TWI615858B - Conductive particles, conductive materials, and connection structures - Google Patents

Description

Conductive particles, conductive materials, and connection structures

The present invention relates to a conductive particle in which a conductive layer is disposed on a surface of a substrate particle, and more particularly, for example, a conductive particle which can be used for electrical connection between electrodes. Further, the present invention relates to a conductive material and a connection structure using the above conductive particles.

An anisotropic conductive material such as an anisotropic conductive paste or an anisotropic conductive film is known. The anisotropic conductive material is obtained by dispersing conductive particles in a binder resin.

The anisotropic conductive material is used for connection between an IC chip and a flexible printed circuit board, and connection of an IC chip to a circuit board having an ITO (Indium Tin Oxide) electrode. For example, after an anisotropic conductive material is disposed between the electrode of the IC chip and the electrode of the circuit board, the electrodes can be electrically connected by heating and pressurization.

As an example of the above-mentioned conductive particles, in the following Patent Document 1, the following conductive particles are disclosed: on the surface of spherical substrate particles having an average particle diameter of 1 to 20 μm, by electroless plating A nickel conductive layer or a nickel alloy conductive layer is formed. The conductive particles have minute protrusions of 0.05 to 4 μm in the outermost layer of the conductive layer. The conductive layer is substantially continuously connected to the protrusion.

Patent Document 2 discloses a conductive particle including a plastic core body, a polymer electrolyte layer covering the plastic core body, and a metal particle which is adsorbed to the plastic material via the polymer electrolyte layer. nuclear And an electroless metal plating layer formed around the plastic core body so as to cover the metal particles.

Patent Document 3 listed below discloses conductive particles in which a conductive layer containing a plurality of layers of a metal plating film layer of nickel and phosphorus and a gold layer is formed on the surface of the substrate particles. The conductive particles are placed on the surface of the substrate particles, and a core material is disposed, and the core material is coated with a conductive layer. The conductive layer is embossed by the core material, so that protrusions are formed on the surface of the conductive layer.

[Advanced technical literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2000-243132

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2011-108446

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2006-228475

In the above Patent Documents 1 to 3, conductive particles having protrusions on the surface on the outer side of the conductive layer are disclosed. An oxide film is often formed on the surface of the electrode to be connected by the conductive particles and the conductive layer of the conductive particles. The protrusion of the conductive layer is formed in such a manner that when the electrodes are pressure-bonded between the electrodes via the conductive particles, the oxide film on the surface of the electrode and the conductive particles is removed, and the conductive layer is brought into contact with the electrode.

However, when the surface on the outer side of the conductive layer has a protruding conductive particle and is connected between the electrodes, there is a case where the oxide film on the surface of the electrode and the conductive particle cannot be sufficiently excluded, and the connection resistance is changed. high.

An object of the present invention is to provide a conductive particle which can reduce the connection resistance between electrodes when a connection structure is obtained between the electrodes, a conductive material using the conductive particles, and a connection structure.

According to a broad aspect of the present invention, there is provided an electroconductive particle comprising: a substrate particle; a conductive layer covering the conductive layer of the substrate particle; and a plurality of core materials embedded in the conductive layer; The conductive layer has a plurality of protrusions on the outer surface, and the core material is disposed inside the protrusion of the conductive layer, and the conductive layer is disposed between the substrate particle and the core material, and the surface of the substrate particle The distance from the surface of the core material is such that the average distance between the surface of the substrate particles and the surface of the core material exceeds 5 nm.

In a specific aspect of the conductive particles of the present invention, the average distance between the surface of the substrate particles and the surface of the core material is more than 5 nm and 800 nm or less.

In a specific aspect of the conductive particles of the present invention, in the total number of 100% of the core material, one of the core materials having a distance between the surface of the substrate particle and the surface of the core material exceeding 5 nm The ratio of the number is more than 80% and less than 100%.

In a specific aspect of the conductive particles of the present invention, the metal element containing the most metal element in the core material is the same as the metal element containing the most in the conductive layer.

In another specific aspect of the conductive particles of the present invention, the conductive layer includes: a first conductive layer covering the substrate particles; and a second conductive layer, The first conductive layer and the core material are covered; and the core material is disposed on a surface of the first conductive layer and embedded in the second conductive layer, and the second conductive layer has a plurality of surfaces on the outer side In the protrusion, the core material is disposed inside the protrusion of the second conductive layer, and the first conductive layer is disposed between the substrate particle and the core material.

In another specific aspect of the conductive particles of the present invention, the metal element containing the most of the core material is the same as the metal element containing the most of the second conductive layer.

In still another specific aspect of the electroconductive particle of the present invention, the conductive layer is a single layer of a conductive layer.

In another specific aspect of the conductive particles of the present invention, the core material is a metal particle.

In other specific aspects of the conductive particles of the present invention, an insulating material attached to the surface of the conductive layer is further included.

The conductive material of the present invention comprises the above-mentioned conductive particles and a binder resin.

The connection structure according to the present invention includes a first connection target member, a second connection target member, and a connection portion that connects the first and second connection target members, and the connection portion is formed of the conductive particles or includes The conductive particles are formed of a conductive material of a binder resin.

The conductive particles of the present invention include substrate particles, a conductive layer covering the substrate particles, and a plurality of core materials embedded in the conductive layer, and the conductive layer has protrusions on the outer surface, and the conductive layer is Protruding The core material is disposed on the inner side, and the conductive layer is disposed between the substrate particles and the core material, and a surface of the substrate particle is spaced apart from a surface of the core material, and a surface of the substrate particle and the core are Since the average distance between the surfaces of the substances exceeds 5 nm, when the conductive particles of the present invention are applied to the connection between the electrodes, the connection resistance between the electrodes can be lowered.

Hereinafter, the details of the present invention will be described.

The conductive particles of the present invention include substrate particles, a conductive layer covering the substrate particles, and a plurality of core materials embedded in the conductive layer. The conductive layer is attached to the outer surface and has a plurality of protrusions. The core material is disposed inside the protrusion of the conductive layer. The conductive layer is disposed between the substrate particles and the core material. A region of one of the conductive layers is disposed between the substrate particles and the core material. The surface of the substrate particles is spaced apart from the surface of the core material. The average distance between the surface of the substrate particles and the surface of the core material exceeds 5 nm.

In the case where the surface of the electrode connected by the conductive particles is formed, an oxide film is often formed. Further, an oxide film is often formed on the surface of the outer side of the conductive layer. The conductive layer has a plurality of protrusions on the outer surface, whereby the conductive particles are placed between the electrodes and then pressed, whereby the oxide film is removed by the protrusions. Therefore, the electrode can be brought into contact with the conductive particles, so that the connection resistance between the electrodes can be reduced.

Further, in the conductive particles of the present invention, the conductive layer is disposed between the substrate particles and the core material, and the surface of the substrate particles is as described above The surface of the core material is separated by a distance, and the average distance between the surface of the substrate particle and the surface of the core material exceeds 5 nm. Therefore, when the conductive particles are compressed between the electrodes, it is difficult for the core material to be pressed into the substrate particles. Therefore, it is difficult to embed a region of a part of the core material into the substrate particles. In particular, even if the substrate particles are relatively soft resin particles, it is difficult for the core material to be pressed into the substrate particles, and it is difficult to embed a portion of the core material into the substrate particles. Therefore, when the electrodes are crimped, the protrusions of the conductive layer are strongly pressed to the electrodes. As a result, the oxide film is effectively removed by the protrusions. Therefore, the electrode can be effectively brought into contact with the conductive particles, so that the connection resistance between the electrodes can be effectively reduced.

Further, since the conductive particles of the present invention have the above-described configuration, when the conductive particles are compressed and the electrodes are connected to each other, an appropriate indentation can be formed on the electrodes. Further, the indentation formed on the electrode is a concave portion of the electrode which is generated by the conductive particles pressing the electrode. Further, when a conductive material (an anisotropic conductive material or the like) in which conductive particles are dispersed in a binder resin is used for the pressure bonding between the electrodes, the adhesive resin between the conductive layer and the electrode can be effectively excluded. . It is also possible to reduce the connection resistance between the electrodes by effectively eliminating the binder resin. Further, when conductive particles including an insulating material are used, the insulating material between the conductive layer and the electrode can be effectively removed by the protrusions, so that the conduction reliability between the electrodes can be effectively improved.

Further, the electrode film and the oxide film on the surface of the conductive particles are further effectively excluded, and the average distance between the surface of the substrate particle and the surface of the core material is higher from the viewpoint of further improving the conduction reliability between the electrodes. Preferably, it is 5 nm or more, more preferably 10 nm or more. Table of the above substrate particles The upper limit of the average distance between the surface and the surface of the core material is not particularly limited, and is appropriately determined in consideration of the thickness of the conductive layer and the like. The average distance between the surface of the substrate particles and the surface of the core material may be 800 nm or less, or may be 100 nm or less. The average distance between the surface of the substrate particles and the surface of the core material is preferably 30 nm or less, more preferably 20 nm or less. The average distance between the surface of the substrate particle and the surface of the core material may be 9/10 or less of the thickness of the conductive layer, and may be 1/2 or less, and may be 1/3 or less.

Further, in order to further effectively exclude the oxide film on the surface of the electrode and the conductive particles, and further improve the conduction reliability between the electrodes, the surface of the substrate particle is 100% of the total number of the core materials. The ratio of the number of core materials having a distance of more than 5 nm from the surface of the above-mentioned core material is preferably 50% or more, more preferably more than 80% and 100% or less. In all of the above core materials, the distance between the surface of the substrate particles and the surface of the core material may exceed 5 nm.

The average distance between the surface of the substrate particle and the surface of the core material means that after measuring the distance between the surface of the substrate particle and each surface of the plurality of core materials (the shortest distance of the gap), The measured values were averaged and calculated. When the conductive particles include five core materials A to E embedded in the conductive layer, the distance between the surface of the substrate particles and the surface of the core material A and the surface of the substrate particles are measured. The distance between the surface of the core material B, the distance between the surface of the substrate particle and the surface of the core material C, the distance between the surface of the substrate particle and the surface of the core material D, and the distance between the surface of the substrate particle and the surface of the core material E And thus determined The five values are averaged. Further, in the case where the core material is 10 or more, it is preferred to measure the distance between the surface of the substrate particles and each surface of all the core materials, but it is also possible to measure the surface of the substrate particles and optionally select 10 core materials. The distance between the respective surfaces is used to calculate the above average distance based on the measured 10 values.

The distance between the surface of the substrate particle and the surface of the core material can be accurately determined by taking a cross section of a plurality of portions of the conductive particles to obtain an image, and forming a volume map based on the obtained image. Like, thus using the obtained stereoscopic image. The imaging of the above cross section can be performed using a concentrated ion beam-scanning electron microscope (FIBSEM, Focused Ion Beam Scanning Electron Microscope) or the like. For example, a film slice of conductive particles is produced using a focused ion beam, and the cross section is observed by a scanning electron microscope. This operation is repeated hundreds of times to perform image analysis, whereby a stereoscopic image of the particles can be obtained.

The conductive layer has protrusions on the outer surface. The protrusions are plural. An oxide film is often formed on the surface of the conductive layer and the surface of the electrode connected by the conductive particles. The conductive particles are protruded between the electrodes by the conductive particles used on the surface on the outer side of the conductive layer, whereby the oxide film is effectively removed by the protrusions. Therefore, the electrode and the conductive layer of the conductive particles can be more reliably contacted, and the connection resistance between the electrodes can be reduced. Further, when the conductive particles include an insulating material on the surface or when the conductive particles are dispersed in the binder resin to be used as a conductive material, the conductive particles can be effectively excluded by the protrusion of the conductive particles. Insulation between the electrode, Or binder resin. Therefore, the conduction reliability between the electrodes can be improved.

The average height of the plurality of protrusions is preferably 0.001 μm or more, more preferably 0.05 μm or more, and is preferably 0.9 μm or less, more preferably 0.2 μm or less. When the average height of the protrusions is not less than the above lower limit and not more than the above upper limit, the connection resistance between the electrodes can be effectively reduced.

Hereinafter, the details of the conductive particles, the conductive material, and the connection structure will be described.

(conductive particles)

Fig. 1 is a cross-sectional view showing conductive particles according to a first embodiment of the present invention.

The conductive particles 1 shown in FIG. 1 include a substrate particle 2, a conductive layer 3, a plurality of core materials 4, and an insulating material 5. The conductive layer 3 is disposed on the surface of the substrate particles 2. In the conductive particles 1, a single layer of the conductive layer 3 is formed. The conductive layer 3 is coated with the substrate particles 2. The conductive layer 3 has a plurality of protrusions 3a on the outer surface. A plurality of core materials 4 are disposed on the surface of the substrate particles 2 and embedded in the conductive layer 3. The core material 4 is disposed inside the protrusion 3a. One core material 4 is disposed inside one protrusion 3a. The surface of the outer side of the conductive layer 3 is embossed by the plurality of core materials 4, thereby forming a plurality of protrusions 3a.

A conductive layer 3 is disposed between the surface of the substrate particle 2 and the surface of the core material 4. The surface of the substrate particles 2 is spaced apart from the surface of the core material 4. The core material 4 is not in contact with the substrate particles 2. In the conductive particles 1, the average distance between the surface of the substrate particles 2 and the surface of the core material 4 exceeds 5 nm. Therefore, between the surface of the substrate particle 2 and the surface of the core material 4, a charge is disposed. Part of the conductive layer 3 (conductive layer portion 3b). The distance between the surface of the substrate particle 2 and the surface of the core material 4 is the thickness of the conductive layer portion 3b disposed between the surface of the substrate particle 2 and the surface of the core material 4.

The insulating material 5 is disposed on the surface of the conductive layer 3. The insulating material 5 is an insulating particle. The insulating material 5 is formed of a material having an insulating property. The conductive particles may not necessarily include an insulating material. Further, the conductive particles may include an insulating layer covering the surface on the outer side of the conductive layer as an insulating material in addition to the insulating particles.

In Fig. 2, the conductive particles of the second embodiment of the present invention are shown in a cross-sectional view.

The conductive particles 11 shown in FIG. 2 include a substrate particle 2, a conductive layer 12, a plurality of core materials 4, and an insulating material 5. The conductive layer 12 is disposed on the surface of the substrate particles 2. The conductive layer 12 is coated with the substrate particles 2. The conductive layer 12 is attached to the outer surface and has a plurality of protrusions 12a.

The conductive particles 11 are formed with a plurality of conductive layers 12. The conductive layer 12 has a first conductive layer 16 and a second conductive layer 17. The first conductive layer 16 is disposed on the surface of the substrate particles 2 . The first conductive layer 16 is coated with the substrate particles 2 . The first conductive layer 16 is a single layer. The first conductive layer may also be a plurality of layers.

The core material 4 is disposed on the first conductive layer 16. The core material 4 is embedded in the conductive layer 12 and the second conductive layer 17. The first conductive layer 16 is disposed between the substrate particles 2 and the core material 4. The first conductive layer 16 is disposed between the substrate particles 2 and the core material 4, whereby the surface of the substrate particles 2 is spaced apart from the surface of the core material 4. The average distance between the surface of the substrate particle 2 and the surface of the core material 4 is more than 5 nm. In the conductive particles 11, the surface of the substrate particles 2 and the core The distance between the surfaces of the mass 4 is the thickness of the conductive layer portion 12b and the first conductive layer 16 (the first conductive layer 16 portion) disposed between the surface of the substrate particle 2 and the surface of the core material 4.

The second conductive layer 17 is formed separately from the first conductive layer 16. The second conductive layer 17 is formed on the surface of the first conductive layer 16 after the first conductive layer 16 is formed. The second conductive layer 17 is disposed on the surface of the first conductive layer 16. The second conductive layer 17 covers the core material 4 and the first conductive layer 16. The second conductive layer 17 is on the outer surface and has a plurality of protrusions 17a. A plurality of core materials 4 are buried in the second conductive layer 17. The core material 4 is disposed inside the protrusion 17a. The surface of the outer side of the second conductive layer 17 is embossed by the plurality of core materials 4, whereby the protrusions 17a are formed.

In Fig. 3, the conductive particles of the third embodiment of the present invention are shown in a cross-sectional view.

The conductive particles 21 shown in FIG. 3 include a substrate particle 2, a conductive layer 22, a plurality of core materials 4, and an insulating material 5. The conductive layer 22 is disposed on the surface of the substrate particles 2. The conductive layer 22 coats the substrate particles 2. The conductive layer 22 is attached to the outer surface and has a plurality of protrusions 22a.

The conductive particles 21 are formed with a plurality of conductive layers 22. The conductive layer 22 has a first conductive layer 26 and a second conductive layer 27. The first conductive layer 26 is disposed on the surface of the substrate particles 2 . The first conductive layer 26 coats the substrate particles 2 .

The core material 4 is disposed on the first conductive layer 26. The core material 4 is embedded in the conductive layer 22 and in the second conductive layer 27. The first conductive layer 26 is disposed between the substrate particles 2 and the core material 4 . The first conductive layer 26 is disposed between the substrate particles 2 and the core material 4, whereby the surface of the substrate particles 2 is separated from the surface of the core material 4. Open distance. The average distance between the surface of the substrate particle 2 and the surface of the core material 4 exceeds 5 nm. In the conductive particles 21, the distance between the surface of the substrate particle 2 and the surface of the core material 4 is disposed between the surface of the substrate particle 2 and the surface of the core material 4, the conductive layer portion 22b and the first conductive layer. The thickness of the 26 part.

The second conductive layer 27 is disposed on the surface of the first conductive layer 26. The second conductive layer 27 is a core material 4 and a first conductive layer 26 . The second conductive layer 27 has a plurality of protrusions 27a on the outer surface. The core material 4 is disposed inside the protrusion 27a. The surface of the outer side of the second conductive layer 27 is embossed by the plurality of core materials 4, whereby the projections 27a are formed.

The third conductive layer 28 is disposed on the surface of the second conductive layer 27. The third conductive layer 28 is coated with the second conductive layer 27. The third conductive layer 28 has a plurality of protrusions 28a on the outer surface. The core material 4 is disposed inside the protrusion 28a. The surface of the outer side of the third conductive layer 28 is embossed by the plurality of core materials 4, whereby the protrusions 28a are formed.

Preferably, the metal element containing the most of the core material is the same as the metal element containing the most of the conductive layer. In this case, the adhesion between the core material and the conductive layer is improved, and as a result, the connection resistance of the connection structure is further improved. Furthermore, the metal element which is most contained in the core material and the metal element which is most contained in the conductive layer may have a concentration gradient in the core material, in the conductive layer, or in the core material and the conductive layer. Further, the metal element containing the most of the core material and the metal element containing the most of the conductive layer may be alloyed with other metals. Further, the metal contained in the core material and the metal system included in the conductive layer are also Can be alloyed at the interface.

Preferably, the metal element containing the most of the core material is the same as the metal element containing the most of the first conductive layer. In this case, the adhesion between the core material and the conductive layer is improved, and as a result, the connection resistance of the connection structure is further improved. Furthermore, the metal element containing the most of the core material and the metal element containing the most of the first conductive layer may be in the core material, in the first conductive layer, or in the core material and the first conductive layer. Medium with a concentration gradient. The metal element containing the most of the first conductive layer may be alloyed with other metals. The metal contained in the core material and the metal contained in the first conductive layer may be alloyed at the interface.

Preferably, the metal element containing the most of the core material is the same as the metal element containing the most of the second conductive layer. In this case, the adhesion between the core material and the conductive layer is improved, and as a result, the connection resistance of the connection structure is further improved. Furthermore, the metal element containing the most metal element and the metal element containing the most of the second conductive layer may be in the core material, in the second conductive layer, or in the core material and the second conductive layer. Medium with a concentration gradient. The metal element containing the most of the second conductive layer may be alloyed with other metals. The metal contained in the core material and the metal contained in the second conductive layer may be alloyed at the interface.

Preferably, the Mohs hardness of the core material is the same as the Mohs hardness of the portion of the conductive layer disposed between the substrate particles and the core material, or the Mohs hardness of the core material is greater than that of the substrate particles and The Mohs hardness of the portion of the conductive layer between the above core materials. Further, preferably, the Mohs hardness of the core material is the same as the Mohs hardness of the first conductive layer, or the core The Mohs hardness of the substance is greater than the Mohs hardness of the first conductive layer. In such cases, it is difficult for the core material to be pressed into the substrate particles, so that a portion of the core material is difficult to be buried in the substrate particles. As a result, the connection resistance between the electrodes can be further reduced. From the viewpoint of further reducing the connection resistance between the electrodes, it is preferable that the Mohs hardness of the core material is larger than a Mohs portion disposed between the substrate particles and the core material or a Mohs layer of the first conductive layer hardness.

When the Mohs hardness of the core material is equal to or higher than the Mohs hardness of the conductive layer portion disposed between the substrate particles and the core material or the first conductive layer, the connection resistance is further lowered. In view of the above, the absolute value of the difference between the Mohs hardness of the core material and the Moiré hardness of the conductive layer portion disposed between the substrate particles and the core material or the first conductive layer is preferably 0.1 or more. More preferably 0.5 or more.

Preferably, the core material has a Mohs hardness which is smaller than a Mohs hardness of a portion of the conductive layer disposed between the substrate particles and the core material. Preferably, the core material has a Mohs hardness which is smaller than a Mohs hardness of the first conductive layer. In such cases, the conductive layer portion and the first conductive layer have a certain degree of cushioning properties. In this case, it is possible to reduce not only the connection resistance generated by the conductive layer portion disposed between the substrate particles and the core material but also the first conductive layer, but also the connection structure between the electrodes by the conductive particles. Impact also becomes difficult to cause poor conduction. That is, the impact resistance of the connection structure can also be improved.

The Mohs hardness of the core material is smaller than a portion of the conductive layer disposed between the substrate particles and the core material, or the first conductive layer In the case of the Mohs hardness, the Mohs hardness of the core material and the conductive layer portion disposed between the substrate particles and the core material, or the first conductive layer, from the viewpoint of further improving the impact resistance. The absolute value of the difference in the Mohs hardness is preferably 0.1 or more, more preferably 0.5 or more.

[Substrate particles]

Examples of the substrate particles include resin particles, metal-removing inorganic particles, organic-inorganic hybrid particles, and metal particles. The substrate particles are preferably substrate particles from which metal particles are removed, more preferably resin particles, metal-removing inorganic particles, or organic-inorganic hybrid particles.

Preferably, the substrate particles are resin particles formed of a resin. When the substrate particles are resin particles, the effect of reducing the connection resistance obtained by the configuration of the conductive layer and the core material of the present invention becomes extremely large. When the conductive particles are used to connect the electrodes, the conductive particles are compressed by pressure bonding after the conductive particles are placed between the electrodes. When the base material particles are resin particles, the conductive particles are easily deformed at the time of the pressure bonding, and the contact area between the conductive particles and the electrode is increased. Therefore, the conduction reliability between the electrodes becomes high.

As the resin for forming the above resin particles, various organic materials are preferably used. Examples of the resin for forming the resin particles include polyolefin resins such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polypropylene, polyisobutylene, and polybutadiene; Acrylic resin such as methacrylate and polymethyl acrylate; polyalkylene terephthalate, polycarbonate, polyamine, phenol formaldehyde resin, melamine-formaldehyde resin, benzoguanamine formaldehyde resin, urea formaldehyde resin , phenolic resin, melamine Resin, benzoguanamine resin, urea resin, epoxy resin, unsaturated polyester resin, saturated polyester resin, polyfluorene, polyphenylene ether, polyacetal, polyimine, polyamidimide, poly Ether ether ketone, polyether oxime, and a polymer obtained by polymerizing one or two or more kinds of polymerizable monomers having an ethylenically unsaturated group. The resin particles suitable for the physical properties of the conductive material can be designed and synthesized, and the hardness of the substrate particles can be controlled within a preferred range. Therefore, the resin for forming the resin particles is preferably polymerized. A polymer of two or more kinds of polymerizable monomers having a plurality of ethylenically unsaturated groups.

When the monomer having an ethylenically unsaturated group is polymerized to obtain the above-mentioned resin particles, examples of the monomer having the ethylenically unsaturated group include a monomer having no crosslinkability and a crosslinkable monomer.

Examples of the non-crosslinkable monomer include styrene monomers such as styrene and α-methylstyrene; and carboxyl groups such as (meth)acrylic acid, maleic acid, and maleic anhydride. Monomer; methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, (a) Base (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, isobutyl methacrylate, etc. Ester; 2-hydroxyethyl (meth)acrylate, glyceryl (meth)acrylate, polyoxyethylene (meth)acrylate, glycidyl (meth)acrylate, etc. Ester; a nitrile group-containing monomer such as (meth)acrylonitrile; a vinyl ether such as methyl vinyl ether, ethyl vinyl ether or propyl vinyl ether; vinyl acetate, vinyl butyrate, laurel Acid vinyl ester, stearic acid B Acid vinyl esters such as alkenyl esters; unsaturated hydrocarbons such as ethylene, propylene, isoprene, butadiene; trifluoromethyl (meth)acrylate, pentafluoroethyl (meth)acrylate, vinyl chloride, fluorine A halogen-containing monomer such as ethylene or chlorostyrene.

Examples of the crosslinkable monomer include tetramethylol methane tetra(meth)acrylate, tetramethylol methane tri(meth)acrylate, and tetramethylolmethane di(meth)acrylate. Ester, trimethylolpropane tri(meth)acrylate, dipentaerythritol hexa(meth) acrylate, dipentaerythritol penta (meth) acrylate, tris(meth) acrylate, di(meth)acrylic acid Glycerides, (poly)ethylene glycol di(meth)acrylate, (poly)propylene glycol di(meth)acrylate, (poly)butanediol di(meth)acrylate, 1,4-butanediol Polyfunctional (meth) acrylates such as di(meth) acrylate; triallyl (iso) cyanurate, triallyl trimellitate, divinyl benzene, diallyl phthalate , dipropylene acrylamide, diallyl ether, γ-(meth) propylene methoxy propyl trimethoxy decane, trimethoxy decyl styrene, vinyl trimethoxy decane, etc. Monomers, etc.

The above-mentioned resin particles can be obtained by polymerizing a polymerizable monomer having the above ethylenically unsaturated group by a known method. As such a method, for example, suspension polymerization is carried out in the presence of a radical polymerization initiator; and the monomer is swelled and polymerized together with the radical polymerization initiator using non-crosslinked particles. .

In the case where the substrate particles are inorganic particles or organic-inorganic hybrid particles from which metal particles are removed, examples of the inorganic material for forming the substrate particles include alumina and carbon black. The particles formed of the above-described alumina are not particularly limited, and examples thereof include those obtained by the following methods. The hydrazine compound having two or more hydrolyzable alkoxyalkylene groups is hydrolyzed to form crosslinked polymer particles, and then calcined as necessary. Examples of the organic-inorganic hybrid particles include organic-inorganic hybrid particles formed by crosslinking alkoxysilane alkyl polymer and an acrylic resin.

In the case where the substrate particles are metal particles, examples of the metal for forming the metal particles include silver, copper, nickel, rhodium, gold, titanium, and the like. However, it is preferred that the substrate particles are not metal particles.

The particle diameter of the substrate particles is preferably 0.1 μm or more, more preferably 0.5 μm or more, still more preferably 1 μm or more, further preferably 1.5 μm or more, particularly preferably 2 μm or more, and more preferably 1000 μm or less, more preferably 500 μm or less, still more preferably 300 μm or less, further preferably 50 μm or less, further preferably 30 μm or less, particularly preferably 5 μm or less, and most preferably 3 μm or less. . When the particle diameter of the substrate particles is at least the above lower limit, the contact area between the conductive particles and the electrode is increased, so that the conduction reliability between the electrodes is further increased, and the connection resistance between the electrodes connected via the conductive particles is further increased. Go low. Further, when the conductive layer is formed on the surface of the substrate particles by electroless plating, aggregation becomes difficult, and it becomes difficult to form the aggregated conductive particles. When the particle diameter is at most the above upper limit, the conductive particles are easily compressed sufficiently, and the connection resistance between the electrodes is further lowered, and the interval between the electrodes is further reduced. The particle diameter of the substrate particles is a diameter when the substrate particles are in a spherical shape, and indicates a maximum diameter when the substrate particles are not spherical.

The particle diameter of the substrate particles is particularly preferably 0.1 μm or more and 5 μm or less. If When the particle diameter of the substrate particles is in the range of 0.1 to 5 μm, the interval between the electrodes becomes small, and even if the thickness of the conductive layer is made thick, smaller conductive particles are obtained. The particle diameter of the substrate particles is preferably 0.5 μm or more, more preferably from the viewpoint of further reducing the interval between the electrodes or increasing the thickness of the conductive layer to obtain further smaller conductive particles. 2 μm or more, and preferably 3 μm or less.

[conductive layer]

The metal for forming the above conductive layer is not particularly limited. Further, in the case where the conductive particles are metal particles of the entire conductive layer, the metal for forming the metal particles is not particularly limited. Examples of the metal include gold, silver, copper, palladium, platinum, zinc, iron, tin, lead, aluminum, cobalt, indium, nickel, chromium, titanium, lanthanum, cerium, lanthanum, cerium, cadmium, cerium, and tungsten. , molybdenum and these alloys. Further, examples of the metal include tin-doped indium oxide (ITO), solder, and the like. Among them, the connection resistance between the electrodes can be further lowered, and therefore it is preferably an alloy containing tin, nickel, palladium, copper or gold, more preferably nickel or palladium. The metal element constituting the above conductive layer preferably contains nickel. The conductive layer preferably contains at least one selected from the group consisting of nickel, tungsten, molybdenum, palladium, phosphorus, and boron, and more preferably contains nickel, phosphorus, or boron. The material constituting the above conductive layer may be an alloy containing phosphorus or boron. The above conductive layer may also alloy nickel with tungsten or molybdenum.

In the case where the conductive layer contains phosphorus or boron, the total content of phosphorus and boron in 100% by weight of the conductive layer is preferably 4% by weight or less. When the total content of phosphorus and boron is at most the above upper limit, the content of metal such as nickel is relatively increased, and thus the connection resistance between the electrodes is further lowered. Above The content of the total of phosphorus and boron in 100% by weight of the conductive layer is preferably 0.1% by weight or more, more preferably 0.5% by weight or more.

The core material, the conductive layer, and the metal element containing the most of the second conductive layer are preferably an alloy containing tin, nickel, palladium, copper or gold, more preferably nickel or palladium.

For example, the conductive particles 1 may be formed of one layer. Further, as the conductive particles 11 and 21, the conductive layer may be formed of a plurality of layers. That is, the conductive layer may be a single layer or may have a laminated structure of two or more layers. In the case where the conductive layer is formed of a plurality of layers, the outermost layer is preferably a gold layer, a nickel layer, a palladium layer, a copper layer, or an alloy layer containing tin and silver, more preferably a gold layer or a palladium layer. It is a gold layer. In the case where the outermost layer is such a preferred conductive layer, the connection resistance between the electrodes is further lowered. Further, when the outermost layer is a gold layer, the corrosion resistance is further increased.

A method of forming a conductive layer on the surface of the substrate particles is not particularly limited. Examples of the method of forming the conductive layer include a method using electroless plating, a method using electroplating, a physical vapor deposition, and a metal powder or a paste containing a metal powder and a binder. The surface of the particle. Among them, the formation of the conductive layer is relatively simple, and therefore it is preferable to use a method of electroless plating. Examples of the method of using the above physical vapor deposition include vacuum vapor deposition, ion plating, and ion sputtering.

The average particle diameter of the conductive particles is preferably 0.11 μm or more, more preferably 0.5 μm or more, further preferably 0.51 μm or more, particularly preferably 1 μm or more, and more preferably 100 μm or less, more preferably 20 It is preferably 5.6 μm or less, and particularly preferably 3.6 μm or less. If the conductive particles are flat When the average particle diameter is not less than the above lower limit and not more than the above upper limit, when the conductive particles are connected between the electrodes, the contact area between the conductive particles and the electrode is sufficiently increased, and when the conductive layer is formed, it becomes difficult to form a via. Condensed conductive particles. Moreover, the interval between the electrodes connected via the conductive particles is excessively large, and the conductive layer is less likely to be peeled off from the surface of the substrate particles.

The "average particle diameter" of the above conductive particles means a number average particle diameter. The average particle diameter of the conductive particles was determined by observing 50 arbitrary conductive particles by an electron microscope or an optical microscope to calculate an average value.

The thickness of the above conductive layer is preferably 0.005 μm or more, more preferably 0.01 μm or more, and is preferably 1 μm or less, more preferably 0.3 μm or less. When the thickness of the conductive layer is not less than the above lower limit and not more than the above upper limit, sufficient conductivity is obtained, and the conductive particles are not excessively hard, and the conductive particles are sufficiently deformed at the time of connection between the electrodes.

When the conductive layer is formed of a plurality of layers, the thickness of the outermost conductive layer is preferably 0.001 μm or more, more preferably 0.01 μm or more, and is preferably 0.5 μm or less, more preferably 0.1 μm or less. When the thickness of the outermost conductive layer is not less than the above lower limit and not more than the above upper limit, the coating of the outermost conductive layer can be made uniform, the corrosion resistance can be sufficiently improved, and the connection between the electrodes can be sufficiently reduced. resistance.

The thickness of the conductive layer is measured by, for example, observing a cross section of conductive particles or conductive particles with insulating particles using a transmission electron microscope (TEM).

Protrusions on the outer surface of the above-mentioned conductive layer of each of the above conductive particles It is preferably 3 or more, more preferably 5 or more. The upper limit of the number of the above protrusions is not particularly limited. The upper limit of the number of protrusions can be appropriately selected in consideration of the average particle diameter of the conductive particles and the like.

[core material]

The core material is embedded in the conductive layer, whereby the conductive layer has a plurality of protrusions on the outer surface.

As a method of forming the protrusions, a method of forming a first conductive layer on the surface of the substrate particles, disposing a core material on the first conductive layer, and then forming a second conductive layer; On the surface of the material particles, a core material is added in the middle of the formation of the conductive layer.

Examples of the material constituting the core material include a conductive material and a non-conductive material. Examples of the conductive material include a metal, a metal oxide, a conductive non-metal such as graphite, and a conductive polymer. Examples of the conductive polymer include polyacetylene and the like. Examples of the non-conductive material include alumina, alumina, barium titanate, and zirconia. Among them, since the conductivity can be improved and the connection resistance can be effectively lowered, the metal is preferable. The above core material is preferably a metal particle.

Examples of the metal include metals such as gold, silver, copper, platinum, zinc, iron, lead, tin, aluminum, cobalt, indium, nickel, chromium, titanium, ruthenium, osmium, iridium, and cadmium, and tin-lead alloys. An alloy composed of two or more kinds of metals such as tin-copper alloy, tin-silver alloy, tin-lead-silver alloy, and tungsten carbide. Among them, nickel, copper, silver or gold is preferred. The metal constituting the core material may be the same as or different from the metal constituting the above-mentioned conductive layer. The metal constituting the core material preferably contains a metal constituting the conductive layer. Constituting the above core The metal of the substance preferably contains nickel. The metal constituting the core material preferably contains nickel.

The shape of the core material is not particularly limited. The shape of the core material is preferably a block shape. Examples of the core material include a particulate block, agglomerates in which a plurality of fine particles are agglomerated, and an amorphous block.

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

The "average diameter (average particle diameter)" of the above-mentioned core material means a number average diameter (number average particle diameter). The average diameter of the core material was determined by observing 50 arbitrary core materials by an electron microscope or an optical microscope to calculate an average value.

Inorganic particles may also be disposed on the surface of the above-mentioned core material. The inorganic particles disposed on the surface of the core material are preferably plural. Inorganic particles may also be attached to the surface of the core material. Composite particles including such inorganic particles and core materials can also be used. The size (average diameter) of the inorganic particles is preferably smaller than the size (average diameter) of the core material, and the inorganic particles are preferably inorganic fine particles.

Examples of the material of the inorganic particles disposed on the surface of the core material include barium titanate (Mohs hardness of 4.5), alumina (cerium oxide, Mohs hardness of 6 to 7), and zirconia (Mohs Hardness is 8 to 9), alumina (Mohs hardness is 9), tungsten carbide (Mohs hardness is 9), and diamond (Mohs hardness is 10). The above inorganic particles are preferably alumina, zirconia, alumina, carbonization. Tungsten or diamond is also preferably alumina, zirconia, alumina or diamond. The Mohs hardness of the inorganic particles is preferably 5 or more, and more preferably 6 or more. The Mohs hardness of the inorganic particles is preferably greater than the Mohs hardness of the conductive layer. The Mohs hardness of the inorganic particles is greater than the Mohs hardness of the second conductive layer. The absolute value of the difference between the Mohs hardness of the inorganic particles and the Mohs hardness of the conductive layer, and the absolute value of the difference between the Mohs hardness of the inorganic particles and the Mohs hardness of the second conductive layer is preferably 0.1 or more. More preferably, it is 0.2 or more, further preferably 0.5 or more, and particularly preferably 1 or more. Further, in the case where the conductive layer is formed of a plurality of layers, the effect of lowering the connection resistance is more effectively exhibited than the harder particles of all the metals constituting the plurality of layers.

The average particle diameter of the inorganic particles is preferably 0.0001 μm or more, more preferably 0.005 μm or more, and is preferably 0.5 μm or less, more preferably 0.1 μm or less. When the average particle diameter of the inorganic particles is not less than the above lower limit and not more than the above upper limit, the connection resistance between the electrodes can be effectively reduced.

The "average particle diameter" of the above inorganic particles means a number average particle diameter. The average particle diameter of the inorganic particles was determined by observing 50 arbitrary inorganic particles by an electron microscope or an optical microscope to calculate an average value.

In the case where the composite particles of the inorganic particles are disposed on the surface of the core material, the average diameter (average particle diameter) of the composite particles is preferably 0.0012 μm or more, more preferably 0.0502 μm or more, and is preferably It is 1.9 μm or less, more preferably 1.2 μm or less. When the average diameter of the composite particles is not less than the above lower limit and not more than the above upper limit, the connection resistance between the electrodes can be effectively reduced.

The "average diameter (average particle diameter)" of the above composite particles means a number average diameter (number average particle diameter). The average diameter of the composite particles was determined by observing 50 arbitrary composite particles by an electron microscope or an optical microscope to calculate an average value.

[insulating substance]

The conductive particles of the present invention preferably include an insulating material disposed on the surface of the conductive layer. In this case, when the conductive particles are used for the connection between the electrodes, the short circuit between the adjacent electrodes can be prevented. Specifically, when a plurality of conductive particles are in contact with each other, an insulating material is present between the plurality of electrodes, so that short circuits between adjacent electrodes in the lateral direction can be prevented, and short circuits between the upper and lower electrodes are not obtained. Further, when the electrodes are connected, the conductive particles are pressurized by the two electrodes, whereby the insulating material between the conductive layers of the conductive particles and the electrodes can be easily removed. Since the conductive particles have a plurality of protrusions on the surface on the outer side of the conductive layer, the insulating material between the conductive layer of the conductive particles and the electrode can be easily excluded.

In the case of pressure bonding between the electrodes, the insulating material can be further removed more easily, and therefore the insulating material is preferably insulating particles.

Specific examples of the insulating resin which is a material of the insulating material include a polyolefin, a (meth) acrylate polymer, a (meth) acrylate copolymer, a block polymer, a thermoplastic resin, and a thermoplastic resin. Linkage, thermosetting resin and water-soluble resin.

Examples of the polyolefins include polyethylene, an ethylene-vinyl acetate copolymer, and an ethylene-acrylate copolymer. Examples of the (meth) acrylate polymer include poly(methyl) propylene methyl ester and (meth) propylene polyethylene. Ester and (meth) propylene polybutyl ester. Examples of the block polymer include polystyrene, styrene-acrylate copolymer, SB (Styrene Butadiene) type styrene-butadiene block copolymer, and SBS (Styrene Butadiene Styrene) type styrene-butyl a diene block copolymer, such hydrogen additives, and the like. Examples of the thermoplastic resin include a vinyl polymer and a vinyl copolymer. Examples of the thermosetting resin include an epoxy resin, a phenol resin, and a melamine resin. Examples of the water-soluble resin include polyvinyl alcohol, polyacrylic acid, polyamidamide, polyvinylpyrrolidone, ethylene oxide, and methyl cellulose. Among them, a water-soluble resin is preferred, and polyvinyl alcohol is more preferred.

Examples of the method of disposing the insulating material on the surface of the conductive layer include chemical methods, physical or mechanical methods, and the like. Examples of the chemical method include an interfacial polymerization method, a suspension polymerization method in the presence of particles, and an emulsion polymerization method. Examples of the physical or mechanical method include spray drying, hybridization, electrostatic adhesion, spray, immersion, and vacuum evaporation. Among them, since the insulating material is hard to be desorbed, it is preferable to dispose the insulating material on the surface of the conductive layer via chemical bonding.

The average diameter (average particle diameter) of the insulating material can be appropriately selected depending on the particle diameter of the conductive particles and the use of the conductive particles. The average diameter (average particle diameter) of the insulating material is preferably 0.005 μm or more, more preferably 0.01 μm or more, and is preferably 1 μm or less, more preferably 0.5 μm or less. When the average diameter of the insulating material is at least the above lower limit, when the conductive particles are dispersed in the binder resin, the conductive layers of the plurality of conductive particles become different. It is difficult to get in touch. When the average diameter of the insulating particles is not more than the above upper limit, in order to remove the insulating material between the electrode and the conductive particles during the connection between the electrodes, it is not necessary to increase the pressure, and it is not necessary to heat at a high temperature.

The "average diameter (average particle diameter)" of the above insulating material means a number average diameter (number average particle diameter). The average diameter of the insulating material is determined using a particle size distribution measuring device or the like.

(conductive material)

The conductive material of the present invention comprises the above-mentioned conductive particles and a binder resin. The conductive particles are preferably dispersed in a binder resin and used as a conductive material. The above conductive material is preferably an anisotropic conductive material.

The above binder resin is not particularly limited. As the above-mentioned binder resin, a known insulating resin is used.

Examples of the binder resin include a vinyl resin, a thermoplastic resin, a curable resin, a thermoplastic block copolymer, and an elastomer. The binder resin may be used alone or in combination of two or more.

Examples of the vinyl resin include a vinyl acetate resin, an acrylic resin, and a styrene resin. Examples of the thermoplastic resin include a polyolefin resin, an ethylene-vinyl acetate copolymer, and a polyamide resin. Examples of the curable resin include an epoxy resin, a urethane resin, a polyimide resin, and an unsaturated polyester resin. Further, the curable resin may be a room temperature curing resin, a thermosetting resin, a photocurable resin, or a moisture curing resin. The curable resin may be used in combination with a curing agent. As the above thermoplastic block copolymer, for example, Listed styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, hydrogen addition of styrene-butadiene-styrene block copolymer, and benzene Hydrogen additive of ethylene-isoprene-styrene block copolymer, and the like. Examples of the elastomer include a styrene-butadiene copolymer rubber and an acrylonitrile-styrene block copolymer rubber.

The conductive material may contain, in addition to the conductive particles and the binder resin, a filler, a bulking agent, a softener, a plasticizer, a polymerization catalyst, a curing catalyst, a colorant, an antioxidant, and a heat. Various additives such as stabilizers, light stabilizers, ultraviolet absorbers, lubricants, antistatic agents, and flame retardants.

The method of dispersing the above-mentioned conductive particles in the above-mentioned binder resin can be a conventionally known dispersion method, and is not particularly limited. As a method of dispersing the above-mentioned conductive particles in the above-mentioned binder resin, for example, a method in which the conductive particles are added to the binder resin and then kneaded by a planetary mixer or the like is dispersed; After the conductive particles are uniformly dispersed in water or an organic solvent, the conductive particles are added to the binder resin to be dispersed by a planetary mixer or the like, and are dispersed by water or an organic solvent. After the binder resin is diluted, the conductive particles are added and dispersed by a planetary mixer or the like.

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

The content of the binder resin 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, based on 100% by weight of the conductive material. It is preferably 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 effectively disposed between the electrodes, and the connection reliability of the member to be joined connected by the conductive material is further increased.

The content of the conductive particles is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, and preferably 40% by weight or less, and more preferably 20% by weight or less, based on 100% by weight of the conductive material. Further, it is preferably 10% by weight or less. When the content of the conductive particles is not less than the above lower limit and not more than the above upper limit, the conduction reliability between the electrodes is further increased.

(connection structure)

The connection structure can be obtained by using the conductive particles of the present invention or by using a conductive material containing the conductive particles and the binder resin to connect the connection member.

Preferably, the connection structure includes a first connection target member, a second connection target member, and a connection portion that connects the first and second connection target members, and the connection portion is electrically conductive according to the present invention. It is formed of a magnetic particle or a conductive material (an anisotropic conductive material or the like) containing the conductive particle and the binder resin. In the case where conductive particles are used, the connecting portion itself is a conductive particle. In other words, the first and second connection target members are connected by conductive particles.

In Fig. 4, a front cross-sectional view schematically shows a connection structure using the conductive particles according to the first embodiment of the present invention.

The connection structure 51 shown in FIG. 4 includes a first connection object member 52, a second connection object member 53, and a connection portion 54 that connects the first and second connection object members 52 and 53. The connecting portion 54 is formed by curing the conductive material containing the conductive particles 1. In addition, in FIG. 4, for the convenience of illustration, the electroconductive particle 1 is shown in the outline.

The first connection object member 52 is attached to the upper surface 52a (surface) and has a plurality of electrodes 52b. The second connection object member 53 has a plurality of electrodes 53b on the lower surface 53a (surface). The electrode 52b and the electrode 53b are electrically connected by one or a plurality of conductive particles 1. Therefore, the first and second connection target members 52 and 53 are electrically connected by the conductive particles 1 .

The method for producing the above-described connection structure is not particularly limited. An example of the method of manufacturing the connection structure is a method in which the conductive material is placed between the first connection member and the second connection member to obtain a laminate, and then the laminate is heated and pressurized. .

The pressure of the above pressurization is about 9.8 × 10 ⁴ to 4.9 × 10 ⁶ Pa. The heating temperature is about 120 to 220 °C.

Specific examples of the connection target member include electronic components such as a semiconductor wafer, a capacitor, and a diode, and electronic components such as a printed circuit board, a flexible printed circuit board, and a circuit board such as a glass substrate. The connection target member is preferably an electronic component. The conductive particles are preferably electrically connected to electrodes of an electronic component.

Examples of the electrode provided in the connection target member include a gold electrode, Metal electrodes such as a nickel electrode, a tin electrode, an aluminum electrode, a copper electrode, a molybdenum electrode, and a tungsten electrode. In the case where the connection target member is a flexible printed circuit board, the electrode system is preferably a gold electrode, a nickel electrode, a tin electrode, or a copper electrode. In the case where the connection target member is a glass substrate, the electrode system is preferably an aluminum electrode, a copper electrode, a molybdenum electrode or a tungsten electrode. Further, in the case where 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 the 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, Ga, and the like.

Hereinafter, the present invention will be specifically described by way of examples and comparative examples. The invention is not limited to the following examples.

(Example 1) (1) Palladium attachment step

Divinylbenzene resin particles ("Micropearl SP-205" manufactured by Sekisui Chemical Co., Ltd.) having a particle diameter of 5.0 μm were prepared. The resin particles were etched and washed with water. Next, to 100 mL of a 100 mL palladium catalyst solution containing 8 wt% of a palladium catalyst, resin particles were added and stirred. Thereafter, filtration and washing are carried out. To the dimethylamine borane solution having a pH of 6 at 0.5% by weight, resin particles were added to obtain resin particles to which palladium adhered.

(2) Electroless nickel plating step

In order to form a nickel-phosphorus conductive layer, a nickel plating solution containing 0.25 mol/L of nickel sulfate, 0.25 mol/L of sodium hypophosphite, 0.15 mol/L of sodium citrate, and 0.01 mol/L of sodium molybdate is prepared. (pH 8.0).

The obtained palladium-attached resin particles were added to 1000 mL of pure water, and dispersed by an ultrasonic disperser, thereby obtaining a suspension. While the obtained suspension was stirred at 60 ° C, the nickel plating solution was gradually dropped to the suspension to carry out electroless nickel plating. Thereafter, the particles were taken out by filtration of the suspension, washed with water, and dried, whereby a nickel-phosphorus layer (nickel-molybdenum-phosphorus layer (Ni-Mo-P layer)), that is, a first conductive layer (thickness: 5.2) was used. The resin particles are coated with nm to obtain particles in which the first conductive layer is formed.

(3) Core substance attachment step and electroless nickel plating step

A slurry of alumina (Al ₂ O ₃ ) particles (having an average particle diameter of 100 nm) was prepared. The particles in which the first conductive layer is formed are coated with the metal particle slurry.

In order to form a nickel-phosphorus conductive layer, a nickel plating solution containing 0.25 mol/L of nickel sulfate, 0.25 mol/L of sodium hypophosphite, 0.15 mol/L of sodium citrate, and 0.01 mol/L of sodium molybdate is prepared. (pH 8.0).

While stirring the obtained suspension at 60 ° C, the nickel plating solution was gradually dropped to the suspension to carry out electroless nickel plating to form a second conductive layer (nickel-molybdenum-phosphorus layer having a thickness of 90 nm). Ni-Mo-P layer)). Thereafter, the particles were taken out by filtration of the suspension, washed with water, and dried to obtain conductive particles. The conductive particles obtained have protrusions on the outer surface of the second conductive layer, and a core material is disposed inside the protrusions of the second conductive layer. Further, a first conductive layer is disposed between the resin particles and the core material.

(Example 2)

Conductive particles were obtained in the same manner as in Example 1 except that the alumina (Al ₂ O ₃ ) particle slurry (average particle diameter: 100 nm) was changed to an alumina particle slurry (average particle diameter: 100 nm).

(Example 3)

Conductive particles were obtained in the same manner as in Example 1 except that the alumina (Al ₂ O ₃ ) particle slurry (average particle diameter: 100 nm) was changed to a tungsten carbide (WC) particle slurry (average particle diameter: 100 nm). .

(Examples 4 to 8)

Conductive particles were obtained in the same manner as in Example 1 except that the thickness of the first conductive layer, which is a nickel-phosphorus layer, was changed to the value shown below.

Thickness of the first conductive layer:

Example 4: 10 μm

Example 5: 20 μm

Example 6: 100 μm

Example 7: 750 μm

Example 8: 860 μm

(Example 9) (1) Production of insulating particles

In a 1000 mL separable flask equipped with four separable caps, agitating blades, a three-way cock, a cooling tube and a temperature probe, a solid content of 5 wt% will contain 100 mmol of methyl group. Methyl acrylate, 1 mmol of N,N,N-trimethyl-N-2-methylpropenyloxyethylammonium chloride, and 1 mmol of 2,2'-azobis(2-indenyl) The monomer composition of propane) dihydrochloride was weighed to ion-exchanged water, stirred at 200 rpm, and polymerized at 70 ° C for 24 hours under a nitrogen atmosphere. After the reaction is completed, lyophilization is carried out to obtain an ammonium group on the surface, and the average particle diameter is 220 nm and Insulating particles having a CV (Coefficient of Variation) value of 10%.

The insulating particles were dispersed in ion-exchanged water under ultrasonic irradiation to obtain an aqueous dispersion in which the insulating particles were 10% by weight.

10 g of the conductive particles obtained in Example 1 was dispersed in 500 mL of ion-exchanged water, and 4 g of an aqueous dispersion of insulating particles was added thereto, followed by stirring at room temperature for 6 hours. After filtering by a 3 μm mesh filter, the mixture was washed with methanol and dried to obtain conductive particles to which insulating particles were attached.

Observation by a scanning electron microscope (SEM, Scanning Electron Microscope) revealed that only one layer of the coating layer due to the insulating particles was formed on the surface of the conductive particles. The coverage area of the insulating particles with respect to the area of 2.5 μm from the center of the conductive particles (that is, the projected area of the particle diameter of the insulating particles) was calculated by image analysis, and as a result, the coverage ratio was 30%.

(Embodiment 10)

In addition to the divinylbenzene resin particles ("Micropearl SP-205" manufactured by Sekisui Chemical Co., Ltd.) having a particle size of 5.0 μm, the divinyl benzene resin particles having a particle size of 5.0 μm are coated with alumina (Shuishui Chemical Industry Co., Ltd.) Conductive particles were obtained in the same manner as in Example 1 except that the organic-inorganic hybrid particles (having a particle diameter of 5.1 μm) of "Micropearl SP-205" manufactured by the company.

(Comparative Example 1)

Conductive particles were obtained in the same manner as in Example 1 except that the thickness of the nickel-phosphorus layer, that is, the first conductive layer was changed to 4.5 nm.

(Comparative Example 2)

Divinylbenzene resin particles ("Micropearl SP-205" manufactured by Sekisui Chemical Co., Ltd.) having a particle diameter of 5.0 μm were prepared. Further, an alumina (Al ₂ O ₃ ) particle slurry (having an average particle diameter of 100 nm) was prepared. The resin particles and the metal particle slurry were used to coat the surface of the resin particles with a core material to obtain a suspension.

In order to form a nickel-phosphorus conductive layer, a nickel plating solution containing 0.25 mol/L of nickel sulfate, 0.25 mol/L of sodium hypophosphite, 0.15 mol/L of sodium citrate, and 0.01 mol/L of sodium molybdate is prepared. (pH 8.0).

While the obtained suspension was stirred at 60 ° C, the nickel plating solution was gradually dropped to the suspension to carry out electroless nickel plating to form a conductive layer having a thickness of 100 nm. Thereafter, the particles were taken out by filtration of the suspension, washed with water, and dried to obtain conductive particles. The obtained conductive particle-based core material is in contact with the substrate particles.

(Example 11) (1) Palladium attachment step

The palladium-attached resin particles obtained in Example 1 were prepared.

(2) Electroless nickel plating step

A nickel plating solution (pH 8.5) containing 0.23 mol/L of nickel sulfate, 0.92 mol/L of dimethylamine borane, 0.5 mol/L of sodium citrate, and 0.01 mol/L of sodium tungstate was prepared.

The obtained palladium-attached resin particles were added to 1000 mL of pure water, and dispersed by an ultrasonic disperser, thereby obtaining a suspension. While stirring the obtained suspension at 60 ° C, the nickel plating solution was slowly dropped on one side. The suspension is passed down to perform electroless nickel plating. Thereafter, the particles were taken out by filtration of the suspension, washed with water, and dried to coat the resin particles with a nickel-tungsten-boron layer, which is a first conductive layer (having a thickness of 5.1 nm), thereby obtaining a first conductive layer. Layer particles.

(3) Core substance attachment step and electroless nickel plating step

A slurry of alumina (Al ₂ O ₃ ) particles (having an average particle diameter of 100 nm) was prepared. The particles in which the first conductive layer is formed are coated with the metal particle slurry.

A nickel plating solution (pH 8.5) containing 0.23 mol/L of nickel sulfate, 0.92 mol/L of dimethylamine borane, 0.5 mol/L of sodium citrate, and 0.01 mol/L of sodium tungstate was prepared.

While the obtained suspension was stirred at 60 ° C, the nickel plating solution was gradually dropped to the suspension to carry out electroless nickel plating to form a second conductive layer having a thickness of 90 nm. Thereafter, the particles are taken out by filtration of the suspension, washed with water, and dried to obtain conductive particles. The conductive particles obtained have protrusions on the outer surface of the second conductive layer, and a core material is disposed inside the protrusions of the second conductive layer. Further, a first conductive layer is disposed between the resin particles and the core material.

(Embodiment 12)

Conductive particles were obtained in the same manner as in Example 11 except that the thickness of the nickel-tungsten-boron layer, that is, the first conductive layer was changed to 10 nm.

(Example 13)

Conductive particles were obtained in the same manner as in Example 11 except that the thickness of the nickel-tungsten-boron layer, that is, the first conductive layer was changed to 20 nm.

(Example 14)

The insulating particles obtained in Example 9 were prepared as an aqueous dispersion of 10% by weight. 10 g of the conductive particles obtained in Example 11 was dispersed in 500 mL of ion-exchanged water, and 4 g of an aqueous dispersion of insulating particles was added thereto, followed by stirring at room temperature for 6 hours. After filtering by a 3 μm mesh filter, the mixture was washed with methanol and dried to obtain conductive particles to which insulating particles were attached.

Observation by a scanning electron microscope (SEM) revealed that only one layer of the coating layer due to the insulating particles was formed on the surface of the conductive particles. The coverage area of the insulating particles with respect to the area of 2.5 μm from the center of the conductive particles (that is, the projected area of the particle diameter of the insulating particles) was calculated by image analysis, and as a result, the coverage ratio was 30%.

(Comparative Example 3)

Conductive particles were obtained in the same manner as in Example 11 except that the thickness of the nickel-tungsten-boron layer, that is, the first conductive layer was changed to 3 nm.

(Comparative Example 4)

Divinylbenzene resin particles ("Micropearl SP-205" manufactured by Sekisui Chemical Co., Ltd.) having a particle diameter of 5.0 μm were prepared. Further, an alumina (Al ₂ O ₃ ) particle slurry (having an average particle diameter of 100 nm) was prepared. The resin particles and the metal particle slurry were used to coat the surface of the resin particles with a core material to obtain a suspension.

A nickel plating solution (pH 8.5) containing 0.23 mol/L of nickel sulfate, 0.92 mol/L of dimethylamine borane, 0.5 mol/L of sodium citrate, and 0.01 mol/L of sodium tungstate was prepared.

One side of the suspension obtained by stirring at 60 ° C, while the above nickel plating solution is slowed down Electroless nickel plating was slowly dropped to the suspension to form a conductive layer having a thickness of 100 nm. Thereafter, the particles are taken out by filtration of the suspension, washed with water, and dried to obtain conductive particles. The obtained conductive particle-based core material is in contact with the substrate particles.

(Example 15) (1) Palladium attachment step

The palladium-attached resin particles obtained in Example 1 were prepared.

(2) Electroless nickel plating step

A nickel plating solution (pH 8.5) containing 0.23 mol/L of nickel sulfate, 0.92 mol/L of dimethylamine borane, 0.5 mol/L of sodium citrate, and 0.01 mol/L of sodium tungstate was prepared.

The obtained palladium-attached resin particles were added to 1000 mL of pure water, and dispersed by an ultrasonic disperser, thereby obtaining a suspension. While the obtained suspension was stirred at 60 ° C, the nickel plating solution was gradually dropped to the suspension to carry out electroless nickel plating. Thereafter, the particles are taken out by filtration of the suspension, washed with water, and dried to coat the resin particles with a nickel-tungsten-boron layer, that is, a first conductive layer having a thickness of 10 nm, thereby obtaining a first conductive layer. Particles.

(3) Core substance attachment step and electroless nickel plating step

A slurry of barium titanate (BaTiO ₃ ) particles (having an average particle diameter of 100 nm) was prepared. The particles of the first conductive layer and the metal particle slurry were used, and the surface of the first conductive layer was coated with metal particles to obtain a suspension.

A nickel plating solution (pH 7.0) containing 0.23 mol/L of nickel sulfate, 0.92 mol/L of dimethylamine borane, and 0.5 mol/L of sodium citrate was prepared.

While the obtained suspension was stirred at 60 ° C, the nickel plating solution was gradually dropped to the suspension to carry out electroless nickel plating, thereby obtaining a second conductive layer having a thickness of 90 nm. Thereafter, the particles are taken out by filtration of the suspension, washed with water, and dried to obtain conductive particles. The conductive particles obtained have protrusions on the outer surface of the second conductive layer, and a core material is disposed inside the protrusions of the second conductive layer. Further, a first conductive layer is disposed between the resin particles and the core material.

(Embodiment 16)

Conductive particles were obtained in the same manner as in Example 15 except that the thickness of the nickel-tungsten-boron layer, that is, the first conductive layer was changed to 5.1 nm.

(Example 17)

Conductive particles were obtained in the same manner as in Example 15 except that the thickness of the nickel-tungsten-boron layer, that is, the first conductive layer was changed to 20 nm.

(Embodiment 18)

The same procedure as in Example 15 was carried out except that a barium titanate (BaTiO ₃ ) particle slurry (having an average particle diameter of 100 nm) was changed to an alumina (Al ₂ O ₃ ) particle slurry (average particle diameter: 100 nm). Conductive particles.

(Embodiment 19)

The same procedure as in Example 16 was carried out except that a barium titanate (BaTiO ₃ ) particle slurry (having an average particle diameter of 100 nm) was changed to an alumina (Al ₂ O ₃ ) particle slurry (average particle diameter of 100 nm). Conductive particles.

(Embodiment 20)

The same procedure as in Example 17 was carried out except that a barium titanate (BaTiO ₃ ) particle slurry (having an average particle diameter of 100 nm) was changed to an alumina (Al ₂ O ₃ ) particle slurry (average particle diameter of 100 nm). Conductive particles.

(Example 21)

Conductive particles were obtained in the same manner as in Example 15 except that 0.01 mol/L of sodium tungstate was added to the nickel plating solution for forming the second conductive layer.

(Example 22)

The insulating particles obtained in Example 9 were prepared as an aqueous dispersion of 10% by weight. 10 g of the conductive particles obtained in Example 15 were dispersed in 500 mL of ion-exchanged water, and 4 g of an aqueous dispersion of insulating particles was added thereto, followed by stirring at room temperature for 6 hours. After filtering by a 3 μm mesh filter, the mixture was washed with methanol and dried to obtain conductive particles to which insulating particles were attached.

Observation by a scanning electron microscope (SEM) revealed that only one layer of the coating layer due to the insulating particles was formed on the surface of the conductive particles. The coverage area of the insulating particles with respect to the area of 2.5 μm from the center of the conductive particles (that is, the projected area of the particle diameter of the insulating particles) was calculated by image analysis, and as a result, the coverage ratio was 30%.

(Comparative Example 5)

Divinylbenzene resin particles ("Micropearl SP-205" manufactured by Sekisui Chemical Co., Ltd.) having a particle diameter of 5.0 μm were prepared. Further, a barium titanate (BaTiO ₃ ) particle slurry (having an average particle diameter of 100 nm) was prepared. The resin particles and the metal particle slurry were used to coat the surface of the resin particles with a core material to obtain a suspension.

Prepare nickel plating containing 0.23 mol/L nickel sulfate, 0.92 mol/L dimethylamine borane, 0.5 mol/L sodium citrate, and 0.01 mol/L sodium tungstate Liquid (pH 8.5).

While the obtained suspension was stirred at 60 ° C, the nickel plating solution was gradually dropped to the suspension to carry out electroless nickel plating to form a conductive layer having a thickness of 100 nm. Thereafter, the particles are taken out by filtration of the suspension, washed with water, and dried to obtain conductive particles. The obtained conductive particle-based core material is in contact with the substrate particles.

(Comparative Example 6)

Conductive particles were obtained in the same manner as in Example 18 except that the thickness of the nickel-tungsten-boron layer, that is, the first conductive layer was changed to 1 nm.

(Example 23)

The insulating particles obtained in Example 9 were prepared as an aqueous dispersion of 10% by weight. 10 g of the conductive particles obtained in Example 18 were dispersed in 500 mL of ion-exchanged water, and 4 g of an aqueous dispersion of insulating particles was added thereto, followed by stirring at room temperature for 6 hours. After filtering by a 3 μm mesh filter, the mixture was washed with methanol and dried to obtain conductive particles to which insulating particles were attached.

Observation by a scanning electron microscope (SEM) revealed that only one layer of the coating layer due to the insulating particles was formed on the surface of the conductive particles. The coverage area of the insulating particles with respect to the area of 2.5 μm from the center of the conductive particles (that is, the projected area of the particle diameter of the insulating particles) was calculated by image analysis, and as a result, the coverage ratio was 30%.

(assessment) (1) The average distance between the surface of the substrate particles and the surface of the core material

The obtained conductive particles were cut and the cross section was observed, thereby measuring the substrate particles. The distance between the surface of the child and the plurality of core materials. The distance between the surface of the substrate particle and the surface of the core material is measured by taking a cross section of a plurality of portions of the conductive particles to obtain an image, and using the obtained image as a stereoscopic image, thereby using The stereo image obtained. The above-mentioned cross-section was taken using a concentrating ion beam-scanning electron microscope (FIBSEM) manufactured by FEI Corporation of Japan under the name of Helious NanoLab.650. A thin film section of the conductive particles was produced using a focused ion beam, and the cross section was observed by a scanning electron microscope. This operation was repeated 200 times to perform image analysis, thereby obtaining a stereoscopic image of the particles. From the stereoscopic image, the distance between the surface of the substrate particles and the surface of the core material was determined.

(2) The ratio (%) of the number of core materials whose distance between the surface of the substrate particles and the surface of the core material exceeds 5 nm in 100% by weight of the total amount of the core material

In the same manner as the evaluation item of the above (1), the ratio of the number of core materials in which the distance between the surface of the substrate particles and the surface of the core material exceeds 5 nm is measured in 100% by weight of the total amount of the core material ( %), and thus the determination is made based on the following criteria.

[Criteria for determining the ratio (%) of the number of core materials whose distance between the surface of the substrate particles and the surface of the core material exceeds 5 nm]

A: The ratio of the above number exceeds 80%

B: The ratio of the above number is 80% or less

(3) Connection resistance Production of the connection structure:

10 parts by weight of bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation) "Epikote 1009"), 40 parts by weight of acrylic rubber (weight average molecular weight: about 800,000), 200 parts by weight of methyl ethyl ketone, and 50 parts by weight of microcapsule-type hardener ("HX3941HP" manufactured by Asahi Kasei Chemicals Co., Ltd.) 2 parts by weight of a decane coupling agent ("SH6040" manufactured by Toray Dow Corning Co., Ltd.) was added to the conductive particles so as to have a content of 3% by weight, and dispersed to obtain a resin composition.

The obtained resin composition was applied to a PET (Polyethylene Terephthalate) film having a thickness of 50 μm which was subjected to release treatment on one side, and dried at 70 ° C for 5 minutes in hot air to prepare each. Anisotropic conductive film. The thickness of the anisotropic conductive film obtained was 12 μm.

The obtained anisotropic conductive film was cut into a size of 5 mm × 5 mm. The cut anisotropic conductive film was attached to a glass substrate (having a width of 3 μm and an L/S=20 μm/20 μm) on one side (width: 3 cm, length: 3 cm) At approximately the center of the aluminum electrode side, the aluminum electrode has a wire for resistance measurement. Next, two flexible printed boards (having a width of 2 cm and a length of 1 cm) having the same aluminum electrode were aligned and bonded so that the electrodes overlap each other. The laminated body of the glass substrate and the two layers of the flexible printed circuit board was thermocompression-bonded under pressure conditions of 10 N, 180 ° C, and 20 seconds to obtain a bonded structure. Further, a two-layer flexible printed circuit board in which an aluminum electrode was directly formed on a polyimide film was used.

Determination of connection resistance:

The connection resistance between the opposing electrodes of the obtained connection structure was measured by a four-terminal method. Further, the connection resistance was determined based on the following criteria.

[Determination of connection resistance]

○○: The connection resistance is 2.0 Ω or less

○: The connection resistance exceeds 2.0 Ω and is less than 3.0 Ω.

△: The connection resistance exceeds 3.0 Ω and is less than 5.0 Ω.

×: The connection resistance exceeds 5.0 Ω

(4) Impact resistance

The connection structure obtained by the evaluation of the connection resistance of the above (3) was dropped from a position having a height of 70 cm, and the impact resistance was evaluated by confirming the conduction. The impact resistance was determined based on the rate of increase of the resistance value from the initial resistance value by the following criteria.

[Criteria for determination of impact resistance]

○○: The rate of increase from the initial resistance value is 20% or less

○: The rate of increase of the resistance value from the initial resistance value exceeds 20% and is less than 35%.

△: The increase rate of the resistance value from the initial resistance value exceeds 35% and 50% or less

×: The increase rate of the resistance value from the initial resistance value exceeds 50%

(5) the state of the indentation

Using a differential interference microscope, the electrode provided on the glass substrate was observed from the side of the glass substrate of the bonded structure obtained by the evaluation of the connection resistance of the above (3), and the indentation of the electrode contacting the conductive particles was evaluated by the following criteria. The presence or absence of formation. Furthermore, for the presence or absence of an indentation of the electrodes is formed to be an electrode area of 0.02 mm ² embodiment, by a differential interference microscope to calculate the number of indentations per 0.02 mm ² of area of the electrode. The arbitrary 10 points were observed by a differential interference microscope, and the average value of the number of indentations per 0.02 mm ² of the electrode area was calculated.

[Criteria for judging the state of indentation]

○: The average number of indentations per 0.02 mm ² of electrode area is 20 or more

△: The average value of the number of indentations per 0.02 mm ² of the electrode area is 5 or more and less than 20

×: The average number of indentations per 0.02 mm ² of electrode area is less than 5

The results are shown in Tables 1 to 3 below. Further, in the following Tables 1 to 3, the Mohs hardness of the first and second conductive layers and the core material is shown. Further, in the following Tables 1 to 3, "-" indicates that it was not evaluated.

1‧‧‧Electrical particles

2‧‧‧Substrate particles

3‧‧‧ Conductive layer

3a‧‧‧ Protrusion

3b‧‧‧ Conductive layer

4‧‧‧ core material

5‧‧‧Insulating substances

11‧‧‧Electrical particles

12‧‧‧ Conductive layer

12a‧‧‧ Protrusion

12b‧‧‧ Conductive layer

16‧‧‧1st conductive layer

17‧‧‧2nd conductive layer

17a‧‧‧ Protrusion

21‧‧‧Electrical particles

22‧‧‧ Conductive layer

22a‧‧‧ Protrusion

22b‧‧‧ Conductive layer

26‧‧‧1st conductive layer

27‧‧‧2nd conductive layer

27a‧‧‧Protrusion

28‧‧‧3rd conductive layer

28a‧‧‧Protrusion

51‧‧‧Connection structure

52‧‧‧1st connection object component

52a‧‧‧Upper surface

52b‧‧‧electrode

53‧‧‧2nd connection object component

53a‧‧‧ lower surface

53b‧‧‧electrode

54‧‧‧Connecting Department

Fig. 1 is a cross-sectional view showing conductive particles according to a first embodiment of the present invention.

Fig. 2 is a cross-sectional view showing conductive particles according to a second embodiment of the present invention.

Fig. 3 is a cross-sectional view showing conductive particles according to a third embodiment of the present invention.

Fig. 4 is a front cross-sectional view schematically showing a connection structure using conductive particles according to the first embodiment of the present invention.

1‧‧‧Electrical particles

2‧‧‧Substrate particles

3‧‧‧ Conductive layer

3a‧‧‧ Protrusion

3b‧‧‧ Conductive layer

4‧‧‧ core material

5‧‧‧Insulating substances

Claims (17)

An electroconductive particle comprising: a substrate particle; a conductive layer covering the substrate particle; and a plurality of core materials embedded in the conductive layer; wherein the conductive layer includes a plurality of protrusions on the outer surface The core material is disposed inside the protrusion of the conductive layer, and the conductive layer is disposed between the substrate particle and the core material, and a surface of the substrate particle is spaced apart from a surface of the core material, and the substrate The average distance between the surface of the particles and the surface of the above core material exceeds 5 nm. The conductive particle of claim 1, wherein an average distance between a surface of the substrate particle and a surface of the core material exceeds 5 nm and 800 nm or less. The conductive particle of claim 1, wherein a ratio of the number of core materials having a distance between the surface of the substrate particle and the surface of the core material exceeding 5 nm exceeds 80 in a total number of 100% of the core material % and less than 100%. The conductive particle of claim 1, wherein an average distance between a surface of the substrate particle and a surface of the core material exceeds 5 nm and 800 nm or less, and the substrate particle is in a total of 100% of the core material. The ratio of the number of core materials whose distance between the surface and the surface of the above-mentioned core material exceeds 5 nm exceeds 80% and 100% or less. The conductive particle of claim 1, wherein the conductive layer has a conductive layer portion disposed between the substrate particle and the core material, and a Mohs hardness of the core material is disposed between the substrate particle and the core material The Mohs hardness of the conductive layer portion is the same, or the Mohs hardness of the core material is larger than the Mohs hardness of the conductive layer portion disposed between the substrate particles and the core material. The conductive particle of claim 2, wherein the conductive layer has a conductive layer portion disposed between the substrate particle and the core material, and a Mohs hardness of the core material is disposed between the substrate particle and the core material The Mohs hardness of the conductive layer portion is the same, or the Mohs hardness of the core material is larger than the Mohs hardness of the conductive layer portion disposed between the substrate particles and the core material. The conductive particle of claim 3, wherein the conductive layer has a conductive layer portion disposed between the substrate particle and the core material, and a Mohs hardness of the core material is disposed between the substrate particle and the core material The Mohs hardness of the conductive layer portion is the same, or the Mohs hardness of the core material is larger than the Mohs hardness of the conductive layer portion disposed between the substrate particles and the core material. The conductive particle of claim 4, wherein the conductive layer has a conductive layer portion disposed between the substrate particle and the core material, and a Mohs hardness of the core material is disposed between the substrate particle and the core material The Mohs hardness of the conductive layer portion is the same, or the Mohs hardness of the core material is larger than the Mohs hardness of the conductive layer portion disposed between the substrate particles and the core material. The conductive particle according to any one of claims 5 to 8, wherein the conductive layer has a conductive layer portion disposed between the substrate particle and the core material, and the core material has a Mohs hardness greater than that disposed on the substrate The Mohs hardness of the portion of the above-mentioned conductive layer between the particles and the above-mentioned core material. The electroconductive particle according to any one of claims 1 to 8, wherein the metal element containing the most of the above-mentioned core material is the same as the metal element containing the most of the above-mentioned conductive layer. The conductive particles according to any one of claims 1 to 8, wherein the conductive layer includes a first conductive layer covering the substrate particles, and a second conductive layer covering the first conductive layer and the core material, the core The substance is disposed on the surface of the first conductive layer and embedded in the second conductive layer. The second conductive layer has a plurality of protrusions on the outer surface, and is disposed inside the protrusion of the second conductive layer. In the core material, the first conductive layer is disposed between the substrate particles and the core material. The conductive particle of claim 11, wherein the metal element containing the most of the core material is the same as the metal element containing the most of the second conductive layer. The electroconductive particle according to any one of claims 1 to 8, wherein the electroconductive layer is a single layer of a conductive layer. The electroconductive particle according to any one of claims 1 to 8, wherein the core material is a metal particle. The electroconductive particle according to any one of claims 1 to 8, which further comprises an insulating substance attached to a surface of the above-mentioned conductive layer. A conductive material comprising the conductive particles according to any one of claims 1 to 15, and a binder resin. A connection structure comprising: a first connection target member; a second connection target member; and a connection portion that connects the first and second connection target members; and the connection portion is as claimed in claims 1 to 15 Any one of the conductive particles is formed or formed of a conductive material containing the conductive particles and the binder resin.