JP2013069678A - Particle for insulation coating, insulation coating conductive particle, anisotropic conductive material and connection structure - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide particles for insulation coating which allows for highly reliable conductive interconnection of the electrodes of a circuit member disposed to face each other, and are useful for obtaining an anisotropic conductive material capable of reliably preventing conduction between adjoining electrodes insulation of which must be ensured, and to provide insulation conductive particles including the same.SOLUTION: The particles for insulation coating for forming insulation coating conductive particles by coating base material particles composed of a metal having conductive surface includes a core shell structure having core particles and a shell layer. The core particles contains an organic polymer, and the shell layer contains a silicon based compound having at least one kind of unit selected from a group consisting of an SiOunit, an RSiOunit and an RSiOunit. The R represents at least one kind selected from a group consisting of an alkyl radical of 1-4C, an aromatic group of 6-24C, a vinyl group, and a γ-(meta) acryloxy propyl group.

Description

  The present invention relates to an insulating coating particle, an insulating coating conductive particle, an anisotropic conductive material, and a connection structure.

  By covering a part of the surface of the base particle with resin, the base particle has performance such as heat resistance, abrasion resistance, insulation, conductivity, water repellency, adhesiveness, dispersibility, gloss, and coloring. It is known that it can be granted. The particles so coated are used as various fillers or modifiers in films, pressure-sensitive adhesives, adhesives, paints and the like.

  As one of the coated particles, insulating coated conductive particles in which the surfaces of conductive particles having a metal surface are coated with an insulating resin are known. And in anisotropic conductive film and anisotropic conductive adhesive prepared by dispersing insulating coated conductive particles in adhesive, it is possible to prevent conduction between adjacent conductive particles by insulating resin used for coating Therefore, improvement of connection reliability is expected.

As such insulating coated conductive particles, for example, Patent Document 1 discloses insulating coated conductive particles in which an insulating layer is formed on the surface of the conductive particles by hybridization. Further, for example, Patent Document 2 discloses insulating coated conductive particles in which the surface of conductive particles is coated with particles for insulating coating having a particle size smaller than that of the conductive particles and having a different charge sign from the conductive particles. Has been. When the surface of the conductive particles is coated with the insulating coating particles, polymer particles or silica particles are mainly used.

  Patent Document 3 discloses particles that are insulation-coated with hollow particles. Furthermore, Patent Document 4 discloses coated conductive particles coated with core-shell particles.

JP-A-7-105716 JP 2003-26813 A JP 2005-203319 A JP-A-2005-149774

  When polymer particles are used as insulating coating particles, even if they have a binding functional group on the particle surface, the particle surface dissolves in the solvent during resin kneading, and the insulating coating particles peel off from the conductive particle surface. Therefore, the insulation reliability is likely to be lowered. In addition, polymer particles tend to be inferior in connection reliability because of low heat resistance and a large coefficient of thermal expansion.

  On the other hand, when silica particles are used as the insulating coating particles, they have high elasticity and are not easily deformed, so that the insulating properties are good. Silica particles are characterized by high solvent resistance. However, when low-pressure mounting is performed as an anisotropic conductive film, conductivity tends to be low. Silicone particles can be considered as an alternative material for silica particles, but they have not been adopted due to the problem of monodispersity in particle size.

  In addition, the insulation-coated particles of Patent Document 3 tend to inhibit conduction due to bubbles remaining in the particles, and also absorb the solvent and other compounds blended in the resin, and thus cause curing inhibition. is there.

  Further, since the insulating coating particles used for the coated conductive particles of Patent Document 4 are polymer particles, similarly to the above polymer particles, the solvent resistance is low, and peeling is performed when the coated conductive particles are mounted as an anisotropic conductive film. However, the insulation tends to be low.

  In view of the above circumstances, the present invention provides an anisotropic conductive material that can electrically connect electrodes of circuit members arranged opposite to each other with high reliability and can reliably prevent conduction between adjacent electrodes that should ensure insulation. It is an object of the present invention to provide insulating coating particles useful for obtaining and insulating coated conductive particles including the same. Another object of the present invention is to provide an anisotropic conductive material containing the insulating coated conductive particles and a connection structure in which circuit members are connected using the anisotropic conductive material.

  As a means for solving the above problems, the present invention provides an insulating coating particle comprising a structure having a core particle containing an organic polymer and a shell layer containing a silicone compound as a particle covering a base particle. I found it useful.

That is, the present invention is an insulating coating particle for forming insulating coated conductive particles by coating base particles made of a metal having a conductive surface, and has a core-shell structure having a core particle and a shell layer, The core particle includes an organic polymer, and the shell layer includes a silicone compound having at least one unit selected from the group consisting of SiO _4/2 units, RSiO _3/2 units, and R ₂ SiO _2/2 units. Insulating coating particles are provided. Here, R represents at least one selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, an aromatic group having 6 to 24 carbon atoms, a vinyl group, and a γ- (meth) acryloxypropyl group. . In the present specification, the “silicone compound” is a name including silicone and silica.

  The particles for insulating coating can be used for surface coating of conductive particles. According to this, it is useful for obtaining an anisotropic conductive material that can electrically connect the electrodes of the circuit members arranged opposite to each other with high reliability and can reliably prevent conduction between adjacent electrodes that should ensure insulation. It is. Moreover, solvent resistance and heat resistance can be provided by forming a silica film or a silicone film as a shell layer.

  When a silica film is formed as the shell layer, the shell layer is broken even at the time of low-pressure mounting, so that the conductivity is good. Moreover, since it is apparently elastic in a direction different from the direction compressed during mounting, high insulation can be obtained. Furthermore, since silica can be surface-treated, the dispersibility of the particles can be improved in accordance with the binder resin described later.

  When a silicone film is formed as the shell layer, the insulating coating particles are easily deformed even at low compression, so that the conductivity is good. Further, due to the characteristics of silicone, the dispersibility of the insulating coated conductive particles in the resin can be improved, and the hygroscopicity can be reduced.

  The shell layer preferably has a functional group having a binding property to the base particles. When the shell layer has a binding functional group, the insulating coating particles can uniformly form a covalent bond to the base particle, and the adhesion between the shell layer and the base particle is improved.

  Here, when the above-mentioned “functional group having a binding property to the base particle” is an epoxy group or a glycidyl group, the insulating coating particle can be easily covalently bonded to the base particle to which an amino group or the like is added. This is preferable because it can be formed.

  Moreover, it is preferable that a shell layer is processed by the silicone oligomer which has an epoxy group or a glycidyl group. By subjecting the shell layer to surface treatment using a silicone oligomer having an epoxy group or a glycidyl group, it is possible to improve the ease of adsorption and adhesion to the substrate particles. Such surface treatment is particularly preferable when the shell layer does not have a surface functional group.

  Moreover, it is preferable that the thickness of a shell layer is 1-150 nm. In this case, the conduction resistance between the circuits connected using the insulating coated conductive particles coated with the insulating coating particles of the present invention becomes better.

Moreover, the particle _| grains for insulation coating of this invention are comprised by the silicone type compound in which a shell layer has only _{SiO4 / 2} unit, and the thickness of a shell layer can be 1-50 nm. In this case, the characteristics of the core particle can be utilized.

  The insulating coating particles of the present invention preferably have an average particle size of 1 μm or less and a particle size variation coefficient (CV) of 10% or less. When the average particle diameter is 1 μm or less, both conductivity and insulation can be achieved at the time of pressure bonding of the anisotropically conductive material prepared using the insulating coated conductive particles coated with the insulating coating particles of the present invention. It becomes possible. In addition, by setting the coefficient of variation (CV) of the particle size of the conductive particles to 10% or less, it becomes possible to improve the reproducibility of the insulating characteristics.

  The insulating coating particles of the present invention preferably have a moisture absorption rate of 5% by mass or less. As a result, it is possible to suppress the occurrence of a short circuit due to ion migration or the like.

  Moreover, it is preferable that the particle | grains for insulation coating of this invention are 100 ppm or less in elution ammonium ion concentration. Thereby, it is possible to suppress the occurrence of curing inhibition in the anisotropic conductive material prepared using the insulating coated conductive particles coated with the insulating coating particles of the present invention.

  The shell layer is preferably formed by a reaction using a tertiary amine or a sulfonic acid compound as a catalyst.

  Moreover, it is preferable that the surface of a core particle has an amino group or a carboxyl group. According to this, when the shell layer is formed, the hydrolyzed silanol group is hydrogen-bonded so that the shell layer is easily formed on the core particle surface.

  The core particles preferably have a zwitterionic functional group. According to this, it becomes possible to prevent elution of a counter ion.

  The present invention also provides insulating coated conductive particles comprising the above insulating coating particles and substrate particles having at least a part of the surface coated with the insulating coating particles. The present invention further provides an anisotropic conductive material comprising an insulating binder resin and the insulating coated conductive particles dispersed in the insulating binder resin. According to such insulating coated conductive particles or anisotropic conductive material, the electrodes of the circuit members arranged opposite to each other can be conductively connected with high reliability, and sufficient conduction between adjacent electrodes that should ensure insulation is achieved. Can be prevented.

  The present invention also includes a pair of circuit members arranged opposite to each other and a cured product of the anisotropic conductive material, and the circuit electrodes interposed between the pair of circuit members are electrically connected to each other. A connection structure including a connection portion that bonds the circuit members together is provided. In this connection structure, since the connection part is made of the cured material of the anisotropic conductive material of the present invention, the electrodes of the circuit members can be conductively connected to each other with high reliability and the conductivity between adjacent electrodes that should ensure insulation. Can be sufficiently prevented.

  According to the present invention, it is possible to obtain an anisotropic conductive material that can electrically connect electrodes of circuit members arranged opposite to each other with high reliability and can reliably prevent conduction between adjacent electrodes that should ensure insulation. Useful insulating coating particles and insulating coating conductive particles including the same can be provided. In addition, the present invention can provide an anisotropic conductive material including the insulating coated conductive particles and a connection structure in which circuit members are connected using the anisotropic conductive material. That is, according to the present invention, it is possible to perform conductive connection with good conduction resistance between substrates, insulation reliability and connection reliability, and to prevent leakage between adjacent particles.

It is sectional drawing which shows typically one Embodiment of insulation coating electrically-conductive particle. It is sectional drawing which shows typically one Embodiment of an anisotropic electrically-conductive material. It is sectional drawing which shows typically an example of the connection structure in which circuit electrodes were connected. It is sectional drawing which shows typically an example of the manufacturing method of a connection structure.

  Preferred embodiments of the present invention will be described in detail. As shown in FIG. 1, the insulating coating particles 1 of the present embodiment constitute the insulating coated conductive particles 10 by coating the surfaces of the base particles 2. Hereinafter, each configuration will be described.

<Insulation coating particles>
[Core shell structure]
As shown in FIG. 1, the insulating coating particle 1 has a core-shell structure composed of a core particle 1a and a shell layer 1b formed on the surface of the core particle 1a. As materials for the core particle 1a and the shell layer 1b, the core particle 1a includes an organic polymer, and the shell layer 1b includes a silicone compound. Since the thermal characteristics of the insulating coating particles 1 can be adjusted by appropriately selecting the types of materials constituting the core particles 1a and the shell layer 1b, the particles are easily deformed, and pressure bonding between the substrates is performed. In this case, the conductivity is good. In addition, the materials of the core particle 1a and the shell layer 1b can be appropriately selected from different combinations based on thermal characteristics, optical characteristics, mechanical characteristics, and the like as necessary.

[Core particles]
The core particle is an insulating particle made of an organic polymer. The organic polymer is not particularly limited as long as it has insulating properties. For example, a resin used for base material particles described later can also be used.

  Examples of the polymerizable monomer that can be used in the production of the core particles include the following non-crosslinkable monomers and crosslinkable monomers.

  Specific examples of non-crosslinkable monomers include i) styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, α-methyl styrene, o-ethyl styrene, m-ethyl styrene, p-ethyl styrene, 2 , 4-dimethylstyrene, pn-butylstyrene, pt-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, p- Styrenes such as n-dodecylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, (ii) methyl acrylate, ethyl acrylate, propyl acrylate, n-acrylate Butyl, isobutyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate , Dodecyl acrylate, lauryl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, methyl α-chloroacrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, methacryl (Meth) acrylic acid esters such as isobutyl acid, hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, lauryl methacrylate, stearyl methacrylate, (iii) vinyl acetate, vinyl propionate, Vinyl esters such as vinyl benzoate and vinyl butyrate, (iv) N-vinyl compounds such as N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole, N-vinyl pyrrolidone, (v) vinyl fluoride, fluorinated Bi Fluorinated alkyl group-containing (meth) acrylates such as redene, tetrafluoroethylene, hexafluoropropylene, trifluoroethyl acrylate, tetrafluoropropyl acrylate, and (vi) conjugated dienes such as butadiene and isoprene Can be mentioned.

  Specific examples of crosslinkable monomers include divinyl compounds such as divinylbenzene, divinylbiphenyl, divinylnaphthalene; (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, (poly) tetramethylene glycol di (Poly) alkylene glycol-based di (meth) acrylates such as (meth) acrylate; 1,6-hexanediol di (meth) acrylate, 1,8-octanediol di (meth) acrylate, 1,9-nonanediol di ( (Meth) acrylate, 1,10-decanediol di (meth) acrylate, 1,12-dodecanediol di (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) acrylate, 2,4-diethyl- 1,5-pentanediol di (me ) Alkanediol di-types such as acrylate, butylethylpropanediol di (meth) acrylate, 3-methyl-1,7-octanediol di (meth) acrylate, 2-methyl-1,8-octanediol di (meth) acrylate (Meth) acrylate; neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, ethoxy Cyclohexanedimethanol di (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, propoxylated ethoxylated bisphenol Di- (meth) acrylate, 1,1,1-trishydroxymethylethane di (meth) acrylate, 1,1,1-trishydroxymethylethanetri (meth) acrylate, 1,1,1-trishydroxymethyl Examples include propane triacrylate, diallyl phthalate and isomers thereof, and triallyl isocyanurate and derivatives thereof.

  Monomers having a silyl group can also be used as crosslinkable monomers, specifically, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacrylate. Roxypropylmethyldiethoxysilane, γ-acryloxypropylmethyldimethoxysilane, γ-methacryloxypropylbis (trimethoxy) methylsilane, 11-methacryloxyundecamethylenetrimethoxysilane, vinyltriethoxysilane, 4-vinyltetramethylenetrimethoxy Silane, 8-vinyloctamethylenetrimethoxysilane, 3-trimethoxysilylpropyl vinyl ether, vinyltriacetoxysilane, p-trimethoxysilylstyrene, p-triethoxysilane Styrene, p-trimethoxysilyl-α-methylstyrene, p-triethoxysilyl-α-methylstyrene, γ-acryloxypropyltrimethoxysilane, vinyltrimethoxysilane and N-β (N-vinylbenzylaminoethyl-γ -Aminopropyl) trimethoxysilane hydrochloride.

  The said monomer may be used 1 type or in mixture of 2 or more types.

  The method for producing the core particles can be a conventionally known method and is not particularly limited. For example, the emulsion polymerization method, phase inversion emulsion polymerization, soap-free emulsion polymerization method, microsuspension polymerization method, miniemulsion polymerization method, dispersion weight Known methods such as legal methods can be used. Especially, it is preferable to manufacture by an emulsion polymerization method or a soap-free emulsion polymerization method from the point which control of a particle size is easy and it is suitable also for industrial production. Moreover, the said core particle can also use what is marketed.

  In the production of the core particles, the content of the polymerizable monomer in the reaction solution is preferably 1 to 50% by mass, more preferably 2 to 30% by mass, and further preferably 3 to 20% by mass in the total reaction solution. Most preferably, it is 3 to 15% by mass. In the case of producing crosslinked spherical polymer fine particles, the amount of monomer aggregates in the reaction system does not increase drastically as in the conventional method, but the content of the raw material monomer is 50 mass. % Or less, it becomes easy to obtain the particles in a high yield in a monodispersed state. On the other hand, when the content of the raw material monomer is 1% by mass or more, it does not take a long time until the reaction is completed, and it is practical from an industrial viewpoint.

  The reaction temperature at the time of polymerization varies depending on the type of solvent to be used and cannot be generally defined, but is usually about 10 to 200 ° C, preferably 30 to 130 ° C, more preferably 40 to 90 ° C. It is. The reaction time is not particularly limited as long as it is a time required for the target reaction to be almost completed. The monomer species and the amount of the monomer species, the type of functional group, the viscosity and concentration of the solution, the target particle It depends greatly on the diameter. For example, the reaction time when the reaction temperature is 40 to 90 ° C. is preferably 1 to 72 hours, and more preferably 2 to 24 hours.

  Since the core particle has a carboxyl group, an amino group, or both on the surface, it becomes easy to form a shell layer around the core particle. This is because the silicone compound hydrolyzed to the core particles by electrostatic interaction and hydrogen bonding is easily adsorbed. In this respect, it is particularly preferable to have a zwitterionic functional group. In order to introduce these functional groups into the core particle, it is preferable to use a monomer or initiator containing a carboxyl group or an amino group. In order to improve the dispersibility of the particles, it is preferable to introduce a functional group containing a sulfonic acid group.

  Specific examples of the monomer having a carboxyl group include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, itaconic acid, maleic acid and fumaric acid, and itaconic acid monoC1 such as monobutyl itaconic acid. -8 alkyl esters; maleic acid mono-C1-8 alkyl esters such as monobutyl maleate; various carboxyl group-containing monomers such as vinyl group-containing aromatic carboxylic acids such as vinyl benzoic acid; and salts thereof. In addition, these compounds can be used individually by 1 type or in combination of 2 or more types, and may have counter ions, such as Na, by neutralization.

  Specific examples of the monomer having an amino group include aminoethyl acrylate, acrylic acid-N-propylaminoethyl, (meth) acrylic acid-N-ethylaminopropyl, and (meth) acrylic acid-N-phenylaminoethyl. Amino group-containing (meth) acrylic acid alkyl ester derivatives such as (meth) acrylic acid-N-cyclohexylaminoethyl, allylamine derivatives such as allylamine and N-methylallylamine, amino group-containing styrene derivatives such as p-aminostyrene, Examples include triazine derivatives such as 2-vinyl-4,6-diamino-S-triazine, 1,3-propane sultone adducts of dimethylaminoethyl methacrylate, and the like. Of these, compounds having a primary or secondary amino group are preferred. In addition, these compounds can be used individually by 1 type or in combination of 2 or more types.

  It is also possible to use quaternary ammonium salts. Specific examples of monomers having a quaternary ammonium (salt) group include those obtained by quaternizing a tertiary amine with a quaternizing agent such as C1-12 alkyl chloride, dialkyl sulfuric acid, dialkyl carbonate, benzyl chloride. Can be mentioned. Specific examples include 2- (meth) acryloyloxyethyltrimethylammonium chloride, 2- (meth) acryloyloxyethyltrimethylammonium bromide, (meth) acryloyloxyethyltriethylammonium chloride, (meth) acryloyloxyethyldimethylbenzylammonium chloride, Alkyl (meth) acrylate quaternary ammonium salts such as (meth) acryloyloxyethylmethylmorpholino ammonium chloride, (meth) acryloylaminoethyltrimethylammonium chloride, (meth) acryloylaminoethyltrimethylammonium bromide, (meth) acryloylaminoethyl Triethylammonium chloride, (meth) acryloylaminoethyldimethylbenzyl Alkyl (meth) acrylamide quaternary ammonium salts such as ammonium chloride, dimethyldiallylammonium methylsulfate, trimethylvinylphenylammonium chloride, tetrabutylammonium (meth) acrylate, trimethylbenzylammonium (meth) acrylate, 2- (methacryloyloxy) Examples include ethyl trimethyl ammonium dimethyl phosphate.

  Further, as zwitterionic monomers, acrylates having a sulfobetaine or carbobetaine group can be used. Specifically, sulfobetaine methacrylate (a) acrylate, sulfobetaine acrylamide, sulfobetaine vinyl compound, sulfobetaine epoxide, carboxy Examples include betaine acrylate, carboxybetaine acrylamide, carboxybetaine vinyl compound, and carboxybetaine epoxide.

  A sulfonic acid group-containing monomer for introducing a functional group containing a sulfonic acid group can be used. For example, ethylene sulfonic acid, vinyl sulfonic acid, alkene sulfonic acid such as (meth) allyl sulfonic acid, aromatic sulfonic acid such as styrene sulfonic acid and α-methyl styrene sulfonic acid, C1-10 alkyl (meth) allyl sulfo succinic acid ester , Sulfo C2-6 alkyl (meth) acrylate such as sulfopropyl (meth) acrylate, methyl vinyl sulfonate, 2-hydroxy-3- (meth) acryloxypropyl sulfonic acid, 2- (meth) acryloylamino-2,2- Dimethylethanesulfonic acid, 3- (meth) acryloyloxyethanesulfonic acid, 3- (meth) acryloyloxy-2-hydroxypropanesulfonic acid, 2- (meth) acrylamido-2-methylpropanesulfonic acid, 3- (meth) Acrylamide-2-hydroxy Sulfonic acid group-containing unsaturated esters and salts thereof such as sulfonic acid.

  These monomers can be used individually by 1 type or in combination of 2 or more types. These monomers are preferably used in an amount of 0.1 mol% to 5 mol%, more preferably 0.1 mol% to 2.5 mol%, and more preferably 0.1 to 1 mol in order to improve monodispersibility. More preferably, it is used in%.

  In addition, the following initiators can also be used. For example, 2′-azobis {2- [N- (2-carboxyethyl) amidinopropane, 2,2′-azobis [2- (phenylamidino) propane] dihydrochloride (VA-545, manufactured by Wako Pure Chemical Industries), 2 , 2′-azobis {2- [N- (4-chlorophenyl) amidino] propane} dihydrochloride (VA-546, manufactured by Wako Pure Chemical Industries), 2,2′-azobis {2- [N- (4-hydroxyphenyl) ) Amidino] propane} dihydrochloride (VA-548, manufactured by Wako Pure Chemical Industries), 2,2′-azobis [2- (N-benzylamidino) propane] dihydrochloride (VA-552, manufactured by Wako Pure Chemical Industries), 2, 2'-azobis [2- (N-allylamidino) propane] dihydrochloride (VA-553, manufactured by Wako Pure Chemical Industries), 2,2'-azobis (2-amidinopropane) di Drochloride (V-50, manufactured by Wako Pure Chemical Industries), 2,2′-azobis {2- [N- (4-hydroxyethyl) amidino] propane} dihydrochloride (VA-558, manufactured by Wako Pure Chemical Industries), 2,2 -Azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride (VA-041, manufactured by Wako Pure Chemical Industries), 2,2-azobis [2- (2-imidazolin-2-yl) Propane] dihydrochloride (VA-044, manufactured by Wako Pure Chemical Industries), 2,2-azobis [2- (4,5,6,7-tetrahydro-1H-1,3-diazepin-2-yl) propane] dihydrochloride (VA-054, manufactured by Wako Pure Chemical Industries), 2,2-azobis [2- (3,4,5,6-tetrahydropyrimidin-2-yl) propane] dihydrochloride (VA-058, manufactured by Wako Pure Chemical Industries), 2 2-azobis [2- (5-hydroxy-3,4,5,6-tetrahydropyrimidin-2-yl) propane] dihydrochloride (VA-059, manufactured by Wako Pure Chemical Industries), 2,2-azobis {2- [ 1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane} dihydrochloride (VA-060, manufactured by Wako Pure Chemical Industries), 2,2-azobis [2- (2-imidazolin-2-yl) propane ] (VA-061, manufactured by Wako Pure Chemical Industries), 2,2′-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] (VA-057, manufactured by Wako Pure Chemical Industries), potassium peroxodisulfate ( Wako Pure Chemical Industries, Ltd.) and ammonium peroxodisulfate (Wako Pure Chemical Industries, Ltd.). These can be used individually by 1 type or in combination of 2 or more types. Further, when a polymerizable monomer having a particle active hydrogen group or a hydrophilic functional group is not used, it is possible to improve the dispersibility of the particles by using a compound having an active hydrogen group or a hydrophilic functional group in the initiator. Preferred above. When using a radical polymerization initiator, the compounding quantity is 0.01-1 mol% normally with respect to a polymerizable monomer. By producing the core particles by a conventional radical polymerization method, the monodispersity of the finally obtained insulating coating particles can be improved. An amino group or a carboxyl group may be imparted by adsorbing a polymer dispersant or a surfactant to the core particles.

  An emulsifier can be used in combination to improve the dispersibility of the core particles. In the present embodiment, an anionic emulsifier or a nonionic emulsifier is preferably used. Specific examples of the anionic emulsifier include sodium alkylbenzene sulfonate, sodium lauryl sulfonate, potassium oleate and the like, and sodium dodecylbenzene sulfonate is particularly preferably used. Specific examples of the nonionic emulsifier include polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, and the like.

  The glass transition temperature (Tg) of the core particles can be arbitrarily adjusted by selecting a polymerizable monomer to be used or by copolymerizing two or more polymerizable monomers having different Tg. For example, isobutyl methacrylate, glycidyl methacrylate, etc. are mentioned as a polymerizable monomer which Tg or softening point temperature becomes 60 degrees C or less independently. Moreover, Tg can be 60 degrees C or less by copolymerizing styrene, methyl methacrylate, etc. whose Tg is 60 degreeC or more, and butyl acrylate, dodecyl methacrylate, etc. whose Tg is less than 60 degreeC. Examples of the resin having a Tg of 80 ° C. or higher include styrene, α-methylstyrene, methyl methacrylate, t-butyl methacrylate, and the like. These may be used alone or in combination of two or more. In order to prevent elution of the core particles into the solvent, the amount of the crosslinkable monomer relative to the non-crosslinkable monomer is preferably less than 5 mol%.

[Shell layer]
The shell layer is made of a silicone compound and has at least one unit selected from the group consisting of SiO _4/2 units, RSiO _3/2 units, and R ₂ SiO _2/2 units. A plurality of R may be the same or different.

The SiO _4/2 unit, RSiO _3/2 unit and R ₂ SiO _2/2 unit can be represented by the following formulae.

Examples of the raw material of the SiO _4/2 unit in the silicone compound include one or more selected from the group consisting of silicon tetrachloride, tetraalkoxysilane, water glass, and metal silicate. Specific examples of the tetraalkoxysilane include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and condensates thereof. These can be used as appropriate by combining one kind or two or more kinds.

R in the RSiO _3/2 unit in the silicone compound is composed of an alkyl group having 1 to 4 carbon atoms, an aromatic group having 6 to 24 carbon atoms, a vinyl group, and a γ- (meth) acryloxypropyl group. It is at least one selected from the group. Depending on the substrate, an organic group having a small amount of vinyl group, γ- (meth) acryloxypropyl group or SH group for R, and a large amount of alkyl group or aromatic group may be selected. Examples of raw materials for RSiO _3/2 units include methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, phenyltrimethoxysilane, and phenyltriethoxy. Examples include silane, phenyltripropoxysilane, γ-mercaptopropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, and the like. One or a combination of two or more can be used as appropriate.

Examples of raw materials for R ₂ SiO _2/2 units (R may be selected from the same group as R in RSiO _3/2 units) in the silicone compound include, for example, dimethyldimethoxysilane, diphenyldimethoxysilane, methylphenyl Dimethoxysilane, dimethyldiethoxysilane, diphenyldiethoxysilane, methylphenyldiethoxysilane, diethyldimethoxysilane, ethylphenyldimethoxysilane, diethyldiethoxysilane, ethylphenyldiethoxysilane, hexamethylcyclotrisiloxane (D3), octa In addition to cyclic compounds such as methylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), dodecamethylcyclohexasiloxane (D6), trimethyltriphenylcyclotrisiloxane, etc. Or branched organosiloxane, γ-mercaptopropylmethyldimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, vinylmethyldimethoxysilane, 3,3,3-trifluoropropylmethyldimethoxysilane, and the like. These can be used as appropriate by combining one kind or two or more kinds.

In the present embodiment, a small amount of R ₂ SiO _2/2 units can be mixed when the particles are desired to have flexibility. The ratio of R ₂ SiO _2/2 units in the silicone compound in the insulating coating particles is preferably 50 mol% or less, more preferably 10 mol% or less, based on the total amount of the silicone compound. When the ratio of R ₂ SiO _2/2 units is 50 mol% or less, the final particles are not too flexible, and shape retention is improved. The lower limit of the ratio of R ₂ SiO _2/2 units in the silicone compound is 0 mol%.

As the silicone compound, a small amount of R ₃ SiO _1/2 unit can be used as long as the effects of the present embodiment are not impaired. The ratio of R ₃ SiO _1/2 units in the silicone compound is preferably 50 mol% or less, and more preferably 1 mol% or less. When the ratio of R ₃ SiO _1/2 units is 5 mol% or less, the heat resistance of the final silicone fine particles is more excellent. The lower limit of the proportion of _R 3 _{SiO 1/2} units of silicone compound is 0 mol%.

[Method for producing insulating coating particles]
For example, when the shell layer is made of silicone, the insulating coating particles are made of a raw material of SiO _4/2 units, a raw material of RSiO _3/2 units, and R ₂ SiO _{2/2 with} respect to a solvent containing core particles and a shell-forming catalyst. By adding an emulsion obtained by emulsifying a mixture of unit raw materials and water with a line mixer or a homogenizer at once or continuously, particles for insulating coating coated with silicone can be obtained. Although it becomes longer in time, it is preferable to employ continuous addition when importance is attached to the stability and particle size distribution of latex particles. If an acid catalyst is added before adding the emulsion and continuous addition is performed under conditions where hydrolysis and condensation proceed immediately, the insulating coating particles grow greatly over time, and as in normal seed polymerization, What shows a narrow particle size distribution can be obtained. In addition, when continuous addition is performed for a relatively short time of 30 minutes to 1 hour, both relatively good productivity and a narrow particle size distribution can be achieved.

Insulating coating particles having a shell layer of silica, for example, a raw material of SiO _4/2 units and water / alcohol or a uniform liquid of alcohol in a batch or continuously with respect to a solvent containing core particles and a shell-forming catalyst. It can be manufactured by adding.

  When the insulating coating particles of the present embodiment are used as an anisotropic conductive material as described later, the preferred lower limit of the particle size of the insulating coating particles is 10 nm, the upper limit is 1 μm, and the more preferred lower limit is 30 nm. The upper limit is 500 nm. When the particle size is 5 nm or more, the distance between adjacent coated conductive particles becomes larger than the electron hopping distance, and leakage is less likely to occur. When the particle size is 1000 nm or less, the pressure and heat required for pressure bonding can be reduced. .

  Note that two or more kinds of insulating coating particles having different particle diameters may be used in combination because small particles can enter the gap covered with the large insulating coating particles and improve the coating density. At this time, the particle size of the small insulating coating particles is preferably ½ or less of the particle size of the large particles, and the number of small particles is preferably ¼ or less of the number of large particles.

[Functional group having bonding properties]
In the coated conductive particles of the present embodiment, it is preferable that the shell layer partially covers the surface of the base particle through a functional group having a binding property to the base particle. In this case, the insulating coating particles are chemically bonded to the substrate particles, and have a stronger binding force than bonds by van der Waals force or electrostatic force alone, and conductive particles coated with insulating coating particles ( When insulating coating conductive particles) are used for anisotropic conductive materials, the insulating coating particles peel off when kneaded into a binder resin or the like, or the insulating coating particles peel off due to contact with adjacent insulating coating conductive particles. Leakage can be prevented. Further, since this chemical bond is formed only between the base material particles and the insulating coating particles and the insulating coating particles do not bind to each other, the base material particles are coated with a single layer of insulating coating particles. It will be. For this reason, if particles having a uniform particle size are used as the base particle and the insulating coating particle, the particle size of the insulating coated conductive particle can be easily made uniform.

  The functional group is not particularly limited as long as it is a group that can be covalently bonded. Silanol group, carboxyl group, amino group, ammonium group, hydroxyl group, carbonyl group, thiol group, sulfonic acid group, sulfonium group, epoxy group, glycidyl group It is preferable from the viewpoint of the speed of reactivity that it has an epoxy group or a glycidyl group. The functional group can be imparted by mixing the silane compound having the functional group at the time of shell formation or by treating the surface of the shell layer with a surfactant or a polymer dispersant. Further, from the viewpoint of improving the adsorptivity to the conductive particles, it is preferable to treat the surface of the shell layer with an oligomer (silicone oligomer) obtained by oligomerizing the silane compound having the functional group.

[Shell-forming catalyst]
A shell formation catalyst is a catalyst used for the sol-gel reaction of silicon alkoxide, and an acid or an alkali is used. Examples of the acid catalyst include sulfonic acids such as aliphatic sulfonic acid, aliphatic substituted benzenesulfonic acid, and aliphatic substituted naphthalenesulfonic acid, and mineral acids such as sulfuric acid, hydrochloric acid, and nitric acid. Among these, aliphatic substituted benzenesulfonic acid is preferable and n-dodecylbenzenesulfonic acid is particularly preferable from the viewpoint of excellent emulsion stability of the organosiloxane. Specific examples of the alkali catalyst include methylamine, etheramine, ethylamine, trimethylamine, triethylamine, triethanolamine, N, N-diisopropylethylamine, piperidine, piperazine, morpholine, quinuclidine, 1,4-diazabicyclo [2.2. .2] Octane (DABCO), pyridine, 4-dimethylaminopyridine, ethylenediamine, tetramethylethylenediamine (TMEDA), hexamethylenediamine, aniline, catecholamine, phenethylamine, 1,8-bis (dimethylamino) naphthalene (proton sponge), Amino acids, amantadine, spermidine, spermine and the like can be mentioned. In particular, it is preferable to use a compound having a tertiary amino group, and it is particularly preferable to use triethylamine.

[Average particle diameter, coefficient of variation of particle diameter (C.V.) and shell layer thickness]
The average particle diameter of the insulating coating particles is an average value obtained by observing 100 particle diameters with a scanning electron microscope (SEM). The average particle size of the insulating coating particles varies depending on the particle size of the substrate particles and the intended use of the insulating coating conductive particles, but is preferably 1 μm or less. Thereby, the physical properties of the base particles are hardly controlled by the physical properties of the insulating coating particles, and the effect of using the base particles can be easily obtained. More preferably, the lower limit of the particle diameter of the insulating coating particles is 10 nm, and the upper limit is 1 μm.

The coefficient of variation (CV) of the particle size is calculated using the following formula (1).
C. V. = {(Standard deviation of particle size) / (Average particle size)} × 100 (%) (1)
C. V. Is preferably 10% or less for improving the characteristics, more preferably 7% or less, and most preferably 5% or less. C. V. Is 10% or less, the size of the insulating coated conductive particles obtained is uniform, and when the insulating coated conductive particles are used for anisotropic conductive materials, it is easy to apply a uniform pressure when crimping between the substrates. The conductive connection can be improved.

In the insulating coating particles, the particle diameter of the core particles and the thickness of the shell layer are not particularly limited, but the thickness of the shell layer is preferably 1/100 or more, more preferably 1/50 or more of the particle diameter of the core particles. It is. Moreover, when a shell layer is comprised only by _{SiO4 / 2} unit, it is preferable that the thickness of a shell layer is 1-50 nm. When the thickness is 50 nm or less, the physical properties of the insulating coating particles are not easily controlled by the physical properties of the shell layer, the insulating coating particles are easily deformed, and the surface of the base particle is easily exposed. In this case, it becomes difficult to cause poor conduction between the electrodes.

[Eluted ammonium ion concentration]
When ammonium ions are eluted from the insulating coating particles, the curing agent in the anisotropic conductive material produced using the insulating coating conductive particles may be deactivated, and curing inhibition may occur. Therefore, the concentration of ammonium ions eluted from the insulating coating particles is preferably 150 ppm or less, and more preferably 100 ppm or less. The elution ammonium ion concentration can be measured, for example, by ion chromatography after dispersing 0.5 g of the dried insulating coating particles in 25 g of ion-exchanged water and leaving them in a pressure vessel at 100 ° C. for 12 hours.

[Hygroscopic rate]
The moisture absorption rate of the insulating coating particles is preferably 5% by mass or less. When the moisture absorption is 5% by mass or less, it is possible to suppress the occurrence of a short circuit due to ion migration or the like. The moisture absorption rate can be calculated, for example, by allowing the insulating coating particles whose weights have been measured to stand in a high-temperature and high-humidity test tank (temperature 60 ° C., humidity 90%) for 18 hours, and then measuring the particle weight again.

<Base material particles>
The base particle is made of a metal having a conductive surface and functions as a conductive particle. In this case, as shown in FIG. 1, the base particle 2 may be one in which a conductive metal layer 2 b is formed on the surface of a spherical core particle 2 a made of an inorganic compound or an organic compound, which will be described later. The metal particle which consists only of a metal which has property may be sufficient. Among them, those in which a conductive metal layer is formed on the surface of spherical core particles made of an organic compound can be deformed at the time of pressure bonding when conductively connecting between substrates, so that the bonding area can be increased. This is preferable.

  The conductive metal is not particularly limited. For example, gold, silver, copper, platinum, zinc, iron, tin, lead, aluminum, palladium, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, germanium. And a metal compound such as cadmium and a metal compound such as ITO or solder.

  When the metal layer made of the conductive metal is formed on the surface of the spherical core particles made of an organic compound, the metal layer may have a single layer structure or a laminated structure made up of a plurality of layers. There may be. In the case of a laminated structure, the outermost layer is preferably made of gold, palladium or nickel. When the outermost layer is made of palladium or gold, since the corrosion resistance is high and the contact resistance is small, the obtained coated particles are further improved.

  The method for forming the conductive metal layer on the surface of the spherical core particles made of the organic compound is not particularly limited. For example, a known method such as physical metal vapor deposition or chemical electroless plating may be used. The electroless plating method is preferable because of the simplicity of the process. Examples of the metal layer that can be formed by the electroless plating method include gold, silver, copper, platinum, palladium, nickel, rhodium, ruthenium, cobalt, tin, and alloys thereof. Since a uniform coating can be formed at a high density, it is preferable that a part or all of the metal layer is formed by electroless nickel plating.

  The method for forming the gold layer on the outermost layer of the metal layer is not particularly limited, and examples thereof include known methods such as electroless plating, displacement plating, electroplating, and sputtering.

  Although it does not specifically limit as thickness of the said metal layer, A preferable minimum is 0.005 micrometer and a preferable upper limit is 2 micrometers. When the thickness of the metal layer is less than 0.005 μm, a sufficient effect as the conductive layer may not be obtained. When the thickness exceeds 2 μm, the specific gravity of the obtained insulating coated conductive particles becomes too high, or from the organic compound In some cases, the hardness of the resulting spherical core particle is no longer sufficiently deformable. A more preferable lower limit of the thickness of the metal layer is 0.01 μm, and a more preferable upper limit is 1 μm.

  Moreover, when making the outermost layer of the said metal layer into a gold | metal | money or palladium layer, the minimum with the preferable thickness of a gold | metal | money or palladium layer is 0.001 micrometer, and a preferable upper limit is 0.5 micrometer. If the thickness of the gold or palladium layer is less than 0.001 μm, it may be difficult to uniformly coat the metal layer, and the effect of improving the corrosion resistance or contact resistance value may not be expected. It is expensive for the effect. The more preferable lower limit of the thickness of the gold or palladium layer is 0.01 μm, and the more preferable upper limit is 0.3 μm.

  When the base metal particles are formed with the conductive metal layer on the surface of the spherical core particles, the spherical core particles are not particularly limited, for example, particles having a uniform composition, a plurality of particles Examples thereof include particles having a multilayer structure in which the raw material is formed in a layer form. In particular, when it is desired to impart various properties such as mechanical properties and electrical properties to the substrate particles, particles having a multilayer structure are suitable.

  It does not specifically limit as a material which comprises the said spherical core material particle, Well-known inorganic compounds, such as a silica, an organic compound, etc. are mentioned. In particular, when insulating coated conductive particles are used for anisotropic conductive materials, the bonding area between the surface of the base particle and the electrode can be increased by deformation during pressure bonding when conductively connecting between the substrates, and the connection stability is excellent. Therefore, an organic compound is preferable.

  The organic compound is not particularly limited. For example, polyolefins such as polyethylene, polypropylene, polystyrene, polypropylene, polyisobutylene, and polybutadiene, acrylic resins such as polymethyl methacrylate and polymethyl acrylate, polyester resins such as polyalkylene terephthalate, and phenol formaldehyde. Phenol resins such as resins, melamine resins such as melamine formaldehyde resins, benzoguanamine resins such as benzoguanamine formaldehyde resins, urea formaldehyde resins, epoxy resins, (unsaturated) polyester resins, polyphenylene oxide, polyacetals, polysulfones, polycarbonates, polyamides, polyimides, polyamides Imide, polyetheretherketone, polyethersulfone, etc. Ranaru thing, and the like. Especially, what uses the resin which superposes | polymerizes 1 type (s) or 2 or more types of various polymerizable monomers which have an ethylenically unsaturated group is preferable from being easy to obtain suitable hardness.

  Specific examples of non-crosslinkable monomers include i) styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, α-methyl styrene, o-ethyl styrene, m-ethyl styrene, p-ethyl styrene, 2 , 4-dimethylstyrene, pn-butylstyrene, pt-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, p- Styrenes such as n-dodecylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, (ii) methyl acrylate, ethyl acrylate, propyl acrylate, n-acrylate Butyl, isobutyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate , Dodecyl acrylate, lauryl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, methyl α-chloroacrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, methacryl (Meth) acrylic acid esters such as isobutyl acid, hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, lauryl methacrylate, stearyl methacrylate, (iii) vinyl acetate, vinyl propionate, Vinyl esters such as vinyl benzoate and vinyl butyrate, (iv) N-vinyl compounds such as N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole, N-vinyl pyrrolidone, (v) vinyl fluoride, fluorinated Bi Fluorinated alkyl group-containing (meth) acrylates such as redene, tetrafluoroethylene, hexafluoropropylene, trifluoroethyl acrylate, tetrafluoropropyl acrylate, and (vi) conjugated dienes such as butadiene and isoprene Can be mentioned.

  Specific examples of crosslinkable monomers include divinyl compounds such as divinylbenzene, divinylbiphenyl, divinylnaphthalene; (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, (poly) tetramethylene glycol di (Poly) alkylene glycol-based di (meth) acrylates such as (meth) acrylate; 1,6-hexanediol di (meth) acrylate, 1,8-octanediol di (meth) acrylate, 1,9-nonanediol di ( (Meth) acrylate, 1,10-decanediol di (meth) acrylate, 1,12-dodecanediol di (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) acrylate, 2,4-diethyl- 1,5-pentanediol di (me ) Alkanediol di-types such as acrylate, butylethylpropanediol di (meth) acrylate, 3-methyl-1,7-octanediol di (meth) acrylate, 2-methyl-1,8-octanediol di (meth) acrylate (Meth) acrylate; neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, ethoxy Cyclohexanedimethanol di (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, propoxylated ethoxylated bisphenol Di- (meth) acrylate, 1,1,1-trishydroxymethylethane di (meth) acrylate, 1,1,1-trishydroxymethylethanetri (meth) acrylate, 1,1,1-trishydroxymethyl Examples include propane triacrylate, diallyl phthalate and isomers thereof, and triallyl isocyanurate and derivatives thereof.

  The above monomers and other polymerizable monomers may be used alone or in combination. As a method for producing such spherical core particles, conventionally known methods can be used and are not particularly limited. For example, emulsion polymerization, phase inversion emulsion polymerization, suspension polymerization, dispersion polymerization, seed polymerization And a soap-free precipitation polymerization method. Among these, a seed polymerization method having excellent particle size controllability is preferable. Moreover, what is marketed can also be used for the said spherical core material particle.

<Insulation coated conductive particles>
The insulating coated conductive particles of this embodiment are obtained by coating the surface of the substrate particles with the insulating coating particles. Here, it is preferable that 20% or less of the surface area of the insulating coating particles is in contact with the surface of the substrate particles. When the surface area to be contacted is 20% or less, the deformation of the particles for insulating coating is small, the size of the coated conductive particles obtained is more uniform, and the shell layer is less likely to be broken and the core-shell structure tends to be maintained. There is. The lower limit is not particularly limited, and may be substantially 0% when the insulating coating particles and the base particles are bound by, for example, a polymer having a long chain length.

  In the insulating coated conductive particles of this embodiment, it is preferable that 5% or more of the surface area of the substrate particles is coated with the insulating coating particles. When the coated surface area is 5% or more, it becomes easy to ensure insulation of the insulating coated conductive particles. Further, when the insulating coating conductive particles are used for the anisotropic conductive material, the preferable lower limit of the coverage of the insulating coating particles is 5%, and the preferable upper limit is 60%. When the coverage is 5% or more, it is possible to efficiently prevent the lateral leakage from occurring due to contact between the metal surfaces of the base particles between adjacent particles, and when the coverage is 60% or less, sufficient conductivity is obtained. It becomes easy to secure. The coverage with the insulating coating particles on the surface of the substrate particles is controlled by the amount (concentration) of the insulating coating particles added, the amount of functional groups introduced to the surface of the substrate particles (density), the type of reaction solvent, and the like. Is possible.

The coverage with the insulating coating particles on the surface of the substrate particles is a value calculated by the following equation (2).
Covering rate (%) = {(Area of the portion covered with insulating coating particles on the surface of the base particle) / (Total surface area of the base particle)} × 100 (2)

  The insulating coated conductive particles can be produced by dry hybridization or wet heteroaggregation. From the viewpoint of coverage and interparticle distance control, wet heteroaggregation is preferably used. As a method utilizing wet heteroaggregation, a method using a covalent bond between particles or electrostatic attraction is used. In order to prevent the particles for insulating coating from falling off, it is preferable to use a covalent bond. The coverage can be adjusted by appropriately adjusting the ratio of the conductive particles and the insulating coating particles. In addition, when the formation of the covalent bond is slow, the formation of the covalent bond can be promoted by heating the solvent.

  Specifically, the insulating coating particles into which glycidyl groups or epoxy groups are introduced (hereinafter also referred to as “child particles”) and conductive particles to which amino groups have been added are mixed to form a chemical bond. Insulating coated conductive particles can be produced.

  Examples of a method for introducing an amino group into conductive particles having a metal layer made of gold or palladium include the following methods. By treating the surface of the metal layer with a compound having a mercapto group, sulfide group or disulfide group that forms a coordinate bond to gold or palladium and a hydroxyl group, carboxyl group, alkoxy group or alkoxycarbonyl group, the surface A functional group selected from a hydroxyl group, a carboxyl group, an alkoxy group and an alkoxycarbonyl group can be introduced. Examples of the compound used include mercaptoacetic acid, 2-mercaptoethanol, methyl mercaptoacetate, mercaptosuccinic acid, thioglycerin and cysteine.

  The method of treating the surface of the metal layer with the above compound is not particularly limited, but a compound such as mercaptoacetic acid is dispersed in an organic solvent such as methanol or ethanol at a concentration of about 10 to 100 mmol / L, and the metal surface is dispersed therein. There is a method of dispersing the conductive particles.

  The surface potential (zeta potential) of particles having functional groups such as a hydroxyl group, a carboxyl group, an alkoxy group and an alkoxycarbonyl group on the surface is usually negative when the pH is in a neutral region. On the other hand, the surface potential of inorganic oxide particles having a hydroxyl group is usually negative. In many cases, it is difficult to sufficiently cover the surface of particles having a negative surface potential with particles having a negative surface potential. However, by providing a polymer electrolyte layer between them, the particles for insulating coating can be efficiently formed. It can be attached to conductive particles. In addition, by providing the polymer electrolyte layer, the surface of the conductive particles can be uniformly coated with the insulating coating particles without defects, so that the insulating property is ensured even when the circuit electrode interval is narrow and the electrodes are electrically connected. The effect of lowering the connection resistance is even more pronounced.

  As the polymer electrolyte that forms the polymer electrolyte layer, a polymer that is ionized in an aqueous solution and has a charged functional group in the main chain or side chain can be used, and among them, a polycation is preferable. Polycations generally have a positively charged functional group such as polyamine, such as polyethyleneimine (PEI), polyallylamine hydrochloride (PAH), polydiallyldimethylammonium chloride (PDDA), Polyvinylpyridine (PVP), polylysine, polyacrylamide, and a copolymer containing at least one of them can be used. Among them, polyethyleneimine has a high charge density and a strong binding force.

[Silicone oligomer treatment of insulating coated conductive particles]
When the insulating coating particle has a silanol group on its surface, the insulating reliability of the insulating coated conductive particle described later can be improved by treating with a silane coupling agent or a silicone oligomer obtained by oligomerizing the silane coupling agent. it can. Moreover, it is preferable to use the said silane coupling agent after making it a silicone oligomer from the ease of reaction to the particle | grain surface. The silicone oligomer is preferably three-dimensionally crosslinked in advance by a condensation reaction. The silicone oligomer preferably has a hydrophobic group and a functional group that reacts with an inorganic material such as silica.

  Silicone oligomers are generally composed of siloxane units having structures represented by the following chemical formulas.

In the formula, R ¹ and R ² each independently represent a hydrophobic group. R ¹ and R ² are preferably an alkyl group having 1 or 2 carbon atoms such as a methyl group and an ethyl group, an aryl group having 6 to 12 carbon atoms such as a phenyl group, or a vinyl group. More preferably, R ¹ and R ² are each independently a methyl group or a phenyl group. R ¹ and R ² may be the same as or different from each other.

  The degree of polymerization of the silicone oligomer is usually 3 or more, preferably 5 or more, more preferably 6 or more, and still more preferably 10 or more. Moreover, the polymerization degree of a silicone oligomer is 90 or less normally, Preferably it is 80 or less, More preferably, it is 70 or less, More preferably, it is 50 or less. When the degree of polymerization is increased, unevenness of treatment is less likely to occur during surface treatment, and reliability can be improved. Further, when the degree of polymerization is small, the silicone oligomer tends to adhere with a sufficient thickness.

The degree of polymerization of the silicone oligomer is calculated by the following formula (3) based on the weight average molecular weight in terms of standard polystyrene determined by gel permeation chromatography (GPC) measurement.
Degree of polymerization = weight average molecular weight / molecular weight of siloxane unit (3)
In addition, when several types of siloxane units are contained in a silicone oligomer, a polymerization degree is calculated by those average values.

The three-dimensionally crosslinked silicone oligomer generally contains at least one of a trifunctional siloxane unit represented by R ¹ SiO _3/2 and a tetrafunctional siloxane unit represented by SiO _4/2. Is preferred. For example, the silicone oligomer may contain a bifunctional siloxane unit represented by R ² SiO _2/2 and a tetrafunctional siloxane unit represented by SiO _4/2 , or R ² SiO _{2 / A} bifunctional siloxane unit represented by 2 and a trifunctional siloxane unit represented by R ¹ SiO _3/2 may be included.

  The siloxane oligomer preferably contains 15 mol% or more of tetrafunctional siloxane units based on the total siloxane units, and more preferably contains 20 to 60 mol%.

  The silicone oligomer can be synthesized, for example, by a method in which chloro or alkoxysilane corresponding to a desired siloxane unit is condensed using an acid catalyst in the presence of water. The condensation reaction is performed to such an extent that the silicone oligomer does not become a gel state before being attached to the submicron polymer particles. For this purpose, the reaction temperature, the reaction time, the composition ratio of the oligomer, the type and amount of the catalyst are changed and adjusted. As the catalyst, acetic acid, hydrochloric acid, maleic acid, phosphoric acid and the like are preferably used.

  In many cases, the silicone oligomer adheres to the submicron polymer particles and a part thereof also adheres to the conductive particles. The adhesion amount of the silicone oligomer in the whole insulating coated conductive particles is preferably 0.01 to 10% by mass, more preferably 0.05 to 5.00% by mass based on the mass of the submicron polymer particles. If this adhesion amount is 0.01% by mass or more, it tends to be easy to obtain the effect of improving the interfacial adhesion, and if it is 10% by mass or less, it is possible to prevent a decrease in heat resistance.

  Such insulating coated conductive particles can be used as a so-called anisotropic conductive material for electrically connecting small electrical parts such as semiconductor elements to substrates or electrically connecting substrates.

<Anisotropic conductive material>
An adhesive composition can be prepared by dispersing the insulating coated conductive particles in an insulating binder resin. And this adhesive composition can be used as an anisotropic conductive material (circuit connection material). The anisotropic conductive material may be formed into a film and used as an anisotropic conductive film. An anisotropic conductive film 50 shown in FIG. 2 is obtained by forming an adhesive composition in which insulating coated conductive particles 10 are dispersed in an insulating binder resin 20 into a film shape.

<Connection structure>
The connection structure 100 shown in FIG. 3 includes a first circuit member 30 and a second circuit member 40 that face each other, and the connection between the first circuit member 30 and the second circuit member 40. A connecting portion 50a for connecting them is provided.

  The first circuit member 30 includes a circuit board (first circuit board) 31 and a circuit electrode (first circuit electrode) 32 formed on the main surface 31 a of the circuit board 31. The second circuit member 40 includes a circuit board (second circuit board) 41 and a circuit electrode (second circuit electrode) 42 formed on the main surface 41 a of the circuit board 41.

  Specific examples of the circuit member include chip parts such as an IC chip (semiconductor chip), a resistor chip, a capacitor chip, and a driver IC, and a rigid package substrate. These circuit members are provided with circuit electrodes, and generally have many circuit electrodes. Examples of the other circuit member to which the circuit member is connected include a flexible tape substrate having metal wiring, a flexible printed wiring board, and a wiring substrate such as a glass substrate on which indium tin oxide (ITO) is deposited. By using the anisotropic conductive film 50, these circuit members can be connected efficiently and with high connection reliability. Therefore, the anisotropic conductive film 50 is suitable for COG mounting and COF mounting on a wiring board of a chip component having many fine connection terminals (circuit electrodes).

  The connection portion 50a includes a cured product 20a of an insulating binder resin contained in the circuit connection material, and the insulating coated conductive particles 10 dispersed therein. And in the connection structure 100, the circuit electrode 32 and the circuit electrode 42 which oppose are electrically connected through the insulation coating electrically-conductive particle 10. FIG. More specifically, as shown in FIG. 3, in the insulating coated conductive particles 10, the insulating coating particles 1 are deformed by compression and are in direct contact with both the circuit electrodes 32 and 42. On the other hand, in the illustrated horizontal direction, the insulating property is maintained by interposing the insulating coating particles 1 between the substrate particles 2. Therefore, if the anisotropic conductive film 50 is used, it is possible to improve the insulation reliability at a narrow pitch of 10 μm level.

  As the insulating binder resin 20, a mixture of a thermally reactive resin and a curing agent is used, and specifically, a mixture of an epoxy resin and a latent curing agent is preferable.

  Epoxy resins include bisphenol-type epoxy resins derived from epichlorohydrin and bisphenol A, F, AD, etc., epoxy novolac resins derived from epichlorohydrin and phenol novolac or cresol novolac, and naphthalene-based compounds having a skeleton containing a naphthalene ring Various epoxy compounds having two or more glycidyl groups in one molecule such as epoxy resin, glycidylamine, glycidyl ether, biphenyl, and alicyclic can be used alone or in admixture of two or more. .

These epoxy resins are preferably high-purity products in which impurity ions (Na ⁺ , Cl ^−, etc.), hydrolyzable chlorine and the like are reduced to 300 ppm or less. This makes it easier to prevent electromigration.

  Examples of the latent curing agent include imidazole series, hydrazide series, boron trifluoride-amine complex, sulfonium salt, amine imide, polyamine salt, dicyandiamide, and the like. In addition, for the adhesive, a mixture of a radical reactive resin and an organic peroxide or an energy ray curable resin such as ultraviolet rays is used.

  Insulating binder resin 20 can be mixed with butadiene rubber, acrylic rubber, styrene-butadiene rubber, silicone rubber, or the like in order to reduce stress after adhesion or to improve adhesion.

  In order to make the adhesive composition into a film, it is effective to add a thermoplastic resin such as a phenoxy resin, a polyester resin, or a polyamide resin having film-forming properties to the composition. These film-forming polymers are also effective in stress relaxation when the reactive resin is cured. In particular, when the film-forming polymer has a functional group such as a hydroxyl group, the adhesiveness is improved, which is preferable. The film is formed by dissolving or dispersing an adhesive composition composed of an epoxy resin, acrylic rubber, a latent curing agent, and a film-forming polymer in an organic solvent to form a peelable substrate (separator film). ) And then removing the solvent below the activation temperature of the curing agent. The organic solvent used at this time is preferably a mixed solvent of an aromatic hydrocarbon type and an oxygen-containing type in terms of improving the solubility of the material.

  The thickness of the anisotropic conductive film 50 is relatively determined in consideration of the particle diameter of the insulating coated conductive particles and the properties of the adhesive composition, but is preferably 1 to 100 μm. If the thickness is less than 1 μm, sufficient adhesiveness cannot be obtained, and if it exceeds 100 μm, a large amount of insulating coated conductive particles are required to obtain conductivity, which is not realistic. For these reasons, the thickness is more preferably 3 to 50 μm.

<Method for manufacturing connection structure>
FIG. 4 is a process diagram schematically illustrating a process of manufacturing the connection structure using an anisotropic conductive material. In the present embodiment, the anisotropic conductive material is thermally cured to manufacture the connection structure.

  First, the first circuit member 30 and the anisotropic conductive film 50 described above are prepared. The anisotropic conductive film 50 is made of an adhesive composition containing the insulating coated conductive particles 10 as described above.

  Next, the anisotropic conductive film 50 is placed on the surface of the first circuit member 30 on which the circuit electrodes 32 are formed. And the anisotropic conductive film 50 is pressurized to the arrow A and B direction of Fig.4 (a), and the anisotropic conductive film 50 is temporarily connected to the 1st circuit member 30 (FIG.4 (b)).

  Although the pressure at this time will not be restrict | limited especially if it is a range which does not damage a circuit member, Generally it is preferable to set it as 0.1-30.0 MPa. Moreover, you may pressurize, heating, and let heating temperature be the temperature which the anisotropic conductive film 50 does not harden | cure substantially. In general, the heating temperature is preferably 50 to 190 ° C. These heating and pressurization are preferably performed in the range of 0.5 to 120 seconds.

  Next, as shown in FIG. 4C, the second circuit member 40 is placed on the anisotropic conductive film 50 so that the second circuit electrode 42 faces the first circuit member 30. And the whole is pressurized in the arrow A and B direction of FIG.4 (c), heating the anisotropic conductive film 50. FIG.

  The heating temperature at this time is set to a temperature at which the anisotropic conductive film 50 can be cured. The heating temperature is preferably 60 to 200 ° C, more preferably 70 to 190 ° C, and still more preferably 80 to 160 ° C. When the heating temperature is less than 60 ° C, the curing rate tends to be slow, and when it exceeds 200 ° C, unwanted side reactions tend to proceed. The heating time is preferably 0.1 to 180 seconds, more preferably 0.5 to 180 seconds, and still more preferably 1 to 180 seconds.

  The connection part 50a is formed by hardening the anisotropic conductive film 50, and the connection structure 100 as shown in FIG. 3 is obtained. The connection conditions are appropriately selected depending on the application to be used, the adhesive composition, and the circuit member. In addition, when what is hardened | cured with light is used as the insulating binder resin 20 in the anisotropic conductive film 50, what is necessary is just to irradiate the anisotropic conductive film 50 with an actinic ray or an energy ray suitably. Examples of the active light include ultraviolet light, visible light, and infrared light. Examples of energy rays include electron beams, X-rays, γ rays, and microwaves.

  The preferred embodiment of the present invention has been described above, but the present invention is not limited to the above embodiment.

  Hereinafter, the contents of the present invention will be described more specifically with reference to examples and comparative examples. In addition, this invention is not limited to the following Example.

<Preparation of particles for insulation coating>
(Preparation of core particle 1)
The following compounds were charged all at once into a 500 ml flask, and the dissolved oxygen was replaced with nitrogen for 1 hour, followed by heating and stirring in a water bath at a temperature of 70 ° C. for about 6 hours to obtain core particles 1.

Styrene 40.4g (388mmol)
1.6 g (12 mmol) of divinylbenzene
2,2'-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] (VA-057) 1.4 g (4 mmol)
1,3-propane sultone adduct of dimethylaminoethyl methacrylate (DMAEMAPS) 0.6 g (2 mmol)
400 g of water

  When the core particle 1 was observed by SEM, the average particle size was 262 nm, and the coefficient of variation (CV) of the particle size was 4.1%.

(Preparation of core particles 2 to 4)
Core particles 2 to 4 were produced in the same manner as the production procedure of the core particle 1 except that the materials shown in Table 1 were used. In Table 1, “KBE-503” represents γ-methacryloxypropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name).

(Preparation of insulating coating particles 1)
The following compounds are charged all at once into a 500 ml flask, and the following shell raw material dispersion 1 is added dropwise over 1 hour while stirring in a water bath at a temperature of 35 ° C., followed by heating and stirring for 6 hours, and then particles for insulation coating A dispersion was obtained.

5 mass% core particle 1 aqueous solution 100g
Ethanol 100g
Triethylamine 2g

[Shell Raw Material Dispersion 1]
Tetraethoxysilane 12.5g
Ethanol 300g

  The obtained dispersion liquid for insulating coating particles was centrifuged, and redispersion in methanol was repeated several times. Thereafter, when the insulating coating particles were observed with an SEM, the average particle size was 300 nm, and the coefficient of variation (CV) in the particle size was 4.2%. Further, after 1 g of the obtained insulating coating particles were left in a high-temperature and high-humidity test tank (temperature 60 ° C., humidity 90%) for 18 hours, the moisture absorption was calculated by measuring the particle weight again. The moisture absorption rate was 1.5% by mass. Further, after drying the obtained particles, 0.5 g was dispersed in 25 g of ion-exchanged water, and after standing for 12 hours at 100 ° C. in a pressure vessel, the concentration of eluted ammonium ions was measured by ion chromatography. .

  Subsequently, 60 g of γ-glycidoxypropyltrimethoxysilane, 3 g of methanol, 14 g of water and hydrochloric acid (1% by mass of the total amount) were mixed and stirred at 60 ° C. for 4 hours, whereby the silicone oligomer 1 having a glycidyl group was obtained. Synthesized. This silicone oligomer 1 was added to the above dispersion for insulating coating particles in the same amount as the particle weight and stirred for 2 hours to obtain insulating coating particles 1 whose surface was treated with a silicone oligomer. Thereafter, centrifugation was performed three times, and after washing the particles, they were dispersed in methanol.

(Preparation of insulating coating particles 2)
A dispersion of insulating coating particles was prepared in the same manner except that the amount of tetraethoxysilane in the shell raw material dispersion was doubled in the synthesis of the insulating coating particles 1. When observed by SEM, the average particle diameter was 325 nm, and the coefficient of variation (CV) of the particle diameter was 4.0%. It was 2.0 mass% when the moisture absorption rate was computed. The elution ammonium ion concentration was measured and found to be 31 ppm.
Further, the same amount of the silicone oligomer 1 as the particle weight was added to the above dispersion for insulating coating particles and stirred for 2 hours to obtain insulating coating particles 2 whose surface was treated with the silicone oligomer. Thereafter, centrifugation was performed three times, and after washing the particles, they were dispersed in methanol.

(Preparation of insulating coating particles 3)
A dispersion of insulating coating particles was prepared in the same manner except that the amount of tetraethoxysilane in the shell raw material dispersion was tripled in the synthesis of the insulating coating particles 1. When observed by SEM, the average particle size was 363 nm, and the coefficient of variation (CV) of the particle size was 4.4%. It was 3.0 mass% when the moisture absorption rate was computed. The eluted ammonium ion concentration was measured and found to be 19 ppm.
Further, the same amount of the silicone oligomer 1 as the particle weight was added to the dispersion liquid for the insulating coating particles and stirred for 2 hours to obtain insulating coating particles 3 whose surface was treated with the silicone oligomer. Thereafter, centrifugation was performed three times, and after washing the particles, they were dispersed in methanol.

(Preparation of insulating coating particles 4)
The following compounds are charged all at once into a 500 ml flask, and the following shell raw material dispersion 2 is added dropwise over 1 hour while stirring in a water bath at a temperature of 80 ° C., followed by heating and stirring for 5 hours after the addition, and left for 20 hours. Thereafter, a dispersion of the insulating coating particles was obtained.

200% of 2.5 mass% core particle 1 aqueous solution
Dodecylbenzenesulfonic acid Na 2g
2g dodecylbenzenesulfonic acid

[Shell raw material dispersion 2]
Methyltrimethoxysilane 15.0g
20.0 g of water
Dodecylbenzenesulfonic acid Na 0.1g

The obtained particle dispersion was centrifuged, and redispersion in methanol was repeated several times. When observed by SEM, the average particle diameter was 312 nm, and the coefficient of variation (C.V.) of the particle diameter was 4.5. %Met. The moisture absorption rate calculated in the same manner as in Example 1 was 1.2% by mass. The eluted ammonium ion concentration was measured and found to be 21 ppm.
Further, the same amount of the silicone oligomer 1 as the particle weight was added to the above dispersion for insulating coating particles and stirred for 2 hours to obtain insulating coating particles 4 whose surface was treated with the silicone oligomer. Thereafter, centrifugation was performed three times, and after washing the particles, they were dispersed in methanol.

(Preparation of insulating coating particles 5)
The following compounds are charged all at once into a 500 ml flask, and the following shell raw material dispersion 3 is added dropwise over 1 hour while stirring in a water bath at a temperature of 80 ° C. After the dropwise addition, heating and stirring are continued for 5 hours and left for 20 hours. Thereafter, a dispersion of the insulating coating particles was obtained.

200% of 2.5 mass% core particle 1 aqueous solution
Dodecylbenzenesulfonic acid Na 2g
2g dodecylbenzenesulfonic acid

[Shell raw material dispersion 3]
7.3 g of methyltrimethoxysilane
6.4 g of dimethyldimethoxysilane
Tetramethoxysilane 1.3g
Dodecylbenzenesulfonic acid Na 0.1g
20g of water

The obtained particle dispersion was centrifuged, redispersed in methanol several times, and observed by SEM. The average particle size was 315 nm, and the coefficient of variation (CV) of the particle size was 5%. there were. It was 0.7 mass% when the moisture absorption rate was computed. The elution ammonium ion concentration was measured and found to be 30 ppm.
Further, the same amount of the silicone oligomer 1 as the particle weight was added to the above dispersion for insulating coating particles and stirred for 2 hours to obtain insulating coating particles 5 whose surface was treated with the silicone oligomer. Thereafter, centrifugation was performed three times, and after washing the particles, they were dispersed in methanol.

(Preparation of insulating coating particles 6)
A dispersion of insulating coating particles was prepared in the same manner except that in the synthesis of the insulating coating particles 4, twice the amount of the shell raw material dispersion 2 was added over 2 hours. When observed by SEM, the average particle diameter was 365 nm, and the coefficient of variation (CV) of the particle diameter was 4.8%. It was 1.0 mass% when the moisture absorption rate was computed. The elution ammonium ion concentration was measured and found to be 40 ppm.
Further, the same amount of the silicone oligomer 1 as the particle weight was added to the above dispersion for insulating coating particles and stirred for 2 hours to obtain insulating coating particles 6 whose surface was treated with the silicone oligomer. Thereafter, centrifugation was performed three times, and after washing the particles, they were dispersed in methanol.

(Preparation of insulating coating particles 7)
Insulating coating particles in the same manner except that the core particles 2 were used instead of the core particles 1 in the synthesis of the insulating coating particles 4 and that 3 times the amount of the shell raw material dispersion 2 was added over 3 hours. A dispersion was prepared. When observed by SEM, the average particle diameter was 316 nm and the coefficient of variation (CV) of the particle diameter was 3.5%. It was 1.2 mass% when the moisture absorption rate was computed. The elution ammonium ion concentration was measured and found to be 20 ppm.
Further, the same amount of the silicone oligomer 1 as the particle weight was added to the dispersion liquid for the insulating coating particles and stirred for 2 hours to obtain the insulating coating particles 7 whose surface was treated with the silicone oligomer. Thereafter, centrifugation was performed three times, and after washing the particles, they were dispersed in methanol.

(Preparation of insulating coating particles 8)
A dispersion of insulating coating particles was prepared in the same manner except that the core particles 2 were used in the synthesis of the insulating coating particles 1. When observed by SEM, the average particle diameter was 152 nm, and the coefficient of variation (CV) of the particle diameter was 4.8%. It was 1.0 mass% when the moisture absorption rate was computed. The elution ammonium ion concentration was measured and found to be 18 ppm.
Further, the same amount of the silicone oligomer 1 as the weight of the particles was added to the dispersion liquid for the insulating coating particles and stirred for 2 hours to obtain insulating coating particles 8 whose surface was treated with the silicone oligomer. Thereafter, centrifugation was performed three times, and after washing the particles, they were dispersed in methanol.

(Preparation of insulating coating particles 9)
A dispersion of insulating coating particles was prepared in the same manner except that the core particles 4 were used instead of the core particles 1 in the synthesis of the insulating coating particles 1. When observed by SEM, the average particle diameter was 405 nm, and the coefficient of variation (CV) of the particle diameter was 5.0%. It was 1.2 mass% when the moisture absorption rate was computed. The elution ammonium ion concentration was measured and found to be 22 ppm.
Further, the same amount of silicone oligomer 1 as the weight of the particles was added to the dispersion liquid of the insulating coating particles, followed by stirring for 2 hours to obtain insulating coating particles 9 whose surface was treated with the silicone oligomer. Thereafter, centrifugation was performed three times, and after washing the particles, they were dispersed in methanol.

(Preparation of insulating coating particles 10)
The core particle 1 was used as the insulating coating particle 10. It was 0.5 mass% when the moisture absorption rate was computed. The elution ammonium ion concentration was measured and found to be 30 ppm.

(Preparation of insulating coating particles 11)
After preparing the core particles 3, a mixture of the following compounds was added dropwise to the dispersion of the core particles 3 obtained above over 1 hour, and polymerization was further performed for 4 hours to prepare insulating coating particles 11.

Styrene 40.4g
1.6g divinylbenzene
VA-057 1.4g
DMAEMAPS 0.6g

  When the particles were observed by SEM, the average particle size was 320 nm, and the coefficient of variation (CV) in the particle size was 6%. It was 1.0 mass% when the moisture absorption rate was computed. The elution ammonium ion concentration was measured and found to be 40 ppm.

(Preparation of insulating coating particles 12)
A colloidal silica dispersion (concentration 20% by mass, manufactured by Fuso Chemical Industries, trade name Quatron PL-13, average particle size 130 nm) was used as insulating coating particles 12. It was 4.0 mass% when the moisture absorption rate was computed. The elution ammonium ion concentration was measured and found to be 12 ppm.

(Measurement of shell layer thickness)
For the insulating coating particles 1 to 12, the thickness of the shell layer was calculated from the average particle size before and after shell formation. The results are shown in Table 2.

<Mounting test of conductive particle insulation coating and anisotropic conductive film>
(Conductive particles)
A nickel layer having a thickness of 0.2 μm is formed by electroless plating on the surface of a crosslinked polystyrene particle having an average particle diameter of 3.0 μm, and a palladium layer having a thickness of 0.04 μm is further formed on the outer side of the nickel. Obtained.

(Insulation coating of conductive particles)
A reaction solution was prepared by dissolving 8 mmol of mercaptoacetic acid in 200 mL of methanol. 10 g of conductive particles were added to the reaction solution, and the mixture was stirred with a three-one motor and a stirring blade having a diameter of 45 mm at room temperature for 2 hours, and the surface of the conductive particles was treated with mercaptoacetic acid. The treated conductive particles were taken out by filtration using a membrane filter (manufactured by Millipore) having a pore size of 3 μm, and the taken out conductive particles were washed with methanol to obtain 1 g of conductive particles having a carboxyl group on the surface. .

  A 30% polyethyleneimine aqueous solution (manufactured by Wako Pure Chemical Industries, Ltd.) having a molecular weight of 70,000 was diluted with ultrapure water to obtain a 0.3 mass% polyethyleneimine aqueous solution. To this polyethyleneimine aqueous solution, 1 g of conductive particles having a carboxyl group on the surface obtained above was added and stirred at room temperature for 15 minutes. Next, the conductive particles were taken out by filtration using a φ3 μm membrane filter (manufactured by Millipore), and the taken out conductive particles were put in 200 g of ultrapure water and stirred at room temperature for 5 minutes. Thereafter, the conductive particles were removed by filtration using a φ3 μm membrane filter (manufactured by Millipore), and the conductive particles on the membrane filter were washed twice with 200 g of ultrapure water to remove non-adsorbed polyethyleneimine. Through the above operation, conductive particles having polyethyleneimine adsorbed on the surface were obtained.

  Next, the conductive particles treated with polyethyleneimine were immersed in isopropyl alcohol, and the dispersions of the insulating coating particles 1 to 12 were dropped to produce insulating coated conductive particles having a fine particle coverage of 30%. The coverage was adjusted by the dropping amount.

  Next, the conductive particles were taken out by filtration using a φ3 μm membrane filter (manufactured by Millipore), and the taken out conductive particles were put in 200 g of ultrapure water and stirred at room temperature for 5 minutes. Thereafter, the conductive particles are removed by filtration using a φ3 μm membrane filter (manufactured by Millipore), and the conductive particles on the membrane filter are washed twice with 200 g of ultrapure water so that the insulating coating particles are not adsorbed. Particles were removed. Next, the insulating coated conductive particles were dried by heating in the order of 80 ° C. for 30 minutes and 120 ° C. for 1 hour.

  Subsequently, 10 g of the insulating coated conductive particles are put into 100 g of a processing solution in which silicone oligomer 2 (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KR-212) is dissolved in the same amount as the particle weight, and the three-one motor is operated under the condition of room temperature for 1 hour. Used and stirred. Thereafter, the particles were taken out by filtration, and the taken insulating coated conductive particles were washed with methanol and dried to obtain insulating coated conductive particles 1 to 12 having the silicone oligomer 2 attached to the surface.

(Solvent resistance test for insulating coating particles)
The obtained insulating coated conductive particles were immersed in a toluene / ethyl acetate (mixing ratio: 50 parts by mass / 50 parts by mass) solution, irradiated with ultrasonic waves for 5 minutes (24 kHz), and then the insulating coated conductive particles were confirmed by SEM, It was confirmed whether the insulating coating particles were peeled off. The case where there was no change in the amount of adsorption of the insulating coating particles was A, and the case where the insulating coating particles were partially peeled was C. The results are shown in Table 3.

(Production of anisotropic conductive film and circuit connection using this)
100 g of phenoxy resin (Union Carbide, trade name: PKHC), acrylic rubber (40 parts by mass of butyl acrylate, 30 parts by mass of ethyl acrylate, 30 parts by mass of acrylonitrile, 3 parts by mass of glycidyl methacrylate, weight average molecular weight: 850,000) was dissolved in 400 g of toluene / ethyl acetate (mixing ratio: 50 parts by mass / 50 parts by mass) to obtain a 30% by mass solution. To this solution, 300 g of a liquid epoxy resin (Eboxy equivalent 185, manufactured by Asahi Kasei Epoxy Co., Ltd., trade name: Novacure HX-3941) containing a microcapsule type latent curing agent was added and stirred to prepare an adhesive solution.

  Into this adhesive solution, the above-mentioned insulating coated conductive particles having a silicone oligomer adhered on the surface were dispersed. The concentration was 9% by volume based on the amount of the adhesive solution. The obtained dispersion was applied to a separator (silicone-treated polyethylene terephthalate film, thickness 40 μm) using a roll coater, dried by heating at 90 ° C. for 10 minutes, and an anisotropic conductive film having a thickness of 25 μm was placed on the separator. Formed.

  Next, using the produced anisotropic conductive film, a chip (1.7 mm × 1.7 mm, thickness: 0.5 μm) with gold bumps (area: 30 μm × 90 μm, space 12 μm, height: 15 μm, number of bumps 362) ) And an ITO circuit-attached glass substrate (thickness: 0.7 mm) according to the following procedures i) to iii), and connection structure samples (Examples 1 to 9 and Comparative Examples 1 to 3) Was made.

i) An anisotropic conductive adhesive film (2 mm × 19 mm) was attached to a glass substrate with an ITO circuit at 80 ° C. and a pressure of 0.98 MPa (10 kgf / cm ² ).
ii) The separator was peeled off, and the bumps of the chip and the glass substrate with ITO circuit were aligned.
iii) The main connection was performed by heating and pressurizing from above the chip under the conditions of 190 ° C. and 40 MPa (low pressure mounting conditions) and 10 seconds.

(Insulation resistance test and conduction resistance test)
The manufactured connection structure sample was subjected to an insulation resistance test and a conduction resistance test. It is important that the anisotropic conductive film has a high insulation resistance between the chip electrodes and a low conduction resistance between the chip electrode and the glass electrode. The insulation resistance between 10 sample chip electrodes was measured. The insulation resistance was measured as an initial value and a value after a reliability test (migration test) in which the film was allowed to stand for 1000 hours under the conditions of an air temperature of 60 ° C., a humidity of 90%, and 20 V applied. In addition, the yield was calculated when a product having an insulation resistance of 10 ⁹ Ω or more after the reliability test was regarded as a non-defective product.

  Regarding the conduction resistance between the chip electrode and the glass electrode, the average value of 14 samples was measured. The conduction resistance was measured after a reliability test (a hygroscopic heat resistance test) in which the conductive resistance was allowed to stand for 1000 hours under the conditions of an initial value, a temperature of 85 ° C. and a humidity of 85%. Table 3 shows the measurement results.

  A summary of the results of the insulation resistance test and the conduction resistance test in Table 3 is shown in Table 4. As the conductive resistance evaluation, A is a case where the conductive resistance before the reliability test is 1Ω or less, B is a case where the resistance is over 1Ω and 5Ω or less, and C is a case where the resistance is over 5Ω. As the evaluation of the insulation reliability, A was obtained when the yield before the reliability test was 100% or less and 80% or more, B was less than 80% and 50% or more, and C was less than 50%. Furthermore, as the evaluation of connection reliability, the case where the conduction resistance after the reliability test is 0Ω or more and less than 50Ω is A, the case where it is 50Ω or more and less than 100Ω is B, and the case where it is 100Ω or more is C.

  As shown in Table 3, the connection structure samples of Examples 1 to 9 exhibited good conduction resistance, insulation reliability, and connection reliability before and after the reliability test. This is presumed to be because heat resistance and solvent resistance could be imparted to the particles by forming a shell layer with a silicone compound on the core particles. In Examples 1 to 9, the yield was maintained at 100% even after the reliability test.

  When polymer particles having no core-shell structure or particles having the same core and shell were used as the insulating coating particles, the initial conduction resistance was good, but the insulation reliability and connection reliability were poor. (Comparative Examples 1 and 2). This is presumably because the polymer particles have poor solvent resistance, so that the insulating coating particles peeled during the resin kneading, resulting in low insulation reliability. Further, it is presumed that the connection reliability was affected because the heat resistance of the polymer particles was low and the coefficient of thermal expansion was high. In addition, when silica particles were used as the insulating coating particles, the result was high conduction resistance (Comparative Example 3). It is presumed that this is because the elastic modulus of the particles is high, so that the deformation of the particles becomes difficult and the conduction becomes difficult.

  DESCRIPTION OF SYMBOLS 1 ... Particle | grains for insulation coating, 1a ... Core particle, 1b ... Shell layer, 2 ... Base material particle, 2a ... Spherical core material particle, 2b ... Metal layer, 10 ... Insulation coating conductive particle, 20 ... Insulating binder resin , 20a ... hardened material of insulating binder resin, 30 ... first circuit member, 31 ... circuit board (first circuit board), 31a ... main surface of the first circuit board, 32 ... circuit electrode (first Circuit electrode), 40 ... second circuit member, 41 ... circuit board (second circuit board), 41a ... main surface of the second circuit board, 42 ... circuit electrode (second circuit electrode), 50 ... Anisotropic conductive film, 50a ... connection part, 100 ... connection structure.

Claims (15)

Insulating coating particles for forming insulating coated conductive particles by coating base particles made of metal having conductive surface,
A core-shell structure having core particles and a shell layer;
The core particles include an organic polymer;
Insulating coating particles, wherein the shell layer contains a silicone compound having at least one unit selected from the group consisting of SiO _4/2 units, RSiO _3/2 units, and R ₂ SiO _2/2 units. (Here, R is at least one selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, an aromatic group having 6 to 24 carbon atoms, a vinyl group, and a γ- (meth) acryloxypropyl group). Is shown.)   The particle | grains for insulation coating of Claim 1 in which the said shell layer has a functional group which has the bondability with respect to the said base material particle.   The particle | grains for insulation coating of Claim 2 whose functional group which has the bondability with respect to the said base particle is an epoxy group or a glycidyl group.   The said shell layer is the particle | grains for insulation coating as described in any one of Claims 1-3 processed by the silicone oligomer which has an epoxy group or a glycidyl group.   The particle | grains for insulation coating as described in any one of Claims 1-4 whose thickness of the said shell layer is 1-150 nm. The particle | grains for insulation coating as described in any one of Claims 1-4 in which the said shell layer is comprised with the silicone type compound which has only _{SiO4 / 2} unit, and the thickness of the said shell layer is 1-50 nm.   The particle | grains for insulation coating as described in any one of Claims 1-6 whose average particle diameter is 1 micrometer or less and whose coefficient of variation of a particle diameter is 10% or less.   The particle | grains for insulation coating as described in any one of Claims 1-7 whose moisture absorption is 5 mass% or less.   The particle | grains for insulation coating as described in any one of Claims 1-8 whose elution ammonium ion concentration is 100 ppm or less.   The insulating coating particles according to any one of claims 1 to 9, wherein the shell layer is formed by a reaction using a tertiary amine or a sulfonic acid compound as a catalyst.   The particle | grains for insulation coating as described in any one of Claims 1-10 in which the surface of the said core particle has an amino group or a carboxyl group.   The particle | grains for insulation coating as described in any one of Claims 1-11 in which the said core particle has a zwitterionic functional group.   Insulating coated conductive particles comprising: the insulating coating particles according to any one of claims 1 to 12; and substrate particles having at least part of a surface coated with the insulating coating particles.   An anisotropic conductive material comprising: an insulating binder resin; and the insulating coated conductive particles according to claim 13 dispersed in the insulating binder resin. A pair of circuit members disposed opposite to each other;
The circuit members are bonded to each other so as to be electrically connected to each other that are interposed between the pair of circuit members and are electrically connected to each other. A connecting structure comprising: a connecting portion;

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