 5)

[Production of Core Particles]

The target core was carried out in the same manner as in Example 1, except that the amount of sodium lauryl sulfate was changed to 0.005 parts by weight, and when the oil phase was dispersed in the aqueous phase, stirring was performed for 10 minutes at a stirring speed of 200 rpm without using a homomixer. The hydrous cake body of particles was obtained.

[Preparation of conductive resin particles]

In the same manner as in Example 1, except that the hydrated cake body of the core particles obtained in the previous step was used in place of the core particles of Example 1, the target conductive resin particles were obtained. The obtained electroconductive resin particles had a volume average particle diameter of 198 µm, a coefficient of variation of a volume-based particle diameter of 49%, and a 10% compressive strength of 1.7 MPa.

[Conductivity measurement]

As a result of measuring the conductivity of the conductive resin particles obtained in the previous step, it was 2.0 × 10 ^-2 S/cm.

(Example 6)

[Production of Core Particles]

Instead of 60 parts by weight of n-butyl acrylate, 15 parts by weight of methyl acrylate and 10 parts by weight of 2-ethylhexyl acrylate, 45 parts by weight of n-butyl acrylate is used, and instead of 10 parts by weight of ethylene glycol dimethacrylate, urethane acrylate Except having used 50 parts by weight of oligomer (product name "New Frontier (registered trademark) RST-402", manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.), a water-containing cake body of the target core particles was obtained in the same manner as in Example 1.

[Preparation of conductive resin particles]

Except for changing the amount of deionized water used to obtain the core particle dispersion liquid by dispersing the core particles, using the hydrated cake body of the core particles obtained in the previous step in place of the core particles of Example 1 It carried out similarly to Example 1, and obtained the objective electroconductive resin particle. The obtained electroconductive resin particles had a volume average particle diameter of 16.2 µm, a coefficient of variation of a volume-based particle diameter of 44%, and a 10% compressive strength of 1.2 MPa.

[Conductivity measurement]

As a result of measuring the conductivity of the conductive resin particles obtained in the previous step, it was 2.6×10 ^-2 S/cm.

(Example 7)

[Production of Core Particles]

In the same manner as in Example 1, a water-containing cake body of the target core particles was obtained.

[Preparation of conductive resin particles]

The same as in Example 3, except that the core particles obtained in the previous process were used instead of the core particles of Example 3, and the amount of deionized water used when dispersing the core particles to obtain the core particle dispersion was changed to 50 parts by weight. To obtain the target conductive resin particles. The obtained electroconductive resin particles had a volume average particle diameter of 16.5 µm, a coefficient of variation of a particle diameter based on a volume of 42%, and a 10% compressive strength of 1.2 MPa.

[Conductivity measurement]

As a result of measuring the conductivity of the conductive resin particles obtained in the previous step, it was 2.9×10 ^-2 S/cm.

(Comparative Example 1)

[Production of Core Particles]

As a monofunctional (meth)acrylic acid ester monomer, 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, Core particles were obtained in the same manner as in Example 1, except that 95 parts by weight of methyl methacrylate was used and the amount of ethylene glycol dimethacrylate used was changed to 5 parts by weight.

[Preparation 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 when obtaining the core particle dispersion. The 10% compressive strength of the obtained conductive resin particles was 34.3 MPa.

[Conductivity measurement]

As a result of measuring the conductivity of the conductive resin particles obtained in the previous step, it was 2.2×10 ^-3 S/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 instead of pyrrole, and the stirring time during polymerization was changed to 24 hours. The 10% compressive strength of the obtained conductive resin particles was 36.4 MPa.

[Conductivity measurement]

As a result of measuring the conductivity of the conductive resin particles obtained in the previous step, it was 2.2×10 ^-3 S/cm.

(Comparative Example 3)

[Production of Core Particles]

In the seed polymerization, 70 parts by weight of n-butyl acrylate, 5 parts by weight of methyl acrylate, 5 parts by weight of 2-ethylhexyl acrylate, and poly(ethylene glycol-propylene glycol) monomethacrylate ("Blemmer( Registered trademark) 50PEP-300") In the same manner as in Example 4, except that 70 parts by weight of methyl methacrylate was used instead of 5 parts by weight, and the amount of ethylene glycol dimethacrylate used was changed to 30 parts by weight. Got it. The volume average particle diameter of the obtained core particles was 1.1 µm.

[Preparation of conductive resin particles]

In the same manner as in Example 4, except that the core particles obtained in the previous step were used instead of the core particles of Example 4, the target conductive resin particles were obtained. The obtained electroconductive resin particles had a volume average particle diameter of 1.2 µm, a coefficient of variation of the particle diameter based on a volume of 9%, and a 10% compressive strength of 36.1 MPa.

[Conductivity measurement]

As a result of measuring the conductivity of the conductive resin particles obtained in the previous step, it was 3.5×10 ^-3 S/cm.

The composition of the monomer mixture in which the volume average particle diameter of the conductive resin particles obtained in Examples 1 to 7 and Comparative Examples 1 to 3, the coefficient of variation of the particle diameter on a volume basis, the compressive strength of 10%, and the electrical conductivity were used for the production of the core particles. In Example 4 and Comparative Example 3, the composition of the monomer mixture used for seed polymerization) and the type of the monomer used for forming the shell are summarized in Table 1 and shown. On the other hand, in Table 1, n-butyl acrylate is "BA", methyl acrylate is "MA", 2-ethylhexyl acrylate is "2EHA", methyl methacrylate is "MMA", and poly(ethylene glycol-propylene glycol) Monomethacrylate “Blemmer (registered trademark) 50PEP-300”) is “50PEP-300”, ethylene glycol dimethacrylate is “EGDMA”, tetradecaethylene glycol dimethacrylate is “14EG”, urethane acrylate "New Frontier (registered trademark) RST-402" is abbreviated as "RST-402", respectively.

As described above, the conductive resin particles of Examples 1 to 7 have a 10% compressive strength of 0.1 to 30 MPa (1.2 to 2.5 MPa), and the 10% compressive strength of Comparative Examples 1 to 3 is greater than 30 MPa (34.3 to 36.4 MPa) Compared with the electrical conductivity (2.2 to 3.5 × 10 ^-3 S/cm) of the conductive resin particles, it was found that it had an excellent electrical conductivity (1.5 to 2.9 × 10 ^{-2 S/cm).}

(Example 8)

Conductive resin particles obtained in Example 1 were dissolved in 10 parts by weight of an acrylic resin as a binder resin (manufactured by Mitsubishi Chemical Co., Ltd., brand name "Dianal (registered trademark) BR-106") and 50 parts by weight of toluene as an organic solvent. 10 parts by weight was blended and uniformly dispersed to prepare a coating agent.

This coating agent was applied on a PET film having a thickness of 100 µm as a base film using a 30 µm applicator to form a coating film. It left to stand in a 70 degreeC high temperature bath for 2 hours, and the coating film on a PET film was dried, and the film which has conductivity was obtained.

The present invention can be implemented in various other forms without departing from the idea or main features. For this reason, the above-described embodiment is merely an illustration in all respects, and should not be interpreted as limiting. The scope of the present invention is indicated by the claims and is not limited to the text of the specification. In addition, all modifications and changes falling within the scope of equality of the claims are within the scope of the present invention.

In addition, this application claims priority based on Japanese Patent Application No. 2016-194260 filed in Japan on September 30, 2016. By mentioning this, all of its contents are incorporated into this application.

Claims (11)

A core particle made of a polymer,
As conductive resin particles having a shell made of a conductive polymer covering the core particles,
The compressive strength at the time of 10% compression deformation is 0.1 to 17 MPa,
The conductivity is 5.0×10 ^-3 ∼5.0×10 ^-1 S/cm,
The polymer is a monofunctional (meth)acrylic acid ester monomer,
Formula (I)

(In the formula, R ₁ is hydrogen or a methyl group, n is an integer of 1 to 4) and a monomer,
Formula (II)

(In the formula, R ₂ is hydrogen or a methyl group, m is an integer of 5 to 15) A conductive resin particle comprising a polymer of a monomer mixture containing a monomer represented by. delete delete The method of claim 1,
The conductive resin particles, wherein the conductive polymer is a polymer of at least one monomer selected from the group consisting of nitrogen-containing heteroaromatic compounds and sulfur-containing heteroaromatic compounds. The method of claim 1,
Conductive resin particles having a volume average particle diameter of 1 to 200 µm. The method of claim 1,
Electroconductive resin particles, characterized in that the coefficient of variation of the particle diameter on a volume basis is 10% or more. The method of claim 1,
The conductive resin particles, wherein the variation in the thickness of the shell is 50% or less. A conductive resin composition comprising the conductive resin particles of claim 1 and a matrix resin. A coating agent comprising the conductive resin particles of claim 1 and a binder resin. A film comprising the conductive resin particles of claim 1. A gap material comprising the conductive resin particles according to claim 1.