JP7036872B2 - Conductive particles, conductive materials, and connecting structures - Google Patents

Description

The present invention relates to conductive particles that can be used, for example, for electrical connections between electrodes.

Conventionally, anisotropic conductive materials such as anisotropic conductive pastes and anisotropic conductive films have been used for connection between an IC chip and a flexible printed circuit board, or connection between an IC chip and a circuit board having an ITO electrode. It is used. More specifically, the anisotropic conductive material includes a connection between a flexible printed circuit board and a glass substrate (FOG; Film on Glass), a connection between a semiconductor chip and a flexible printed circuit board (COF; Chip on Film), and a semiconductor chip. It is used for connection between a glass substrate and a glass substrate (COG; Chip on Glass), and for connection between a flexible printed circuit board and a glass epoxy substrate (FOB; Film on Board). The anisotropic conductive material is arranged, for example, between the electrodes of the IC chip and the electrodes of the circuit board, and further, by heating and pressurizing, enables electrical connection between these electrodes.

The anisotropic conductive material as described above is generally formed by dispersing conductive particles in a paste, ink or resin. In recent years, from the viewpoint of improving the performance of the anisotropic conductive material, the development of conductive particles contained in the anisotropic conductive material has been promoted. For example, the surface of the base particle is coated with another material. Therefore, many attempts have been made to improve the performance of conductive particles. For example, Patent Document 1 discloses conductive particles coated with silica. By including such silica-coated conductive particles in the anisotropic conductive material, both conduction reliability and insulation reliability can be improved when the anisotropic conductive material is used for electrical connection between electrodes. Be enhanced.

Japanese Unexamined Patent Publication No. 2014-241281

However, in the technique disclosed in Patent Document 1, silica easily falls off from the conductive particles, and the silica falls off from the conductive particles, causing a decrease in the insulating property of the conductive particles. Further, there is also a problem that when silica is removed from the conductive particles, the conductive particles tend to aggregate with each other, and the monodispersity of the conductive particles is not gradually impaired. From the above viewpoints, it is important to develop a technique for suppressing the deterioration of the insulating property and the cohesiveness of the conductive particles contained in the anisotropic conductive material.

The present invention has been made in view of the above, and the conductive particles which can easily prevent the deterioration of the insulating property of the conductive particles and can also suppress the aggregation of the conductive particles, and the conductive particles. It is an object of the present invention to provide a conductive material and a connecting structure having the above.

As a result of diligent research to achieve the above object, the present inventor has found that the above object can be achieved by coating the particles that are the base material of the conductive particles in combination with a resin and an inorganic material. The invention was completed.

That is, the present invention includes, for example, the subjects described in the following sections.
Item 1. It is a conductive particle having a base particle and a metal layer covering the surface of the base particle.
The surface of the metal layer is a conductive particle coated with a resin and an inorganic material.
Item 2. Item 2. The conductive particles according to Item 1, wherein the resin contains resin particles.
Item 3. Item 2. The conductive particles according to Item 1 or 2, wherein the inorganic material contains inorganic particles.
Item 4. Item 2. The conductive particles according to Item 1, wherein the resin contains resin particles, the inorganic material contains inorganic particles, and the ratio of the average particle diameter of the inorganic particles to the resin particles is 1/50 or more and 1 or less. ..
Item 5. Item 3. The conductive particle according to Item 3 or 4, wherein the coverage of the inorganic particle is 80% or more.
Item 6. A resin layer coated with the resin is formed on the surface of the metal layer, and an inorganic layer coated with the inorganic material is formed on the surface of the resin layer. Items 1 to 5 above. The conductive particle according to any one of the above items.
Item 7. A conductive material containing the conductive particles according to any one of Items 1 to 6 above and a binder resin.
Item 8. A first connection target member having a first electrode on its surface,
A second connection target member having a second electrode on the surface,
A connection portion connecting the first connection target member and the second connection target member is provided.
The material of the connection portion includes the conductive particles according to any one of the above items 1 to 6 or the conductive material according to the above item 7.
A connection structure in which the first electrode and the second electrode are electrically connected by the conductive particles or the conductive material.

The conductive particles according to the present invention have a base material particles and a metal layer covering the surface of the base material particles, and the surface of the metal layer is coated with a resin and an inorganic material, so that the conductive particles It is easy to prevent the deterioration of the insulating property of the particles, and it is difficult for the conductive particles to aggregate with each other.

An example of the connection structure provided with the conductive particles of the present invention is shown, and it is the schematic of the cross section.

Hereinafter, embodiments of the present invention will be described in detail.

In the following description, the chemical substance containing the term "(meth) acrylic" shall mean one or both of "acryl" and "methacryl". For example, "(meth) acrylic" means one or both of "acrylic" and "methacrylic", and "(meth) acrylate" means one or both of "acrylate" and "methacrylate".

Further, in the present specification, the expressions "contains" and "contains" include the concepts of "contains", "contains", "substantially consists" and "consists only".

The conductive particles of the present embodiment include base particles and a metal layer that covers the surface of the base particles, and the surface of the metal layer is coated with a resin and an inorganic material. In such conductive particles, deterioration of insulating property and aggregation of conductive particles are unlikely to occur. Hereinafter, the configuration of the conductive particles of this embodiment will be described in detail.

Examples of the base particles include resin particles, inorganic particles excluding metal particles, organic-inorganic hybrid particles, and metal particles. The base particles are preferably inorganic particles excluding resin particles and metal particles, or organic-inorganic hybrid particles.

For example, when an anisotropic conductive material having conductive particles is used for COG or the like, when connecting the electrodes, generally, the conductive particles are arranged between the electrodes and then the conductive particles are used. Compress. Therefore, since the conductive particles are made of a material that is easily deformed by the compression, the contact area between the conductive particles and the electrodes is large, so that the conduction reliability between the electrodes is high. From such a viewpoint, the base particle is preferably a resin particle which is a material easily deformed by the compression.

When the base particle is a resin particle, various organic substances are preferably used as a material for forming the resin particle. Examples of such materials include polyolefin resins such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyisobutylene and polybutadiene; acrylic resins such as polymethylmethacrylate and polymethylacrylate; polyalkylene terephthalate and polysulfone. Polycarbonate, polyamide, phenolformaldehyde resin, melamineformaldehyde resin, benzoguanamineformaldehyde resin, ureaformaldehyde resin, phenol resin, melamine resin, benzoguanamine resin, epoxy resin, saturated polyester resin, unsaturated polyester resin, polyphenylene oxide, polyacetal, polyimide, polyamideimide , Polyether ether ketone, polyethersulfone, urea resin and the like.

The resin particles can also be obtained by polymerizing one or more of various polymerizable monomers having an ethylenically unsaturated group. In this case, it is possible to design and synthesize resin particles having any compression physical characteristics suitable for anisotropic conductive materials. Further, in this case, the hardness of the base particles can be easily controlled within a suitable range. From this point of view, the material of the resin particles is preferably a polymer obtained by polymerizing one or more polymerizable monomers having a plurality of ethylenically unsaturated groups.

When the resin particles are obtained by polymerizing a monomer having an ethylenically unsaturated group, the monomer having an ethylenically unsaturated group is a non-crosslinkable monomer and / or a crosslinkable monomer. Monomer of.

Examples of the non-crosslinkable monomer include styrene-based monomers such as styrene and α-methylstyrene; carboxyl group-containing monomers such as (meth) acrylic acid, maleic acid, and maleic anhydride; and methyl ( Meta) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) Alkyl (meth) acrylates such as meth) acrylates and isobornyl (meth) acrylates; oxygen atoms such as 2-hydroxyethyl (meth) acrylates, glycerol (meth) acrylates, polyoxyethylene (meth) acrylates and glycidyl (meth) acrylates. Contains (meth) acrylates; nitrile-containing monomers such as (meth) acrylonitrile; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, and propyl vinyl ether; acid vinyl esters such as vinyl acetate, vinyl butyrate, vinyl laurate, vinyl stearate, etc. Class: unsaturated hydrocarbons such as ethylene, propylene, isoprene, and butadiene; halogen-containing monomers such as trifluoromethyl (meth) acrylate, pentafluoroethyl (meth) acrylate, vinyl chloride, vinyl fluoride, and chlorstyrene. Can be mentioned.

Examples of the crosslinkable monomer include tetramethylol methanetetra (meth) acrylate, tetramethylol methanetri (meth) acrylate, tetramethylol methanedi (meth) acrylate, trimethylol propanetri (meth) acrylate, and dipenta. Elythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, glycerol tri (meth) acrylate, glycerol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) Polyfunctional (meth) acrylates such as acrylates, (poly) tetramethylene glycol di (meth) acrylates, 1,4-butanediol di (meth) acrylates; triallyl (iso) cyanurate, triallyl trimellitate, divinylbenzene, Examples thereof include silane-containing monomers such as diallyl phthalate, diallyl acrylamide, diallyl ether, γ- (meth) acryloxypropyltrimethoxysilane, trimethoxysilylstyrene, and vinyltrimethoxysilane.

The crosslinkable and non-crosslinkable monomers are not limited to the monomers listed above, and may be other polymerizable monomers, for example, known polymerizable monomers.

The resin particles can be obtained by polymerizing the polymerizable monomer having an ethylenically unsaturated group by a known method. Examples of this method include suspension polymerization in the presence of a radical polymerization initiator and a method of swelling and polymerizing a monomer together with a radical polymerization initiator using non-crosslinked seed particles (so-called seed weight). Legal) etc.

When the base particle is an inorganic particle other than the metal particle or an organic-inorganic hybrid particle, examples of the inorganic substance as the material of the base particle include silica and carbon black. It is preferable that this inorganic substance is not a metal. The particles formed of the silica are not particularly limited, but for example, after hydrolyzing a silicon compound having two or more hydrolyzable alkoxysilyl groups to form crosslinked polymer particles, firing is performed as necessary. Examples include particles obtained by doing so. Examples of the organic-inorganic hybrid particles include organic-inorganic hybrid particles formed of a crosslinked alkoxysilyl polymer and an acrylic resin.

When the base material particles are metal particles, examples of the metal as the material of the metal particles include silver, copper, nickel, silicon, gold, and titanium. However, it is preferable that the base particles are not metal particles.

The average particle size of the base particles is not particularly limited. For example, the average particle size of the base particles is preferably 0.1 μm or more, more preferably 0.5 μm or more, still more preferably 1 μm or more, still more preferably 1.5 μm or more, particularly preferably 2 μm or more, preferably 2 μm or more. It may be 1000 μm or less, more preferably 500 μm or less, still more preferably 300 μm or less, still more preferably 100 μm or less, still more preferably 50 μm or less, still more preferably 30 μm or less, particularly preferably 5 μm or less, and most preferably 3 μm or less. can. When the average particle size of the base particles is equal to or larger than the above lower limit, the contact area between the conductive particles and the electrodes becomes large, so that the conduction reliability between the electrodes becomes even higher, and the particles are connected via the conductive particles. The connection resistance between the electrodes becomes even lower. Further, when the metal layer is formed on the surface of the base material particles by electroless plating, it becomes difficult to aggregate, and it becomes difficult to form the aggregated conductive particles. When the average particle size of the base particles is not more than the above upper limit, the conductive particles are easily sufficiently compressed, the connection resistance between the electrodes can be further reduced, and the distance between the electrodes can be further narrowed. ..

It is particularly preferable that the average particle size of the base particles is 0.1 μm or more and 5 μm or less. When the average particle diameter of the base particles is in the range of 0.1 or more and 5 μm or less, small conductive particles can be obtained even if the distance between the electrodes is small and the thickness of the metal layer is increased. From the viewpoint that the distance between the electrodes can be further reduced, or even if the thickness of the metal layer is increased, smaller conductive particles can be obtained, the average particle size of the base particles is It is preferably 0.5 μm or more, more preferably 2 μm or more, and preferably 3 μm or less. From the viewpoint of further enhancing the conduction reliability, the average particle size of the base particles is 2.5 μm or more.

The average particle size of the base particles indicates a number average particle size. The average particle size can be measured using, for example, a Coulter counter (manufactured by Beckman Coulter).

The above-mentioned form of the base material particles is an example for use in the conductive particles of the present embodiment, and other known base particles used as the conductive particles are used as the conductive particles of the present embodiment. It can also be applied to.

The metal layer is a layer formed so as to cover the surface of the base particles.

The thickness of the metal layer is preferably 5 nm or more, more preferably 10 nm or more, still more preferably 20 nm or more, particularly preferably 50 nm or more, preferably 1000 nm or less, more preferably 800 nm or less, still more preferably 500 nm or less, and particularly preferably. It is 400 nm or less, most preferably 300 nm or less. When the thickness of the metal layer is at least the above lower limit, the conductivity of the conductive particles becomes even better. When the thickness of the metal layer is not more than the above upper limit, the difference in the thermal expansion rate between the base particles and the metal layer becomes small, and the metal layer is difficult to peel off from the base particles. The metal layer may be formed in multiple layers, and the thickness of the metal layer in this case means the thickness of the entire metal layer formed in multiple layers.

Examples of the method for forming the metal layer on the surface of the base material particles include a method for forming the metal layer by electroless plating, a method for forming the metal layer by electroplating, and the like. In addition, a known method may be adopted as a method for forming the metal layer on the surface of the base particles.

The metal layer is formed of a material containing a metal, and the type of the metal is not particularly limited. Examples of the metal include gold, silver, copper, platinum, palladium, zinc, lead, aluminum, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, germanium and cadmium, and alloys thereof. Further, tin-doped indium oxide (ITO) may be used as the metal. The metal layer may be formed of only one kind of metal, or may be made of two or more kinds of metals.

The above-mentioned form of the metal layer is an example for use in the conductive particles of the present embodiment, and in addition, a known metal layer used as the conductive particles is applied to the conductive particles of the present embodiment. You can also do it.

In the conductive particles of the present embodiment, for example, the base particles may have a plurality of protrusions on the surface thereof. For example, in COG and the like, an oxide film is often formed on the surface of an electrode connected by conductive particles. Therefore, when the conductive particles having protrusions are used, the oxide film is easily effectively removed by the protrusions by arranging the conductive particles between the electrodes and crimping them. As a result, the electrodes and the conductive particles are in contact with each other more reliably, and the connection resistance between the electrodes is further lowered. Further, the protrusions effectively eliminate the insulating layer between the conductive particles and the electrodes, thus increasing the reliability of conduction between the electrodes. The insulating layer referred to here means a layer made of a resin and an inorganic material formed of conductive particles, as will be described later. Further, when the conventional conductive particles coated with silica as in Patent Document 1 have protrusions, the problem of silica falling off may become more serious. When the base particle has protrusions, the above-mentioned problems can be solved, and from this viewpoint as well, it is preferable to have protrusions.

As a method of forming the above-mentioned protrusions, a method of forming a metal layer by electroless plating after adhering a core material to the surface of the base particles, and a method of forming a metal layer by electroless plating on the surface of the base particles. After that, a method of adhering a core material and further forming a metal layer by electroless plating can be mentioned. Further, as another method for forming the protrusions, a first metal layer is formed on the surface of the substrate particles, a core material is placed on the first metal layer, and then a second metal layer is formed. Examples thereof include a method of forming a metal layer and a method of adding a core substance in the middle of forming a metal layer on the surface of the base particle.

As a method of adhering the core substance to the surface of the base particles, for example, the core substance is added to the dispersion liquid of the base particles, and the core substance is applied to the surface of the base particles by, for example, van der Waals force. Examples thereof include a method of accumulating and adhering, and a method of adding a core substance to a container containing the base particles and adhering the core substance to the surface of the base particles by mechanical action such as rotation of the container. Among them, a method of accumulating and adhering the core substance on the surface of the base material particles in the dispersion liquid is preferable from the viewpoint that the amount of the core substance to be adhered can be easily controlled.

Examples of the material of the core substance include a conductive substance and a non-conductive substance. Examples of the conductive substance include metals, metal oxides, conductive non-metals such as graphite, and conductive polymers. Examples of the conductive polymer include polyacetylene and the like. Examples of the non-conductive substance include silica, alumina and zirconia. Among them, metal is preferable in that the conductivity can be increased and the connection resistance can be effectively lowered. The core material is preferably metal particles.

Examples of the metal include metals such as gold, silver, copper, platinum, zinc, iron, lead, tin, aluminum, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, germanium and cadmium, and tin-lead. Examples thereof include alloys composed of two or more kinds of metals such as alloys, tin-copper alloys, tin-silver alloys, tin-lead-silver alloys and tungsten carbide. Of these, nickel, copper, silver or gold is preferred. The metal that is the material of the core material may be the same as or different from the metal that is the material of the metal layer. The material of the core material preferably contains nickel. Examples of the metal oxide include alumina, silica and zirconia.

The shape of the core substance is not particularly limited. The shape of the core material is preferably lumpy. Examples of the core material include particulate lumps, agglomerates in which a plurality of fine particles are aggregated, and amorphous lumps.

The average diameter (average particle size) of the core material is preferably 0.001 μm or more, more preferably 0.05 μm or more, preferably 0.9 μm or less, and more preferably 0.2 μm or less. When the average diameter of the core material is not less than the lower limit and not more than the upper limit, the connection resistance between the electrodes is effectively lowered.

The average diameter (average particle diameter) of the core material indicates a number average diameter (number average particle diameter). The average diameter of the core material is obtained by observing 50 arbitrary core materials with an electron microscope or an optical microscope and calculating an average value. When measuring the average diameter of the core material in the conductive particles, for example, the average diameter of the core material can be measured as follows. Conductive particles are added to "Technobit 4000" manufactured by Kulzer so as to have a content of 30% by weight and dispersed to prepare an embedded resin for conducting a conductive particle inspection. A cross section of the conductive particles is cut out using an ion milling device (“IM4000” manufactured by Hitachi High-Technologies Corporation) so as to pass near the center of the dispersed conductive resin in the embedded resin for inspection. Then, using a field emission scanning electron microscope (FE-SEM), the image magnification was set to 50,000 times, 20 conductive particles were randomly selected, and 50 protrusions of each conductive particle were selected. Observe. The diameter of the core material in the obtained conductive particles is measured and arithmetically averaged to obtain the average diameter of the core material.

The average height of the protrusions in the conductive particles is preferably 0.001 μm or more, more preferably 0.05 μm or more, preferably 0.9 μm or less, and more preferably 0.2 μm or less. When the average height of the protrusions is not less than the lower limit and not more than the upper limit, the connection resistance between the electrodes is effectively lowered.

When measuring the average height of the protrusions in the conductive particles, for example, the average height of the protrusions can be measured as follows. Conductive particles are added to "Technobit 4000" manufactured by Kulzer so as to have a content of 30% by weight and dispersed to prepare an embedded resin for conducting a conductive particle inspection. A cross section of the conductive particles is cut out using an ion milling device (“IM4000” manufactured by Hitachi High-Technologies Corporation) so as to pass near the center of the dispersed conductive resin in the embedded resin for inspection. Then, using a field emission scanning electron microscope (FE-SEM), the image magnification was set to 50,000 times, 20 conductive particles were randomly selected, and 50 protrusions of each conductive particle were selected. Observe. The height from the bottom surface of the protrusion to the top of the protrusion is defined as the height of the protrusion, and is arithmetically averaged to be the average height of the protrusion.

As described above, if the core material is embedded in the metal layer, it is possible to easily form protrusions on the outer surface of the metal layer.

The surface of the above metal layer is further coated with a resin and an inorganic material. That is, the surface of the metal layer includes a layer formed by being coated with a resin and an inorganic material. In the following, a layer formed by being coated with a resin and / or an inorganic material may be referred to as an "insulating layer".

Examples of the above resin include insulating resin materials, and specifically, polyolefins, (meth) acrylate polymers, (meth) acrylate copolymers, block polymers, thermoplastic resins, crosslinked products of thermoplastic resins, and the like. Examples thereof include a thermoplastic resin and a water-soluble resin. In addition, the same resin as the resin forming the base particle may be used.

Examples of the polyolefins include polyethylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid ester copolymer and the like.

Examples of the (meth) acrylate polymer include polymethyl (meth) acrylate, polyethyl (meth) acrylate, and polybutyl (meth) acrylate.

Examples of the block polymer include polystyrene, styrene-acrylic acid ester copolymer, SB type styrene-butadiene block copolymer, SBS type styrene-butadiene block copolymer, and hydrogenated products thereof.

Examples of the thermoplastic resin include other vinyl polymers and vinyl copolymers in addition to the resins listed above.

Examples of the thermosetting resin include epoxy resin, phenol resin, melamine resin and the like.

Examples of the water-soluble resin include polyvinyl alcohol, polyacrylic acid, polyacrylamide, polyvinylpyrrolidone, polyethylene oxide, methyl cellulose and the like. Among them, polyvinyl alcohol is more preferable as the water-soluble resin.

The shape of the resin is not particularly limited. For example, the shape of the resin can be made into particles. That is, the resin preferably contains resin particles. Hereinafter, these resin particles may be particularly referred to as insulating resin particles. When the resin contains insulating resin particles, the average particle size of the insulating particles can be made smaller than the average particle size of the conductive particles. Specifically, the average particle size of the insulating resin particles is preferably 0.01 μm or more, more preferably 0.1 μm or more, preferably 1.0 μm or less, and more preferably 0.5 μm or less. By adjusting the average particle diameter of the insulating resin particles to the above range, the insulating particles are less likely to come off when the binder is dispersed, and particle contact can be prevented. In addition, low resistance can be ensured because it is effectively eliminated when the electrodes are connected. The average particle size of the insulating resin particles referred to here has the same definition as the average particle size of the base particles described above.

The insulating particles can be prepared, for example, by (co) polymerizing one kind or two or more kinds of monomers having unsaturated double bonds. Examples of the monomer having an unsaturated double bond include (meth) acrylic acid; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth). Acrylate, glycidyl (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, trimethylpropantri (meth) acrylate, glycerol tri (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di Examples thereof include (meth) acrylic acid esters such as (meth) acrylate and 1,4-butanediol di (meth) acrylate; vinyl ethers; vinyl chloride; styrene compounds such as styrene and divinyl bezen, and acrylonitrile. In addition, the above-mentioned monomer may be a known polymerizable monomer. Among them, (meth) acrylic acid esters are preferably used.

Further, the resin may not be in the form of particles but may be in the form of a film, for example. When the resin is in the form of a film, its thickness is preferably 10 nm or more, more preferably 100 nm or more, preferably 1000 nm or less, and more preferably 500 nm or less. By adjusting the thickness of the insulating resin within the above range, the insulating particles are less likely to come off when the binder is dispersed, and particle contact can be prevented. In addition, low resistance can be ensured because it is effectively eliminated when the electrodes are connected.

The thickness of the resin can be measured as follows. For example, the conductive particles are added to "Technobit 4000" manufactured by Kulzer so as to have a content of 30% by weight and dispersed to prepare an embedded resin for conducting a conductive particle inspection. A cross section of the conductive particles is cut out using an ion milling device (“IM4000” manufactured by Hitachi High-Technologies Corporation) so as to pass near the center of the conductive particles dispersed in the embedded resin for inspection. Then, using a field emission scanning electron microscope (FE-SEM), the image magnification was set to 50,000 times, 20 conductive particles were randomly selected, and an insulating resin film of each conductive particle was selected. Observe. The thickness of the insulating resin film in the obtained conductive particles is measured, and the thickness of the insulating resin film is obtained by arithmetically averaging the thickness.

The resin may be a polymer electrolyte or the like in addition to the insulating resin particles. As the polymer electrolyte, a polymer (polyanion or polycation) that is ionized in an aqueous solution and has a charged functional group in the main chain or side chain can be used. Examples of the polyanion include those having a functional group capable of being negatively charged, such as sulfonic acid, sulfuric acid, and carboxylic acid, and are appropriately selected depending on the surface potential of the conductive particles and the insulating layer. Can be done. The polycations are generally those having a functional group capable of being positively charged, such as polyamines, for example, PEI, polyallylamine hydrochloride (PAH), PDDA, polyvinylpyridine (PVP), polylysine, polyacrylamide. And a copolymer containing at least one of them can be used.

The inorganic material is not particularly limited as long as it is a material formed of an inorganic substance. In the present embodiment, the inorganic material preferably contains inorganic particles.

Examples of the inorganic particles include silas particles, hydroxyapatite particles, magnesia particles, zirconium oxide particles, silica particles, alumina particles, zirconia particles and the like. In addition, the inorganic particles may be particles formed of a known inorganic element or an inorganic compound.

Examples of the silica particles include pulverized silica and spherical silica. Further, the silica particles may have a chemically bondable functional group such as a carboxyl group or a hydroxyl group on the surface.

The average particle size of the inorganic particles is preferably 0.001 μm or more, more preferably 0.005 μm or more, preferably 1.0 μm or less, more preferably 0.5 μm or less, still more preferably 0.2 μm or less. .. By adjusting the average particle diameter of the inorganic particles to the above range, the insulating particles are less likely to come off when the binder is dispersed, and particle contact can be prevented. In addition, since it is effectively eliminated when connecting electrodes, low resistance can be ensured and appropriate insulation can be exhibited. The average particle size of the inorganic particles referred to here has the same definition as the average particle size of the base particles described above.

The inorganic material is not limited to the inorganic particles, and may be, for example, a film-like form formed of an inorganic compound. The film formed of such an inorganic compound can be formed by, for example, a known method, but the forming method is not particularly limited.

The structure of the insulating layer (that is, the layer containing the resin and the inorganic material) is not particularly limited.

For example, the insulating layer may be formed by laminating a resin layer formed of a resin and an inorganic layer formed of an inorganic material in this order from the metal layer side. That is, in this case, a resin layer coated with the resin is formed on the surface of the metal layer, and an inorganic layer coated with the inorganic material is formed on the surface of the resin layer. Will be. The resin layer may contain a material other than the resin, or may be composed of only the resin. Further, the inorganic layer may contain a material other than the inorganic material, or may be composed of only the inorganic material.

As another form of the insulating layer, the insulating layer may be formed by laminating an inorganic layer formed of an inorganic material and a resin layer formed of a resin in this order from the metal layer side. That is, in this case, the surface of the metal layer is formed with an inorganic layer coated with the inorganic material, and the surface of the inorganic layer is formed with a resin layer coated with the resin. Will be.

The above-exemplified insulating layer is formed in at least a two-layer structure including a resin layer and an inorganic layer, but is not limited thereto. For example, the insulating layer may be formed of a material containing a mixture of the resin and the inorganic material to have a one-layer structure.

Among the above, in particular, the surface of the metal layer is formed with a resin layer coated with the resin, and the surface of the resin layer is formed with an inorganic layer coated with the inorganic material. It is preferably a structure. In this case, even if the outermost inorganic layer is shed, the resin layer is present on the surface, so that the insulating property of the conductive particles is unlikely to be deteriorated. Further, since the presence of the inorganic layer in the outermost layer enhances the repulsive action between the conductive particles, agglutination between the conductive particles is less likely to occur, and the monodispersity of the conductive particles is improved. In particular, when the inorganic layer is composed of silica particles, it is easy to improve the monodispersity of the conductive particles.

When the resin forming the insulating layer is a resin particle and the inorganic material is an inorganic particle, the ratio of the average particle diameter of the inorganic particle to the resin particle is preferably 1/50 or more, more preferably 1/30 or more. It is more preferably 1/10 or more, preferably 1 or less, and more preferably 1/2 or less. When the ratio of the average particle diameter of the inorganic particles to the resin particles is 1/50 or more, the insulating particles tend to aggregate with each other and the covering property is improved. When the ratio of the average particle diameter of the inorganic particles to the resin particles is 1 or less, the adhesion between the plating surface (metal layer) and the resin particles and the inorganic particles is high.

For example, the average particle size of the resin particles can be 0.2 μm or more and 1 μm or less, and the average particle size of the inorganic particles can be 0.01 μm or more and 0.2 μm or less. In this case, since the thickness of the insulating layer is not too thick, the electrical connection by the metal layer is more reliably achieved, and the adhesiveness of the resin particles and the inorganic particles is also enhanced.

The average particle size of the resin particles and the inorganic particles indicates a number average particle size, and can be measured by using a commercially available particle size distribution measuring device or the like. For example, it is obtained by using a particle size distribution measuring device such as a micro truck "UPA-EX-150" manufactured by Nikkiso Co., Ltd. When measuring the average particle size of the resin particles and the inorganic particles in the conductive particles, for example, the average particle size of the resin particles and the inorganic particles can be measured as follows. Conductive particles are added to "Technobit 4000" manufactured by Kulzer so as to have a content of 30% by weight and dispersed to prepare an embedded resin for conducting a conductive particle inspection. A cross section of the conductive particles is cut out using an ion milling device (“IM4000” manufactured by Hitachi High-Technologies Corporation) so as to pass near the center of the dispersed conductive resin in the embedded resin for inspection. Then, using a field emission scanning electron microscope (FE-SEM), the image magnification was set to 50,000 times, 20 conductive particles were randomly selected, and the average particles of the respective resin particles and inorganic particles were selected. Observe 50 particles. The average particle size of the resin particles and the inorganic particles in the obtained conductive particles is measured and arithmetically averaged to obtain the average particle size of the resin particles and the inorganic particles.

The CV value of the resin particles and the inorganic particles is preferably 20% or less. When the CV value is 20% or less, the thickness of the insulating layer becomes uniform. Therefore, for example, when applying conductive particles to applications such as COG, uniform pressure is applied when thermocompression bonding is performed between the electrodes. It becomes easy, and poor continuity is less likely to occur. The CV value of the particle size is calculated by the following formula.
CV value of particle size (%) = standard deviation of particle size / average particle size x 100
The particle size distribution can be measured with a particle size distribution meter or the like before coating the conductive portion of the conductive particles, and can be measured by image analysis or the like of an SEM photograph after coating.

The average thickness of the insulating layer is not limited and may be any thickness. In particular, if the average thickness of the insulating layer is thicker than the thickness of the protrusions described above, the effect of the insulating layer can be sufficiently exerted, the insulating property is less likely to deteriorate, and the aggregation of conductive particles is prevented. It becomes easy to be done.

The average thickness of the insulating layer is preferably 5 nm or more from the viewpoint that when conductive particles are applied to applications such as COG, leakage is unlikely to occur and the pressure and heat required for thermocompression bonding can be reduced. It is more preferably 10 nm or more, preferably 1000 nm or less, and more preferably 500 nm or less.

In the conductive particles of the present embodiment, when the inorganic material forming the insulating layer is an inorganic particle, it is preferable that the coverage of the inorganic particle with respect to the conductive particle is 80% or more. In this case, it is easy to prevent the insulating property of the conductive particles from deteriorating, and since the conductive particles have a shape closer to a spherical shape, it is easy to suppress the aggregation of the conductive particles, and the conductive particles The monodispersity can be improved. The upper limit of the coverage of the inorganic particles is 100%. When the resin forming the insulating layer is resin particles, it is preferable that the coverage of the resin particles with respect to the conductive particles is 40% or more. The upper limit of the coverage of the resin particles is 100%.

The coverage here indicates the ratio of the total area of the portion covered with the inorganic particles to the total surface area of the conductive particles (or the inner layer of the inorganic layer (for example, the resin layer)). The surface area of the inner layer of the inorganic layer can be obtained by calculating the surface area of the sphere by regarding the conductive particles excluding the inorganic layer as a sphere.

For example, using a field emission scanning electron microscope (FE-SEM), the image magnification is set to 50,000 times, 20 conductive particles are randomly selected, and the surface of each conductive particle is observed. .. The percentage of the surface area of the portion of the obtained conductive particles covered with the inorganic particles with respect to the projected area of the entire particles is measured, and the arithmetic mean is used as the coverage.

The coverage of the inorganic layer and the resin layer can also be measured by mapping analysis such as EDX associated with SEM.

Since the coverage can be adjusted by, for example, the amount of the inorganic particles added to the base particles, the mixing time, and the like, the method for adjusting the coverage is not particularly limited.

It is preferable that the above resin (for example, resin particles) and the inorganic material (for example, inorganic particles) have a reactive functional group capable of a chemical bond such as a covalent bond. In this case, the adhesion between the resin (for example, resin particles) and the inorganic material (for example, inorganic particles) becomes stronger, and it becomes easier to prevent these from falling off from the conductive particles.

Examples of the reactive functional group include vinyl group, (meth) acryloyl group, silane group, silanol group, carboxyl group, amino group, ammonium group, nitro group, hydroxyl group, carbonyl group, thiol group, sulfonic acid group and sulfonium. Examples thereof include a group, a boric acid group, an oxazoline group, a pyrrolidone group, a phosphoric acid group and a nitrile group. Of these, vinyl groups and (meth) acryloyl groups are preferable.

The reactive functional group can be introduced by surface treatment with a compound for introducing the reactive functional group into a resin (for example, resin particles) and an inorganic material (for example, inorganic particles). For example, a compound having a (meth) acryloyl group, a compound having an epoxy group, a compound having a vinyl group, and the like can be mentioned.

Examples of the compound (surface treatment substance) for introducing a vinyl group include a silane compound having a vinyl group, a titanium compound having a vinyl group, and a phosphoric acid compound having a vinyl group. The surface treatment substance is preferably a silane compound having a vinyl group. Examples of the silane compound having a vinyl group include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, and vinyltriisopropoxysilane.

Examples of the compound (surface treatment substance) for introducing a (meth) acryloyl group include a silane compound having a (meth) acryloyl group, a titanium compound having a (meth) acryloyl group, and a phosphoric acid having a (meth) acryloyl group. Examples include compounds. The surface treatment substance is also preferably a silane compound having a (meth) acryloyl group. Examples of the silane compound having a (meth) acryloyl group include (meth) acryloxypropyltriethoxysilane, (meth) acryloxypropyltrimethoxysilane, and (meth) acryloxypropyltridimethoxysilane.

The method for forming the insulating layer on the surface of the metal layer is not particularly limited, and a known method can be adopted. Examples of such a method include a chemical method and a physical or mechanical method. As the above-mentioned chemical method, a method of adhering a resin (for example, resin particles) and an inorganic material on the surface of a metal layer by a heteroaggregation method using van der Waals force or electrostatic force, and further chemically bonding them as necessary. Can be mentioned. Further, examples of the physical or mechanical method include spray drying, hybridization, electrostatic adhesion method, spraying method, dipping and vacuum deposition methods. Among them, since the insulating substance is difficult to be detached, a method of adhering a resin (for example, resin particles) and an inorganic material to the surface of the conductive layer via a chemical bond is preferable.

In forming the insulating layer on the surface of the metal layer, it is preferable to first attach the resin to the metal layer and then attach the inorganic material to the metal layer. In this case, the adhesion between the metal surface and the insulating layer tends to be high, so that peeling of the insulating layer can be suppressed. For example, if the resin particles are first attached to the metal layer and then the inorganic particles are attached to the metal layer, the inorganic particles having a small average particle size may be inserted between the resin particles having a large average particle size. , The insulating layer can be formed with the inorganic particles contained in the resin layer. A layer of inorganic particles may be further formed on the surface of the insulating layer thus formed. In this case, the insulating layer is formed of a resin layer containing inorganic particles and an inorganic layer formed of inorganic particles. To. On the other hand, when the size of the inorganic particles does not enter the voids of the resin layer, the inorganic particles do not enter the voids of the resin layer and become an insulating layer in which the inorganic layer is formed on the surface of the resin layer.

In forming the insulating layer on the surface of the metal layer, the resin particles and the inorganic particles can be attached to the metal layer by the same method, but they do not necessarily have to be attached to the metal layer by the same method. For example, a method may be adopted in which the resin particles are adhered to the insulating layer by heteroaggregation and chemically bonded to the surface of the metal layer, and the inorganic particles are physically coated on the surface of the resin layer by a method such as hybridization.

The surface of the metal layer and the insulating layer may not be directly chemically bonded, or may be indirectly chemically bonded by a compound having a reactive functional group. For example, after introducing a carboxyl group on the surface of the metal layer, the carboxyl group may be chemically bonded to a functional group on the surface of the insulating layer via a polyelectrolyte such as polyethyleneimine. The polymer electrolyte that can be used here can be the same as the above-mentioned polymer electrolyte.

The conductive particles of the present embodiment have a base material particle and a metal layer covering the surface of the base material particle, and the surface of the metal layer is coated with a resin and an inorganic material, so that the conventional conductivity is present. It can be a material having a larger coating amount of the insulating layer than the particles. As a result, the insulating property of the conductive particles is improved, and it is easy to prevent a decrease in the insulating property. Further, since the coating amount of the insulating layer in the conductive particles is large, the aggregation of the conductive particles is likely to be suppressed, and as a result, the monodispersity of the conductive particles is also improved. In particular, if the outermost layer of the conductive particles is silica particles, the aggregation of the conductive particles is more likely to be suppressed.

Then, when the conductive particles are applied to, for example, COG or the like to connect the electrodes, a short circuit between adjacent electrodes can be suppressed. Specifically, even if a plurality of conductive particles come into contact with each other between the electrodes, the presence of an insulating substance (insulating layer) between the plurality of electrodes suppresses a short circuit between adjacent electrodes in the lateral direction. You can also do it. By pressurizing the conductive particles with the two electrodes at the time of connection between the electrodes, the insulating substance (insulating layer) existing between the conductive portion (metal layer) of the conductive particles and the electrodes can be easily removed. Be excluded. When the conductive particles have protrusions on the surface of the metal layer, the insulating substance (insulating layer) is more easily removed.

Since the conductive particles of the present embodiment have an insulating layer containing a resin and an inorganic material, they have both appropriate hardness and appropriate recovery after compression. Therefore, the conductive particles of the present embodiment can be particularly preferably used for COG, which requires hardness and recoverability.

Specifically, in the conductive particles of the present embodiment, the stress (10% K value) at 10% compression is preferably 3000 or more and 15000 N / mm ² or less, and the recovery rate is preferably 30% or more and 80% or less. As described above, the conductive particles of the present embodiment are materials having excellent hardness and recoverability because they have the above-mentioned insulating layer. In particular, when the conductive particles of the present embodiment are applied to COG, the stress at 10% compression (10% K value) is preferably 5000 or more and 12000 N / mm ² or less, and the recovery rate is 40. % Or more, preferably 70% or less.

The 10% K value of the conductive particles can be measured as follows. Using a microcompression tester, one conductive particle is compressed with a smooth indenter end face of a cylinder (diameter 50 μm, made of diamond) under the condition that a maximum test load of 90 mN is applied over 30 seconds at 25 ° C. At this time, the load value (N) and the compressive displacement (mm) are measured. From the obtained measured values, the compressive elastic modulus can be obtained by the following formula. As the microcompression tester, for example, "Fisherscope H-100" manufactured by Fisher Co., Ltd. is used.
K value (N / mm ² ) = (3/2 ^1/2 ) ・ F ・ S ^-3/2・ R- ^{1 / 2}
F: Load value (N) when the conductive particles are compressed and deformed by 10%.
S: Compressive displacement (mm) when conductive particles are compressed and deformed by 10%
R: Radius of conductive particles (mm)
The recovery rate is determined by applying a maximum test load of 10 mN to one particle in the same apparatus as above, and then unloading the load. The compression displacement L1 (mm) and the recovery displacement L2 (mm) at this time are measured. It can be obtained from the obtained measured values by the following formula.
Recovery rate (%) = (L2 / L1) x 100
It is preferable that the conductive particles are dispersed in the binder resin and used as a conductive material. The conductive material is preferably an anisotropic conductive material. The conductive material is suitably used for electrical connection of electrodes. The conductive material is preferably a circuit connection material.

The binder resin is not particularly limited. As the binder resin, a known insulating resin is used. The binder resin preferably contains a thermoplastic component (thermoplastic compound) or a curable component, and more preferably contains a curable component. Examples of the curable component include a photocurable component and a thermosetting component.

The photocurable component preferably contains a photocurable compound and a photopolymerization initiator. The thermosetting component preferably contains a thermosetting compound and a thermosetting agent.

Examples of the binder resin include vinyl resins, thermoplastic resins, curable resins, thermoplastic block copolymers, elastomers and the like. Only one kind of the binder resin may be used, or two or more kinds thereof may be used in combination.

Examples of the vinyl resin include vinyl acetate resin, acrylic resin, styrene resin and the like.

Examples of the thermoplastic resin include polyolefin resins, ethylene-vinyl acetate copolymers, and polyamide resins.

Examples of the curable resin include epoxy resin, urethane resin, polyimide resin, unsaturated polyester resin and the like. The curable resin may be a room temperature curable resin, a thermosetting resin, a photocurable resin, or a moisture curable resin. The curable resin may be used in combination with a curing agent.

Examples of the thermoplastic block copolymer include a styrene-butadiene-styrene block copolymer, a styrene-isoprene-styrene block copolymer, a hydrogenated additive of a styrene-butadiene-styrene block copolymer, and a styrene-isoprene. -Hydrogen additives for styrene block copolymers and the like can be mentioned.

Examples of the elastomer include styrene-butadiene copolymer rubber and acrylonitrile-styrene block copolymer rubber.

In addition to the conductive particles and the binder resin, the conductive material includes, for example, a filler, a bulking agent, a softening agent, a plasticizer, a polymerization catalyst, a curing catalyst, a colorant, an antioxidant, a heat stabilizer, and a photostabilizing agent. It may contain various additives such as an agent, an ultraviolet absorber, a lubricant, an antistatic agent and a flame retardant.

The conductive material can be used as a conductive paste, a conductive film, or the like. When the conductive material is a conductive film, a film containing no conductive particles may be laminated on the conductive film containing the conductive particles. The conductive paste is preferably an anisotropic conductive paste. The conductive film is preferably an anisotropic conductive film.

The content of the binder resin in 100% by weight of the conductive material is preferably 10% by weight or more, more preferably 30% by weight or more, still more preferably 50% by weight or more, and particularly preferably 70% by weight or more, preferably 70% by weight or more. It is 99.99% by weight or less, more preferably 99.9% by weight or less. When the content of the binder resin is not less than the above lower limit and not more than the above upper limit, the conductive particles are efficiently arranged between the electrodes, and the connection reliability of the connection target member connected by the conductive material is further improved.

The content of the conductive particles in 100% by weight of the conductive material is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, preferably 80% by weight or less, and more preferably 60% by weight. Below, it is more preferably 40% by weight or less, particularly preferably 20% by weight or less, and most preferably 10% by weight or less. When the content of the conductive particles is not less than the lower limit and not more than the upper limit, the conduction reliability between the electrodes is further increased.

(Connection structure)
A connection structure can be obtained by connecting the members to be connected using the above-mentioned conductive particles or by using a conductive material containing the above-mentioned conductive particles and a binder resin.

As shown as an example in FIG. 1, the connection structure 81 connects a first connection target member 82, a second connection target member 83, a first connection target member, and a second connection target member. It is preferable that the material provided with the connecting portion 84 and forming the connecting portion is the above-mentioned conductive particles 1 or a conductive material containing the above-mentioned conductive particles 1 and a binder resin. It is preferable that the connection portion is a connection structure formed of the above-mentioned conductive particles or a conductive material containing the above-mentioned conductive particles and a binder resin. When the conductive particles are used alone, the connecting portion itself is the conductive particles. That is, the first and second connection target members are connected by the conductive particles. The conductive material used to obtain the connection structure is preferably an anisotropic conductive material.

It is preferable that the first connection target member has the first electrode 82a on the surface. It is preferable that the second connection target member has the second electrode 83a on the surface. It is preferable that the first electrode 82a and the second electrode 83a are electrically connected by the conductive particles 1.

The method for manufacturing the connection structure is not particularly limited. As an example of a method for manufacturing a connection structure, a method of arranging the conductive material between a first connection target member and a second connection target member, obtaining a laminate, and then heating and pressurizing the laminate. And so on. The pressurizing pressure is about 9.8 × 10 ⁴ or more and 4.9 × 10 ⁶ Pa or less. The heating temperature is about 120 or more and 220 ° C. or less. The pressure of the pressurization for connecting the electrodes of the flexible printed substrate, the electrodes arranged on the resin film, and the electrodes of the touch panel is about 9.8 × 10 ⁴ or more and 1.0 × 10 ⁶ Pa or less.

Specific examples of the connection target member include electronic components such as semiconductor chips, capacitors and diodes, and electronic components such as printed circuit boards, flexible printed circuit boards, glass epoxy boards and circuit boards such as glass substrates. The conductive material is preferably a conductive material for connecting electronic components. The conductive paste is a paste-like conductive material, and is preferably applied on the connection target member in the paste-like state.

The conductive particles and the conductive material are also suitably used for a touch panel. Therefore, it is also preferable that the connection target member is a flexible substrate or a connection target member in which electrodes are arranged on the surface of the resin film. The connection target member is preferably a flexible substrate, and is preferably a connection target member in which electrodes are arranged on the surface of the resin film. When the flexible substrate is a flexible printed circuit board or the like, the flexible substrate generally has an electrode on the surface.

Examples of the electrode provided on the connection target member include metal electrodes such as a gold electrode, a nickel electrode, a tin electrode, an aluminum electrode, a copper electrode, a silver electrode, a molybdenum electrode, and a tungsten electrode. When the connection target member is a flexible substrate, the electrode is preferably a gold electrode, a nickel electrode, a tin electrode, or a copper electrode. When the connection target member is a glass substrate, the electrode is preferably an aluminum electrode, a copper electrode, a molybdenum electrode, or a tungsten electrode. When the electrode is an aluminum electrode, it may be an electrode formed only of aluminum, or an electrode in which an aluminum layer is laminated on the surface of a metal oxide layer. Examples of the material of the metal oxide layer include indium oxide doped with a trivalent metal element and zinc oxide doped with a trivalent metal element. Examples of the trivalent metal element include Sn, Al and Ga.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the embodiments of these Examples.

(Example 1)
Formation of metal layer
Divinylbenzene copolymer resin particles (“Micropearl SP-203” manufactured by Sekisui Chemical Co., Ltd.) having a particle diameter of 3.0 μm were prepared as the base particles. The resin particles were dispersed in 100 parts by weight of an alkaline solution containing 5% by weight of a palladium catalyst solution using an ultrasonic disperser, and then the resin particles were taken out by filtering the solution. Next, the resin particles were added to 100 parts by weight of a 1% by weight solution of dimethylamine borane to activate the surface of the resin particles. The surface-activated resin particles were thoroughly washed with water, and then added to 500 parts by weight of distilled water and dispersed to obtain a suspension. Next, 1 g of a metallic nickel particle slurry (average particle diameter 100 nm) was added to the dispersion liquid over 3 minutes to obtain base particles to which a core substance was attached. Substrate particles to which the core material was attached were added to 500 parts by weight of distilled water and dispersed to obtain a suspension.

Further, as a nickel plating solution for the previous step, a mixed solution of nickel sulfate 500 g / L, sodium hypophosphite 150 g / L, sodium citrate 150 g / L, and a plating stabilizer 6 ml / L was adjusted to pH 8 with ammonia. A plating solution was prepared. 150 ml of this plating solution was added dropwise to suspension A through a metering pump at an addition rate of 20 ml / min. The reaction temperature was set to 50 ° C. Then, the mixture was stirred until the pH became stable, and it was confirmed that the foaming of hydrogen stopped, and the first step of electroless plating was performed.

Next, as a nickel plating solution for the latter stage, a plating solution prepared by adjusting a mixed solution of nickel sulfate 500 g / L, dimethylamine borane 80 g / L, and sodium tungstate 10 g / L to pH 11.0 with sodium hydroxide. did. 350 ml of this plating solution was added dropwise to the suspension through a metering pump at an addition rate of 10 ml / min. The reaction temperature was set to 30 ° C. Then, the mixture was stirred until the pH became stable, and it was confirmed that the foaming of hydrogen stopped, and the latter stage of electroless plating was performed.

Then, the suspension was filtered to take out the particles, washed with water, and dried to obtain base particles on which a nickel conductive layer (metal layer) having protrusions was arranged on the surface of the resin particles.

Preparation of resin particles In a 1000 mL separable flask equipped with a 4-neck separable cover, stirring blade, three-way cock, cooling tube and temperature probe, 100 mmol of methyl methacrylate and 13 mmol of ethylene glycol dimethacrylate, N, N, A monomer composition containing 1 mmol of N-trimethyl-N-2-methacryloyloxyethylammonium chloride and 1 mmol of 2,2'-azobis (2-amidinopropane) dihydrochloride having a solid content of 5% by weight. After weighing in ion-exchanged water, the mixture was stirred at 200 rpm and polymerized at 70 ° C. for 24 hours under a nitrogen atmosphere. After completion of the reaction, freeze-drying was performed to obtain insulating resin particles having an average particle diameter of 250 nm and a CV value of 10%. The insulating resin particles were dispersed in ion-exchanged water under ultrasonic irradiation to obtain a 10% by weight aqueous dispersion of the insulating resin particles.

Inorganic particles Aerosil 50 (average particle size 30 nm) manufactured by Nippon Aerosil Co., Ltd. was used.

Preparation of Conductive Particles 10 g of the base particles on which the metal layer obtained as described above was arranged was dispersed in 500 mL of ion-exchanged water, 4 g of an aqueous dispersion of insulating resin particles was added, and the mixture was stirred at room temperature for 6 hours. .. After filtering with a 0.3 μm mesh filter, the mixture was further washed with methanol and dried to obtain conductive particles to which insulating resin particles were attached. The insulating resin particles were covered with 40% of the particle surface.

10 g of the obtained conductive particles with insulating resin particles, 1.5 g of inorganic particles, and 100 g of zirconia spheres having an average particle size of 5 mm were put into a ball mill container having a volume of 1 L, stirred at a rotation speed of 500 rpm for 5 hours, and then zirconia spheres. Was separated to obtain insulating layer-coated conductive particles (also simply referred to as conductive particles). In the obtained conductive particles, the surface of the conductive particles was coated with the insulating resin particles, and the surface of the conductive particles was further coated with the inorganic particles from above. Inorganic particles were covered on 98% of the particle surface.

(Examples 2 to 7)
Conductive particles in the same manner as in Example 1 except that the average particle size of the base particles, the average particle size of the insulating resin particles and the insulating inorganic particles, and the coating amount were changed as shown in Table 1 below. Was produced.

(Example 8)
Conductive particles were prepared in the same manner as in Example 1 except that 100 mmol of methyl methacrylate was changed to 150 mmol of isobutyl methacrylate when the resin particles were prepared.

(Example 9)
Conductive particles were produced in the same manner as in Example 1 except that the inorganic particles were changed to aluminum oxide C (average particle size 13 nm) manufactured by Aerodil Japan.

(Example 10)
The conductive particles, the insulating resin particles, and the inorganic particles obtained in Example 1 were prepared. After mixing 10 parts by weight of the conductive particles and 10 parts by weight of the insulating resin particles, the particles are placed in a hybridizer (manufactured by Nara Kikai Co., Ltd.) and treated for 1 hour to form a resin layer having a thickness of about 100 nm on the surface of the conductive particles. Coated conductive particles were obtained. Next, 15 parts by weight of the inorganic particles were mixed and then put into a hybridizer and treated for 30 minutes to obtain conductive particles in which the inorganic particles were uniformly coated on the resin layer.

(Example 11)
By using the base particles to which the core material is not attached without adding the metal nickel particle slurry at the time of forming the metal layer of Example 1, the nickel conductive layer (metal layer) having no protrusions on the surface of the resin particles. ) Was arranged, and conductive particles were obtained in the same manner as in Example 1.

(Comparative Example 1)
Conductive particles were obtained in the same manner as in Example 1 except that the inorganic particles were not coated.

(Comparative Example 2)
Conductive particles were obtained in the same manner as in Example 1 except that the resin particles were not coated.

(Comparative Example 3)
Conductive particles were obtained in the same manner as in Example 1 except that neither the resin particles nor the inorganic particles were coated.

(evaluation)
(1) Coverage rate The coverage rate here indicates the ratio of the total area of the portion covered with the insulating layer to the total surface area of the conductive particles. Specifically, as described above, 20 insulating layer-coated conductive particles are observed by SEM observation, and the total projected area of the portion covered by the insulating layer occupying the entire surface area of each conductive particle. Was calculated as the coverage ratio. Then, the average value of the coverage of 20 pieces was taken as the coverage of the insulating layer-coated conductive particles.

(2) Compressive modulus (10% K value) when conductive particles are compressed by 10%
The compression elastic modulus (10% K value) of the obtained conductive particles was measured by the above-mentioned method using a microcompression tester (“Fisherscope H-100” manufactured by Fisher).

(3) Recovery rate of conductive particles The recovery rate of the obtained conductive particles was measured by the above-mentioned method using a microcompression tester (“Fisherscope H-100” manufactured by Fisher Co., Ltd.).

(4) 50 parts by weight of a monodisperse phenoxy resin (“PKHC” manufactured by Union Carbide), 30 parts by weight of PGMEA and 20 parts by weight of toluene were stirred and mixed for 24 hours to completely dissolve the phenoxy resin. 0.05 parts by weight of the conductive particles were added to 10 parts by weight of the obtained dissolved resin and stirred with a planetary stirrer to obtain a resin composition. The obtained resin composition was applied onto the stripped polyethylene terephthalate, and the solvent was dried to obtain an anisotropic conductive film having a thickness of 10 μm. When the obtained film was observed with an optical microscope and the equivalent of 1 million conductive particles were observed, the number of particles that were not monodisperse, that is, agglomerated, was counted.
[Judgment criteria for monodispersity]
○○○: The number of agglomerated particles is less than three.
XX: The number of agglomerated particles is 3 or more and less than 10.
◯: The number of aggregated particles is 10 or more and less than 20.
Δ: The number of agglomerated particles is 20 or more and less than 30.
X: The number of agglomerated particles is 30 or more.

(5) Conductivity (between the upper and lower electrodes)
The obtained conductive particles with insulating particles are added to "Stract Bond XN-5A" manufactured by Mitsui Chemicals, Inc. so that the content is 10% by weight, dispersed using a planetary stirrer, and anisotropically conductive. Obtained a paste.

A transparent glass substrate having an IZO electrode pattern formed on the upper surface of an Al—Nd alloy wiring having an L / S of 15 μm / 15 μm was prepared. Further, a semiconductor chip having a gold electrode pattern having an L / S of 15 μm / 15 μm formed on the lower surface was prepared.

The obtained anisotropic conductive paste was applied onto the transparent glass substrate so as to have a thickness of 30 μm to form an anisotropic conductive paste layer. Next, the semiconductor chips were laminated on the anisotropic conductive paste layer so that the electrodes face each other. After that, while adjusting the temperature of the head so that the temperature of the anisotropic conductive paste layer becomes 185 ° C., a pressurized heating head is placed on the upper surface of the semiconductor chip, and a pressure of 70 MPa is applied per bump area to apply anisotropic conductivity. The paste layer was cured at 185 ° C. to obtain a connecting structure.

The connection resistance between the upper and lower electrodes of the obtained 20 connection structures was measured by the 4-terminal method. From the relationship of voltage = current × resistance, the connection resistance can be obtained by measuring the voltage when a constant current is passed. The continuity was judged according to the following criteria.
[Conductivity criteria]
○ ○ ○: The ratio of the number of connection structures having a resistance value of 3Ω or less is 90% or more.
XX: The ratio of the number of connection structures having a resistance value of 3 Ω or less is 80% or more and less than 90%.
◯: The ratio of the number of connection structures having a resistance value of 3 Ω or less is 70% or more and less than 80%.
Δ: The ratio of the number of connection structures having a resistance value of 3 Ω or less is 60% or more and less than 70%.
X: The ratio of the number of connection structures having a resistance value of 3 Ω or less is less than 60%.

(6) Insulation (between adjacent electrodes in the horizontal direction)
In the 20 connection structures obtained in the above (5) Conductivity evaluation, the presence or absence of leakage between adjacent electrodes was evaluated by measuring the resistance with a tester. The insulation was judged according to the following criteria.
[Criteria for insulation]
○ ○ ○: The ratio of the number of connection structures having a resistance value of ¹⁰⁸ Ω or more is 90% or more.
XX: The ratio of the number of connection structures having a resistance value of ¹⁰⁸ Ω or more is 80% or more and less than 90%.
◯: The ratio of the number of connection structures having a resistance value of ¹⁰⁸ Ω or more is 70% or more and less than 80%.
Δ: The ratio of the number of connection structures having a resistance value of ¹⁰⁸ Ω or more is 60% or more and less than 70%.
X: The ratio of the number of connection structures having a resistance value of ¹⁰⁸ Ω or more is less than 60%.

In Table 1, for the conductive particles produced in each Example and Comparative Example, the coverage of the insulating resin particles (or the resin layer) and the inorganic particles, and the 10% K value (N / mm) of the conductive particles are shown. ² ), recovery rate (%), monodispersity, connection resistance value (conductivity) and insulation evaluation results are shown.

As can be seen from Table 1, the conductive particles obtained in each example have any of 10% K value (N / mm ² ), recovery rate (%), monodispersity, connection resistance value, and insulation performance. Has also been shown to be excellent. On the other hand, in the sample obtained in the comparative example, since the base particles are not coated with the resin and the inorganic material, aggregation is likely to occur and the monodispersity is poor, and the insulating property is also the conductivity of the example. The result was inferior to that when the sex particles were used.

Claims (6)

It is a conductive particle having a base particle and a metal layer covering the surface of the base particle.
The surface of the metal layer is coated with a resin and an inorganic material.
The resin contains resin particles and contains resin particles.
Conductive particles in which a resin layer coated with the resin is formed on the surface of the metal layer, and an inorganic layer coated with the inorganic material is formed on the surface of the resin layer . The conductive particle according to claim 1 , wherein the inorganic material contains inorganic particles. The conductive particles according to claim 1, wherein the resin contains resin particles, the inorganic material contains inorganic particles, and the ratio of the average particle diameter of the inorganic particles to the resin particles is 1/50 or more and 1 or less. .. The conductive particle according to claim 2 , wherein the coverage of the inorganic particles is 80% or more. A conductive material containing the conductive particles according to any one of claims 1 to 4 and a binder resin. A first connection target member having a first electrode on its surface,
A second connection target member having a second electrode on the surface,
A connection portion connecting the first connection target member and the second connection target member is provided.
The material of the connection portion includes the conductive particles according to any one of claims 1 to 4 or the conductive material according to claim 5.
A connection structure in which the first electrode and the second electrode are electrically connected by the conductive particles or the conductive material.

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