CN108806824A - Electroconductive particle, conductive material and connection structural bodies - Google Patents

Electroconductive particle, conductive material and connection structural bodies Download PDF

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Publication number
CN108806824A
CN108806824A CN201810695985.2A CN201810695985A CN108806824A CN 108806824 A CN108806824 A CN 108806824A CN 201810695985 A CN201810695985 A CN 201810695985A CN 108806824 A CN108806824 A CN 108806824A
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conductive layer
mentioned
particle
core material
electroconductive particle
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CN108806824B (en
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西冈敬三
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Sekisui Chemical Co Ltd
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Sekisui Chemical Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/18—Non-metallic particles coated with metal
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/52—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating using reducing agents for coating with metallic material not provided for in a single one of groups C23C18/32 - C23C18/50
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/16—Non-insulated conductors or conductive bodies characterised by their form comprising conductive material in insulating or poorly conductive material, e.g. conductive rubber
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R11/00—Individual connecting elements providing two or more spaced connecting locations for conductive members which are, or may be, thereby interconnected, e.g. end pieces for wires or cables supported by the wire or cable and having means for facilitating electrical connection to some other wire, terminal, or conductive member, blocks of binding posts
    • H01R11/01—Individual connecting elements providing two or more spaced connecting locations for conductive members which are, or may be, thereby interconnected, e.g. end pieces for wires or cables supported by the wire or cable and having means for facilitating electrical connection to some other wire, terminal, or conductive member, blocks of binding posts characterised by the form or arrangement of the conductive interconnection between the connecting locations
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1655—Process features
    • C23C18/1662—Use of incorporated material in the solution or dispersion, e.g. particles, whiskers, wires
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Dispersion Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Conductive Materials (AREA)
  • Non-Insulated Conductors (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Chemically Coating (AREA)
  • Powder Metallurgy (AREA)

Abstract

The present invention provides a kind of electroconductive particle that can reduce interelectrode connection resistance.The electroconductive particle (1) of the present invention has：Base particle (2), the conductive layer (3) of cladding base particle (2) and multiple core materials (4) in embedment conductive layer (3).Conductive layer (3) has multiple protrusions (3a) in outer side surface.It is configured with core material (4) in the inside of the protrusion (3a) of conductive layer (3).The surface of base particle (2) and the surface of core material (4) are separated by a distance.Average distance between the surface and the surface of core material (4) of base particle (2) is more than 5nm.

Description

Electroconductive particle, conductive material and connection structural bodies
The application is China application No. is 201280040642.3, and the applying date is on December 19th, 2012, entitled The divisional application of the application for a patent for invention of " electroconductive particle, conductive material and connection structural bodies ".
Technical field
The present invention relates to the electroconductive particles that conductive layer is configured on the surface of base particle, more specifically, It is related to for example can be used for the electroconductive particle of interelectrode electrical connection.Moreover, it relates to use above-mentioned electroconductive particle Conductive material and connection structural bodies.
Background technology
Anisotropic conductive is pasted and the anisotropic conductive materials such as anisotropic conductive film are well known.It should be respectively to different For property conductive material, electroconductive particle is dispersed in adhesive resin.
Above-mentioned anisotropic conductive material can be used for connection and IC chip and the tool of IC chip and flexible printed wiring board There is the connection etc. of the circuit board of ITO electrode.For example, can be by the electricity that anisotropic conductive material is configured to IC chip It is heated and is pressurizeed after between pole and the electrode of circuit board, to realize the electrical connection of these electrodes.
As an example of above-mentioned electroconductive particle, the following patent document 1 discloses a kind of electroconductive particle, Nickel conductive layer is formed using electroless plating method or nickel is closed by the surface of the pellet base material particles in 1~20 μm of average grain diameter Golden conductive layer and obtain.The electroconductive particle has 0.05~4 μm of microspike on the most surface layer of conductive layer.The conductive layer with The protrusion is essentially continuously connected.
A kind of electroconductive particle is disclosed in following patent documents 2, is had：Plastics nucleome covers the plastics nucleome Polyelectrolyte layers, be adsorbed in via the polyelectrolyte layers metallic of above-mentioned plastics nucleome and with covering The mode of the metallic is formed in the non-electrolytic coat of metal around above-mentioned plastics nucleome.
A kind of electroconductive particle is disclosed in following patent documents 3, is formed with and is contained on the surface of base particle There is the plurality of conductive layers of plating the metal envelope layer and layer gold of nickel and phosphorus.In the electroconductive particle, in the table of base particle Core material is configured on face, which is coated by conductive layer.Due to the presence of core material, conductive layer protuberance, in conductive layer Surface is formed with protrusion.
Existing technical literature
Patent document
Patent document 1：(Japan) special open 2000-243132 bulletins
Patent document 2：(Japan) special open 2011-108446 bulletins
Patent document 3：(Japan) special open 2006-228475 bulletins
Invention content
Problems to be solved by the invention
Electroconductive particle of the outer surface with protrusion in conductive layer is disclosed in above patent document 1~3.By The surface of the electrode of electroconductive particle connection and the conductive layer of electroconductive particle is formed with oxide film thereon mostly.Form above-mentioned conduction The purpose of protrusion of layer is, when via electroconductive particle by being pressed between electrode, excludes electrode and electroconductive particle surface Oxide film thereon makes conductive layer and electrode contact.
But there are the feelings that the existing electroconductive particle of protrusion will connect between electrode in the outer surface using conductive layer Under condition, the oxide film thereon of electrode and electroconductive particle surface cannot be fully excluded sometimes, and connection resistance is got higher.
The purpose of the present invention is to provide one kind will be connected between electrode obtain connection structural bodies in the case of, can drop The electroconductive particle of connection resistance between low electrode and the conductive material and connection structural bodies for having used the electroconductive particle.
Solution to the problem
Wide in range aspect according to the present invention, it is possible to provide a kind of electroconductive particle has：Base particle, cladding should The conductive layer of base particle and the multiple core materials being embedded in the conductive layer, above-mentioned conductive layer have in outer side surface Multiple protrusions are configured with above-mentioned core material, in above-mentioned base particle and upper in the inside of the above-mentioned protrusion of above-mentioned conductive layer State and be configured with above-mentioned conductive layer between core material, the surface of the surface of above-mentioned base particle and above-mentioned core material separate away from From, and the average distance between the surface of above-mentioned base particle and the surface of above-mentioned core material is more than 5nm.
In some particular aspects of the electroconductive particle of the present invention, the surface of above-mentioned base particle and above-mentioned core object Average distance between the surface of matter is more than 5nm and is 800nm or less.
It is above-mentioned in the total number 100% of above-mentioned core material in some particular aspects of the electroconductive particle of the present invention The distance between the surface of base particle and the surface of above-mentioned core material are more than that the ratio of the number of the core material of 5nm is more than 80% and be 100% or less.
The present invention electroconductive particle some particular aspects in, in above-mentioned core material the most metallic element of content and The most metallic element of content is identical in above-mentioned conductive layer.
In other particular aspects of the electroconductive particle of the present invention, above-mentioned conductive layer has：Coat above-mentioned basis material First conductive layer of particle and the second conductive layer for coating above-mentioned first conductive layer and above-mentioned core material, above-mentioned core material configuration In on the surface of above-mentioned first conductive layer and in above-mentioned second conductive layer of embedment, above-mentioned second conductive layer has more in outer side surface A protrusion is configured with above-mentioned core material in the inside of the above-mentioned protrusion of above-mentioned second conductive layer, in above-mentioned base particle and Above-mentioned first conductive layer is configured between above-mentioned core material.
The present invention electroconductive particle another particular aspects in, in above-mentioned core material the most metallic element of content and The most metallic element of content is identical in above-mentioned second conductive layer.
In the yet another particular aspect of the electroconductive particle of the present invention, above-mentioned conductive layer is the conductive layer of single layer.
In other particular aspects of the electroconductive particle of the present invention, above-mentioned core material is metallic.
In other particular aspects of the electroconductive particle of the present invention, it is also equipped with and is attached to the exhausted of above-mentioned conductive layer surface Edge substance.
The conductive material of the present invention contains above-mentioned electroconductive particle and adhesive resin.
The connection structural bodies of the present invention has：First connecting object component, the second connecting object component, connect this first, The interconnecting piece of second connecting object component, the interconnecting piece formed by above-mentioned electroconductive particle or by contain the electroconductive particle and The conductive material of adhesive resin is formed.
The effect of invention
The electroconductive particle of the present invention has base particle, the conductive layer for coating the base particle and embedment Multiple core materials in the conductive layer, above-mentioned conductive layer have protrusion in outer side surface, in the above-mentioned protrusion of above-mentioned conductive layer Inside is configured with above-mentioned core material, and above-mentioned conductive layer is configured between above-mentioned base particle and above-mentioned core material, above-mentioned The surface of base particle and the surface of above-mentioned core material separated by a distance, the surface of above-mentioned base particle and above-mentioned core object Average distance between the surface of matter is more than 5nm, therefore, when the electroconductive particle of the present invention is used for interelectrode connection, Interelectrode connection resistance can be reduced.
Description of the drawings
Fig. 1 is sectional view, shows the electroconductive particle of first embodiment of the invention；
Fig. 2 is sectional view, shows the electroconductive particle of second embodiment of the invention；
Fig. 3 is sectional view, shows the electroconductive particle of third embodiment of the invention；
Fig. 4 is front section view, it is schematically shown that has used the electroconductive particle of first embodiment of the invention Connection structural bodies.
Symbol description
1 ... electroconductive particle
2 ... base particles
3 ... conductive layers
3a ... protrusions
3b ... Conductive layer portions
4 ... core materials
5 ... megohmite insulants
11 ... electroconductive particles
12 ... conductive layers
12a ... protrusions
12b ... Conductive layer portions
16 ... first conductive layers
17 ... second conductive layers
17a ... protrusions
21 ... electroconductive particles
22 ... conductive layers
22a ... protrusions
22b ... Conductive layer portions
26 ... first conductive layers
27 ... second conductive layers
27a ... protrusions
28 ... third conductive layers
28a ... protrusions
51 ... connection structural bodies
52 ... first connecting object components
The upper surfaces 52a ...
52b ... electrodes
53 ... second connecting object components
The lower surfaces 53a ...
53b ... electrodes
54 ... interconnecting pieces
Specific implementation mode
Hereinafter, being illustrated to the details of the present invention.
The electroconductive particle of the present invention has：Base particle, the conductive layer for coating the base particle and embedment Multiple core materials in the conductive layer.Above-mentioned conductive layer has multiple protrusions in outer side surface.In the above-mentioned prominent of above-mentioned conductive layer The inside risen is configured with above-mentioned core material.Above-mentioned conductive layer is configured between above-mentioned base particle and above-mentioned core material. A part of region of above-mentioned conductive layer is configured between above-mentioned base particle and above-mentioned core material.Above-mentioned base particle Surface and above-mentioned core material surface separated by a distance.Between the surface of above-mentioned base particle and the surface of above-mentioned core material Average distance be more than 5nm.
It is formed with oxide film thereon mostly on the electrode surface connected by electroconductive particle.Moreover, in above-mentioned conductive layer Oxide film thereon is formed on outer surface mostly.Above-mentioned conductive layer has multiple protrusions in outer side surface, as a result, by electrode Between configuration electroconductive particle after pressed, oxide film thereon is excluded using protrusion.Therefore, electrode and electroconductive particle can be made Contact, can reduce interelectrode connection resistance.
In addition, in the electroconductive particle of the present invention, due to matching between above-mentioned base particle and above-mentioned core material Be equipped with above-mentioned conductive layer, the surface of the surface of above-mentioned base particle and above-mentioned core material separated by a distance, and above-mentioned matrix material Expect that the average distance between the surface and the surface of above-mentioned core material of particle is more than 5nm, therefore, the compression conductive grain between electrode The period of the day from 11 p.m. to 1 a.m, core material are not easy to be pressed into base particle, and the subregion of core material is not easy in embedded base particle.Especially It is that, even if base particle is softer resin particle, core material is not easy to be pressed into base particle, core material Subregion be not easy in embedded base particle.Therefore, when carrying out interelectrode pressing, the protrusion of conductive layer is strong Ground squeezes electrode.As a result, effectively excluding oxide film thereon using protrusion.Therefore, electrode and electroconductive particle can be made to have The contact of effect ground, can be effectively reduced interelectrode connection resistance.
In addition, the present invention electroconductive particle due to having above-mentioned composition, compression conductive particle will connect between electrode When connecing, it is also possible to form appropriate impression on the electrode.It is squeezed it should be noted that the impression for being formed in electrode is electroconductive particle Piezoelectricity pole and the recess portion of electrode formed.In addition, by be dispersed in adhesive resin electroconductive particle conductive material (respectively to Anisotropic conductive material etc.) in the case of interelectrode pressing, can effectively exclude the adhesive between conductive layer and electrode Resin.By effectively excluding adhesive resin, interelectrode connection resistance can be also reduced.In addition, having insulation in use In the case of the electroconductive particle of substance, above-mentioned protrusion is utilized, it is possibility to have effect ground excludes the insulation between conductive layer and electrode Substance, therefore interelectrode conducting reliability can be effectively improved.
Between further effectively excluding the oxide film thereon of electrode and electroconductive particle surface, further improving electrode Conducting reliability from the perspective of, the average distance between the surface of above-mentioned base particle and the surface of above-mentioned core material Preferably 5nm or more, more preferably 10nm or more.Between the surface of above-mentioned base particle and the surface of above-mentioned core material The upper limit of average distance is not particularly limited, it may be considered that thickness of conductive layer etc. and suitable for determine.Above-mentioned base particle Surface and the surface of above-mentioned core material between average distance can be 800nm or less, or 100nm or less.It is above-mentioned Average distance between the surface of base particle and the surface of above-mentioned core material is preferably 30nm hereinafter, more preferably 20nm Below.Average distance between the surface of above-mentioned base particle and the surface of above-mentioned core material can be conductive layer thickness 9/10 or less, or 1/2 or less, or 1/3 or less.
Between further effectively excluding the oxide film thereon of electrode and electroconductive particle surface, further improving electrode Conducting reliability from the perspective of, in the total number 100% of above-mentioned core material, the surface of above-mentioned base particle and upper The ratio for stating the number for the core material that the distance between surface of core material is more than 5nm is preferably 50% or more, more preferably above 80% and be 100% or less.In all above-mentioned core materials, the surface on the surface of above-mentioned base particle and above-mentioned core material The distance between can also be more than 5nm.
Average distance between the surface of above-mentioned base particle and the surface of above-mentioned core material calculates as follows, that is, point It Ce Ding not be behind the surface of base particle and the distance between each surface (shortest distance in gap) of multiple core materials, to surveying Fixed value is averaged.In the case where electroconductive particle has 5 core material A~E being embedded in conductive layer, calculate as follows Go out：Measure the surface of the base particle and distance on the surfaces core material A, the surface of base particle and core material B surface Distance, the surface and distance of core material C Surface of base particle, the surface of the base particle and surfaces core material D Distance and base particle surface and the surfaces core material E distance, and be averaged to 5 values of measurement.It needs Bright, in the case where core material is 10 or more, preferably the surface of measurement base particle and all core materials is each The distance on surface, but can also measure the surface of base particle and each surface of optional 10 core materials away from From, and 10 by measuring values calculate above-mentioned average distance.
The distance between the surface of above-mentioned base particle and the surface of above-mentioned core material can be by shooting electric conductivity The section at multiple positions of particle and obtain image, and by gained image making stereo-picture, stereo-picture obtained by use, to Accurately measure.The shooting of above-mentioned section can use the progress such as focused ion beam scanning electron microscope (FIBSEM).For example, Using focused ion beam, the cut film of electroconductive particle is made, and section is observed using scanning electron microscope.By should Operation repeats hundreds of times and carries out image analysis, and the stereo-picture of particle can be obtained.
Above-mentioned conductive layer has protrusion in outer side surface.The protrusion is multiple.On the surface of conductive layer and by electric conductivity It is formed with oxide film thereon mostly on the electrode surface of particle connection.Leading for protrusion is had by using the outer surface in conductive layer Conductive particles, can be by configuring electroconductive particle between electrode and being pressed, to using protrusion and on effectively excluding State oxide film thereon.Therefore, the conductive layer of electrode and electroconductive particle can be made more effectively to contact, interelectrode company can be reduced Connecting resistance.In addition, in the case where the surface of electroconductive particle has megohmite insulant or electroconductive particle is scattered in adhesive tree In the case of being used in fat and as conductive material, effectively excluded using the protrusion of electroconductive particle electroconductive particle and Megohmite insulant between electrode or adhesive resin.Therefore, it is possible to improve interelectrode conducting reliability.
The average height of multiple above-mentioned protrusions is preferably 0.001 μm or more, more preferably 0.05 μm or more, preferably 0.9 μ M is hereinafter, more preferably 0.2 μm or less.When the average height of above-mentioned protrusion is above-mentioned lower limit or more and the above-mentioned upper limit or less, energy Enough it is effectively reduced interelectrode connection resistance.
Hereinafter, being illustrated to the details of electroconductive particle, conductive material and connection structural bodies.
(electroconductive particle)
Fig. 1 is the sectional view for the electroconductive particle for showing first embodiment of the invention.
Electroconductive particle 1 shown in FIG. 1 has：Base particle 2, conductive layer 3, multiple core materials 4 and megohmite insulant 5.Conductive layer 3 is configured on the surface of base particle 2.In electroconductive particle 1, it is formed with the conductive layer 3 of single layer.It is conductive Layer 3 coats base particle 2.Conductive layer 3 has multiple protrusion 3a in outer side surface.Multiple core materials 4 are configured at matrix material On the surface for expecting particle 2, and it is embedded in conductive layer 3.Core material 4 is configured at the inside of protrusion 3a.Match in the inside of 1 protrusion 3a It is equipped with 1 core material 4.Due to the presence of multiple core materials 4, the outer surface of conductive layer 3 swells, and forms multiple protrusion 3a.
Conductive layer 3 is configured between the surface of base particle 2 and the surface of core material 4.Base particle 2 Surface and the surface of core material 4 are separated by a distance.Core material 4 is not contacted with base particle 2.In electroconductive particle 1, matrix Average distance between the surface and the surface of core material 4 of material particles 2 is more than 5nm.Therefore, in the table of base particle 2 3 part (Conductive layer portions 3b) of conductive layer of abundant thickness is configured between face and the surface of core material 4.Base particle 2 Surface and core material 4 the distance between surface to be configured between the surface of base particle 2 and the surface of core material 4 Conductive layer portions 3b thickness.
Megohmite insulant 5 is configured on the surface of conductive layer 3.Megohmite insulant 5 is insulating properties particle.Megohmite insulant 5 is by having The material of insulating properties is formed.Electroconductive particle can not also must have megohmite insulant.In addition, electroconductive particle can also have packet The insulating layer for covering the outer surface of conductive layer replaces insulating properties particle as megohmite insulant.
Fig. 2 has been shown in section view the electroconductive particle of second embodiment of the invention.
Electroconductive particle 11 shown in Fig. 2 has：Base particle 2, conductive layer 12, multiple core materials 4 and insulant Matter 5.Conductive layer 12 is configured on the surface of base particle 2.Conductive layer 12 coats base particle 2.Conductive layer 12 exists Outer surface has multiple protrusion 12a.
In electroconductive particle 11, it is formed with the conductive layer 12 of multilayer.Conductive layer 12 has the first conductive layer 16 and second Conductive layer 17.First conductive layer 16 is configured on the surface of base particle 2.First conductive layer 16 coats base particle 2.First conductive layer 16 is single layer.First conductive layer may be multilayer.
Core material 4 is configured on the first conductive layer 16.Core material 4 is embedded in conductive layer 12 and the second conductive layer 17.In base The first conductive layer 16 is configured between body material particles 2 and core material 4.By matching between base particle 2 and core material 4 The first conductive layer 16 is set, the surface of base particle 2 and the surface of core material 4 are separated by a distance.The surface of base particle 2 Average distance between the surface of core material 4 is more than 5nm.In electroconductive particle 11, the surface of base particle 2 and core The distance between surface of substance 4 is the conductive layer portion being configured between the surface of base particle 2 and the surface of core material 4 Divide the thickness of 12b and the first conductive layer 16 (16 part of the first conductive layer).
Second conductive layer 17 is different from 16 ground of the first conductive layer and is formed.After forming the first conductive layer 16, the second conductive layer 17 are formed in the surface of the first conductive layer 16.Second conductive layer 17 is configured on the surface of the first conductive layer 16.Second conductive layer 17 cladding core materials 4 and the first conductive layer 16.Second conductive layer 17 has multiple protrusion 17a in outer side surface.Multiple core materials 4 It is embedded in the second conductive layer 17.Core material 4 is configured at the inside of protrusion 17a.Since the presence of multiple core materials 4, second is conductive The outer surface protuberance of layer 17, forms protrusion 17a.
Fig. 3 has been shown in section view the electroconductive particle of third embodiment of the invention.
Electroconductive particle 21 shown in Fig. 3 has：Base particle 2, conductive layer 22, multiple core materials 4 and insulant Matter 5.Conductive layer 22 is configured on the surface of base particle 2.Conductive layer 22 coats base particle 2.Conductive layer 22 exists Outer surface has multiple protrusion 22a.
In electroconductive particle 21, it is formed with the conductive layer 22 of multilayer.There is conductive layer 22 first conductive layer 26, second to lead Electric layer 27 and third conductive layer 28.First conductive layer 26 is configured on the surface of base particle 2.First conductive layer 26 coats Base particle 2.
Core material 4 is configured on the first conductive layer 26.Core material 4 is embedded in conductive layer 22 and in the second conductive layer 27.? The first conductive layer 26 is configured between base particle 2 and core material 4.By between base particle 2 and core material 4 The first conductive layer 26 is configured, the surface of base particle 2 and the surface of core material 4 are separated by a distance.The table of base particle 2 Average distance between face and the surface of core material 4 is more than 5nm.In electroconductive particle 21, the surface of base particle 2 and The distance between surface of core material 4 is the conductive layer being configured between the surface of base particle 2 and the surface of core material 4 The thickness of 26 part part 22b and the first conductive layer.
Second conductive layer 27 is configured on the surface of the first conductive layer 26.Second conductive layer 27 coats core material 4 and first Conductive layer 26.Second conductive layer 27 has multiple protrusion 27a in outer side surface.Core material 4 is configured at the inside of protrusion 27a.By It is swelled in the outer surface of the presence of multiple core materials 4, the second conductive layer 27, forms protrusion 27a.
Third conductive layer 28 is configured on the surface of the second conductive layer 27.Third conductive layer 28 coats the second conductive layer 27. Third conductive layer 28 has multiple protrusion 28a in outer side surface.Core material 4 is configured at the inside of protrusion 28a.Due to multiple core objects The presence of matter 4, the outer surface protuberance of third conductive layer 28, forms protrusion 28a.
It is preferred that the most metallic element phase of content in the most metallic element of content and above-mentioned conductive layer in above-mentioned core material Together.In this case, the adaptation of core material and conductive layer is good, as a result, the connection resistance in connection structural bodies becomes more It is good.It should be noted that the most gold of content in the most metallic element of content and above-mentioned conductive layer in above-mentioned core material Belong to that element can also there are concentration ladders in above-mentioned core material, in above-mentioned conductive layer or in above-mentioned core material and above-mentioned conductive layer Degree.In addition, the most metallic element of content can also in the most metallic element of content and above-mentioned conductive layer in above-mentioned core material Alloy is formed with other metals.In addition, metal included in metal and above-mentioned conductive layer included in above-mentioned core material Alloying can occur in interface.
It is preferred that the most metal member of content in the most metallic element of content and above-mentioned first conductive layer in above-mentioned core material Element is identical.In this case, the adaptation of core material and conductive layer is good, as a result, the connection resistance in connection structural bodies becomes It obtains more good.It should be noted that content in the most metallic element of content and above-mentioned first conductive layer in above-mentioned core material Most metallic elements can also be in above-mentioned core material, in above-mentioned first conductive layer or above-mentioned core material and above-mentioned first is led There are concentration gradients in electric layer.The most metallic element of content can also be formed with other metals and be closed in above-mentioned first conductive layer Gold.Metal can also be closed in interface included in metal included in above-mentioned core material and above-mentioned first conductive layer Aurification.
It is preferred that the most metal member of content in the most metallic element of content and above-mentioned second conductive layer in above-mentioned core material Element is identical.In this case, the adaptation of core material and conductive layer is good, as a result, the connection resistance in connection structural bodies becomes It obtains more good.It should be noted that content in the most metallic element of content and above-mentioned second conductive layer in above-mentioned core material Most metallic elements can also be in above-mentioned core material, in above-mentioned second conductive layer or above-mentioned core material and above-mentioned second is led There are concentration gradients in electric layer.The most metallic element of content can also be formed with other metals and be closed in above-mentioned second conductive layer Gold.In interface alloy can also occur for metal included in the metal and above-mentioned second conductive layer that above-mentioned core material is included Change.
It is preferred that the Mohs' hardness of above-mentioned core material and being configured at leading between above-mentioned base particle and above-mentioned core material The Mohs' hardness of electric layer part is identical or the Mohs' hardness ratio of above-mentioned core material is configured at above-mentioned base particle and above-mentioned core The Mohs' hardness of Conductive layer portions between substance is big.Additionally, it is preferred that the Mohs' hardness of above-mentioned core material is conductive with above-mentioned first The Mohs' hardness of layer is identical or the Mohs' hardness of above-mentioned core material is bigger than the Mohs' hardness of above-mentioned first conductive layer.In these feelings Under condition, core material is not easy to be pressed into base particle, and the subregion of core material is not easy in embedded base particle.It is tied Fruit can further reduce interelectrode connection resistance.From the viewpoint of further reducing interelectrode connection resistance, It is preferred that the Mohs' hardness of above-mentioned core material is than the Conductive layer portions that are configured between above-mentioned base particle and above-mentioned core material Or the Mohs' hardness of above-mentioned first conductive layer is big.
Mohs' hardness in above-mentioned core material and the conduction that is configured between above-mentioned base particle and above-mentioned core material In the case that the Mohs' hardness of layer segment or above-mentioned first conductive layer is same above, from the further sight for reducing connection resistance Point sets out, the Mohs' hardness of above-mentioned core material and the conductive layer portion being configured between above-mentioned base particle and above-mentioned core material Divide or the absolute value of the difference of the Mohs' hardness of above-mentioned first conductive layer is preferably 0.1 or more, more preferably 0.5 or more.
It is preferred that the Mohs' hardness of above-mentioned core material is than being configured at leading between above-mentioned base particle and above-mentioned core material The Mohs' hardness of electric layer part is small.It is preferred that the Mohs' hardness of above-mentioned core material is smaller than the Mohs' hardness of above-mentioned first conductive layer.? In the case of these, above-mentioned Conductive layer portions and above-mentioned first conductive layer have a degree of resiliency.It can not only drop as a result, Resistance is connected caused by low Conductive layer portions or the first conductive layer by being configured between base particle and core material, and And it even if connection structural bodies made of between utilization electroconductive particle connection electrode applies impact, is not easy to that poor flow occurs. I.e., additionally it is possible to improve the impact resistance of connection structural bodies.
Above-mentioned core material Mohs' hardness than the conduction that is configured between above-mentioned base particle and above-mentioned core material In the case that the Mohs' hardness of layer segment or above-mentioned first conductive layer is small, from the viewpoint of further improving impact resistance, The Mohs' hardness of above-mentioned core material and the Conductive layer portions being configured between above-mentioned base particle and above-mentioned core material or on The absolute value of the difference for stating the Mohs' hardness of the first conductive layer is preferably 0.1 or more, and more preferably 0.5 or more.
[base particle]
As above-mentioned base particle, can enumerate：Resin particle, the inorganic particulate in addition to metal, organic-inorganic are miscellaneous Change particle and metallic etc..Above-mentioned base particle is preferably the base particle in addition to metallic, more preferably Inorganic particulate for resin particle, in addition to metal or organic inorganic hybridization particle.
Above-mentioned base particle is preferably the resin particle being formed by resin.If above-mentioned base particle is resin Particle, then the composition of conductive layer and core material through the invention and obtain connection resistance reducing effect it is quite apparent.? When using between above-mentioned electroconductive particle connection electrode, after above-mentioned electroconductive particle is configured between electrode, made by pressing State electroconductive particle compression.If base particle is resin particle, when carrying out above-mentioned pressing, above-mentioned electroconductive particle Easily deformable, the contact area of electroconductive particle and electrode becomes larger.Therefore, interelectrode conducting reliability is got higher.
As the resin for being used to form above-mentioned resin particle, various organic matters are preferably used.It is above-mentioned as being used to form The resin of resin particle, it can be mentioned, for example：Polyethylene, polypropylene, polystyrene, polyvinyl chloride, Vingon, polypropylene, The vistanexes such as polyisobutene, polybutadiene；The acrylic resins such as polymethyl methacrylate and polymethyl acrylate；Poly- pair Alkylene, makrolon, polyamide, phenol formaldehyde resin, melamine resin, benzoguanamine formaldehyde tree Fat, urea-formaldehyde resin, phenolic resin, melmac, benzoguanamine resin, Lauxite, epoxy resin, unsaturation are poly- Ester resin, saturated polyester resin, polysulfones, polyphenylene oxide, polyacetals, polyimides, polyamidoimide, polyether-ether-ketone, polyether sulfone, And by it is one or more kinds of have the various polymerizable monomers of ethylenically unsaturated group it is aggregated obtained from polymer etc.. Due to that can design and synthesize the resin particle with physical property when arbitrarily compressing suitable for conductive material, and can be easily The hardness of base particle is controlled in suitable range, therefore, be used to form the resin of above-mentioned resin particle preferably by Polymer obtained from polymerizable monomer of the one or more with multiple ethylenically unsaturated groups is aggregated.
In the case where making the monomer polymerization with ethylenically unsaturated group and obtain above-mentioned resin particle, as above-mentioned tool There is the monomer of ethylenically unsaturated group, the monomer of the monomer and bridging property of non-crosslinked property can be enumerated.
As the monomer of above-mentioned non-crosslinked property, such as can enumerate：The styrene monomers such as styrene, α-methylstyrene； The carboxyl group-containing monomers such as (methyl) acrylic acid, maleic acid, maleic anhydride；(methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) 2-EHA, (methyl) lauryl acrylate, (methyl) aliphatic acrylate, (methyl) stearyl acrylate, (methyl) cyclohexyl acrylate, the different ice of (methyl) acrylic acid Piece ester etc. (methyl) alkyl-acrylates；(methyl) acrylic acid 2- hydroxy methacrylates, (methyl) glycerol acrylate, polyoxyethylene (methyl) esters of acrylic acid containing oxygen atom such as (methyl) acrylate, (methyl) glycidyl acrylate；(methyl) third Alkene nitrile etc. contains nitrile monomer；The vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether；Vinyl acetate, The vinyl acetates class such as vinyl butyrate, vinyl laurate, stearic acid vinyl ester；Ethylene, propylene, isoprene, butadiene etc. Unsaturated hydrocarbons；(methyl) acrylic acid trifluoromethyl ester, five fluorine ethyl ester of (methyl) acrylic acid, vinyl chloride, vinyl fluoride, chlorostyrene etc. contain Halogen monomer etc..
As the monomer of above-mentioned bridging property, such as can enumerate：Tetramethylol methane four (methyl) acrylate, tetra methylol Methane three (methyl) acrylate, tetramethylol methane two (methyl) acrylate, trimethylolpropane tris (methyl) acrylic acid Ester, dipentaerythritol six (methyl) acrylate, dipentaerythritol five (methyl) acrylate, glycerine three (methyl) acrylic acid Ester, glycerine two (methyl) acrylate, (poly-) ethylene glycol two (methyl) acrylate, (poly-) propylene glycol two (methyl) acrylic acid Multifunctional (methyl) propylene such as ester, (poly-) tetramethylene two (methyl) acrylate, 1,4- butanediols two (methyl) acrylate Esters of gallic acid；(different) triallyl cyanurate, triallyl trimellitate, divinylbenzene, dially phthalate, two allyls Base acrylamide, diallyl ether, γ-(methyl) acryloyloxypropyltrimethoxysilane, trimethoxysilyl benzene Silane-containings monomer such as ethylene, vinyltrimethoxysilane etc..
So that the above-mentioned polymerizable monomer with ethylenically unsaturated group is polymerize by using well known method, can obtain State resin particle.As this method, for example, can enumerate in the presence of radical polymerization initiator carry out suspension polymerisation method, And make monomer swell together with radical polymerization initiator using noncrosslinking kind of particle and the method etc. that polymerize.
In the case that above-mentioned base particle is inorganic particulate or organic inorganic hybridization particle in addition to metallic, As the inorganic matter for being used to form above-mentioned base particle, silica and carbon black etc. can be enumerated.As by above-mentioned titanium dioxide The particle that silicon is formed, is not particularly limited, such as can enumerate the silicon by that will have 2 or more water-disintegrable alkoxysilyls After compound is hydrolyzed and forms cross-linking polymer particle, particle obtained from being fired as needed.Have as above-mentioned Machine inorganic hybridization particle, such as the organic nothing formed by crosslinked alkoxysilyl polymer and acrylic resin can be enumerated Machine hybrid particle etc..
It, can as the metal for being used to form the metallic in the case where above-mentioned base particle is metallic Silver, copper, nickel, silicon, gold and titanium etc. are enumerated, however, it is preferred to which base particle is not metallic.
The grain size of above-mentioned base particle is preferably 0.1 μm or more, more preferably 0.5 μm or more, still more preferably It is 1 μm or more, more preferably 1.5 μm or more, particularly preferably 2 μm or more, preferably 1000 μm hereinafter, more preferably 500 μm Hereinafter, still more preferably be 300 μm hereinafter, more preferably 50 μm hereinafter, be still more preferably 30 μm hereinafter, particularly preferably For 5 μm hereinafter, most preferably 3 μm or less.If the grain size of base particle is above-mentioned lower limit or more, due to electric conductivity grain Son and the contact area of electrode become larger, and therefore, can further improve interelectrode conducting reliability, further reduce via The interelectrode connection resistance of electroconductive particle connection.In addition, being led being formed on base particle surface by electroless plating It when electric layer, is not susceptible to agglomerate, is not easy to form the electroconductive particle of cohesion.If grain size be the above-mentioned upper limit hereinafter, if be easy to fill Partial compression electroconductive particle, interelectrode connection resistance further reduce, and interelectrode interval further reduces.Above-mentioned base The grain size of body material particles indicates diameter, is not just in base particle in the case where base particle is just spherical In the case of spherical, maximum gauge is indicated.
The grain size of above-mentioned base particle is particularly preferably 0.1 μm or more and 5 μm or less.If above-mentioned basis material grain In the range of the grain size of son is 0.1~5 μm, then interelectrode interval reduces, and can be obtained if even if increasing the thickness of conductive layer To smaller electroconductive particle.From can further reduce it is interelectrode interval, even if increase conductive layer thickness when From the perspective of obtaining smaller electroconductive particle, the grain size of above-mentioned base particle is preferably 0.5 μm or more, more preferably 2 μm or more, preferably 3 μm or less.
[conductive layer]
The metal for being used to form above-mentioned conductive layer is not particularly limited.Also, it is generally conductive layer in electroconductive particle Metallic in the case of, the metal for being used to form the metallic is not particularly limited.As the metal, such as can lift Go out：Gold, silver, copper, palladium, platinum, zinc, iron, tin, lead, aluminium, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, thallium, germanium, cadmium, silicon, tungsten, molybdenum and they Alloy etc..In addition, as above-mentioned metal, can enumerate：Tin-doped indium oxide (ITO) and scolding tin etc..Wherein, due to can be more Interelectrode connection resistance is further decreased, it is therefore preferable that the alloy, nickel, palladium, copper containing tin or gold, more preferable nickel or palladium.Structure Nickel is preferably comprised at the metallic element of above-mentioned conductive layer.Above-mentioned conductive layer preferably comprises in nickel, tungsten, molybdenum, palladium, phosphorus and boron At least one, further preferably nickel, phosphorus or boron.The material for constituting above-mentioned conductive layer can also be the alloy containing phosphorus and boron etc.. In above-mentioned conductive layer, nickel and tungsten or molybdenum can also form alloy.
In the case where above-mentioned conductive layer contains phosphorus or boron, in 100 weight % of above-mentioned conductive layer, the total content of phosphorus and boron Preferably 4 weight % or less.If the total content of phosphorus and boron be the above-mentioned upper limit hereinafter, if the metals such as nickel content relativity increase It is more, therefore, it can further reduce interelectrode connection resistance.In 100 weight % of above-mentioned conductive layer, the total content of phosphorus and boron Preferably 0.1 weight % or more, more preferably 0.5 weight % or more.
The most metallic element of content preferably contains tin in above-mentioned core material, above-mentioned conductive layer and above-mentioned second conductive layer Alloy, nickel, palladium, copper or gold, more preferably nickel or palladium.
Such as electroconductive particle 1, above-mentioned conductive layer can be formed by 1 layer.In addition, such as electroconductive particle 11,21, above-mentioned conduction Layer can also be formed by multilayer.That is, conductive layer can be single layer, it is possible to have two layers or more of laminated construction.In conductive layer In the case of being formed by multilayer, preferably outermost layer be layer gold, nickel layer, palladium layers, layers of copper or containing tin and silver alloy-layer, more preferably For layer gold or palladium layers, particularly preferably layer gold.In the case that outermost layer is these preferred conductive layers, can further it reduce Interelectrode connection resistance.In addition, in the case that outermost layer is layer gold, corrosion resistance can be further increased.
The method that conductive layer is formed on the surface of above-mentioned base particle is not particularly limited.As formation conductive layer Method, for example,：Using the method for electroless plating, using electric plating method, using physical vapor deposition method and By metal powder or paste containing metal powder and adhesive in the method etc. on the surface of base particle.Wherein, Since the formation of conductive layer is simple, it is therefore preferable that utilizing the method for electroless plating.As the above-mentioned method using physical vapor deposition, It can enumerate：The methods of vacuum evaporation, ion plating and ion sputtering.
The average grain diameter of above-mentioned electroconductive particle is preferably 0.11 μm or more, more preferably 0.5 μm or more, further preferably It is 0.51 μm or more, particularly preferably 1 μm or more, preferably 100 μm hereinafter, more preferably 20 μm hereinafter, further preferably 5.6 μm hereinafter, particularly preferably 3.6 μm or less.On if the average grain diameter of electroconductive particle is above-mentioned lower limit or more and is above-mentioned Limit can fully increase between electroconductive particle and electrode hereinafter, then between using electroconductive particle connection electrode Contact area, and be not easy to form the electroconductive particle of cohesion when forming conductive layer.In addition, via electroconductive particle connection Interelectrode interval will not become too much, and conductive layer is not easy the sur-face peeling from base particle.
" average grain diameter " of above-mentioned electroconductive particle indicates number average bead diameter.The average grain diameter of electroconductive particle can pass through electricity consumption Sub- microscope or arbitrary 50 electroconductive particles of optical microphotograph sem observation simultaneously calculate average value to acquire.
The thickness of above-mentioned conductive layer is preferably 0.005 μm or more, more preferably 0.01 μm or more, and preferably 1 μm hereinafter, more Preferably 0.3 μm or less.If the thickness of conductive layer be above-mentioned lower limit or more and the above-mentioned upper limit hereinafter, if can be obtained and adequately lead Electrically, and electroconductive particle will not become really up to the mark, electroconductive particle can be made fully to deform when being connected between carrying out electrode.
In the case where above-mentioned conductive layer is formed by multilayer, the thickness of outermost conductive layer is preferably 0.001 μm or more, More preferably 0.01 μm or more, preferably 0.5 μm are hereinafter, more preferably 0.1 μm or less.If above-mentioned outermost conductive layer Thickness is above-mentioned lower limit or more and the above-mentioned upper limit hereinafter, can then make being evenly coated for outermost conductive layer, can fully be improved Corrosion resistance, and can fully reduce interelectrode connection resistance.
The thickness of above-mentioned conductive layer to electroconductive particle or can be carried by using such as transmission electron microscope (TEM) The section of the electroconductive particle of insulating properties particle is observed to measure.
The protrusion of the outer surface of the above-mentioned conductive layer of each above-mentioned electroconductive particle is preferably 3 or more, more preferably 5 More than a.The upper limit of above-mentioned number of projection is not particularly limited.Electroconductive particle can be considered in the upper limit of number of projection Average grain diameter etc. and suitably select.
[core material]
By the way that above-mentioned core material to be embedded in above-mentioned conductive layer, above-mentioned conductive layer has multiple protrusions in outer side surface.
As the method for forming above-mentioned protrusion, can enumerate：After forming the first conductive layer on the surface of base particle, Core material is configured on first conductive layer, the method for being subsequently formed the second conductive layer；And on the surface of base particle The method etc. of the upper midway stage addition core material for forming conductive layer.
As the substance for constituting above-mentioned core material, conductive material and non-conducting material can be enumerated.As above-mentioned conduction Property substance, such as can enumerate：The electrically conductive, non-metallics such as metal, metal oxide, graphite and electric conductive polymer etc..As above-mentioned Electric conductive polymer can enumerate polyacetylene etc..As above-mentioned non-conducting material, can enumerate：Silica, aluminium oxide, titanium Sour barium and zirconium oxide etc..Wherein, since electric conductivity can be improved, and it can be effectively reduced connection resistance, it is therefore preferable that golden Belong to.Above-mentioned core material is preferably metallic.
As above-mentioned metal, such as can enumerate：Gold, silver, copper, platinum, zinc, iron, lead, tin, aluminium, cobalt, indium, nickel, chromium, titanium, antimony, The metals such as bismuth, germanium and cadmium and tin-lead alloy, tin-copper alloy, tin-silver alloy, tin-lead-silver alloy and tungsten carbide etc. are by two Kind or more the alloy etc. that constitutes of metal.Wherein, preferably nickel, copper, silver or gold.The metal of above-mentioned composition core material and above-mentioned composition The metal of conductive layer may be the same or different.The metal of above-mentioned composition core material preferably comprises above-mentioned composition conductive layer Metal.The metal of above-mentioned composition core material preferably comprises nickel.The metal of above-mentioned composition core material preferably comprises nickel.
The shape of above-mentioned core material is not particularly limited.Core material is preferably shaped to bulk.As core material, such as can To enumerate：Block and unbodied piece etc. are agglomerated made of the block of particle shape, the cohesion of multiple fine particles.
The average diameter (average grain diameter) of above-mentioned core material is preferably 0.001 μm or more, more preferably 0.05 μm or more, excellent 0.9 μm is selected as hereinafter, more preferably 0.2 μm or less.If the average diameter of above-mentioned core material is more than above-mentioned lower limit and above-mentioned The upper limit is hereinafter, can then be effectively reduced interelectrode connection resistance.
" average diameter (average grain diameter) " of above-mentioned core material indicates number average diameter (number average bead diameter).Being averaged for core material is straight Diameter by using electron microscope or optical microphotograph sem observation arbitrary 50 core materials and can calculate average value and acquire.
Inorganic particulate can also be configured on the surface of above-mentioned core material.The inorganic particulate being configured on the surface of core material It is preferably several.Inorganic particulate can also be adhered on the surface of core material.Can also use have such inorganic particulate and core The compound particle of substance.It is preferred that the size (average diameter) of inorganic particulate is less than the size (average diameter) of core material, above-mentioned nothing Machine particle is preferably inorganic particles.
As the material for the above-mentioned inorganic particulate being configured on the surface of above-mentioned core material, can enumerate：(Mohs is hard for barium titanate Degree 4.5), silica (silica, Mohs' hardness 6~7), zirconium oxide (Mohs' hardness 8~9), aluminium oxide (Mohs' hardness 9), tungsten carbide (Mohs' hardness 9) and diamond (Mohs' hardness 10) etc..Above-mentioned inorganic particulate be preferably silica, zirconium oxide, Aluminium oxide, tungsten carbide or diamond, preferably also silica, zirconium oxide, aluminium oxide or diamond.Above-mentioned inorganic particulate is not Family name's hardness is preferably 5 or more, and more preferably 6 or more.It is preferred that Mohs of the Mohs' hardness of above-mentioned inorganic particulate than above-mentioned conductive layer Hardness is big.It is preferred that the Mohs' hardness of above-mentioned inorganic particulate is bigger than the Mohs' hardness of above-mentioned second conductive layer.Above-mentioned inorganic particulate The absolute value of the difference of the Mohs' hardness of Mohs' hardness and above-mentioned conductive layer and the Mohs' hardness of above-mentioned inorganic particulate and above-mentioned the The absolute value of the difference of the Mohs' hardness of two conductive layers is preferably 0.1 or more, more preferably 0.2 or more, further preferably 0.5 with On, particularly preferably 1 or more.In addition, in the case where conductive layer is formed by multilayer, the whole of multiple layers than composition of inorganic particulate When metal is hard, the reducing effect of connection resistance can be more effectively played.
The average grain diameter of above-mentioned inorganic particulate is preferably 0.0001 μm or more, more preferably 0.005 μm or more, preferably 0.5 μm hereinafter, more preferably 0.1 μm or less.On if the average grain diameter of above-mentioned inorganic particulate is above-mentioned lower limit or more and is above-mentioned Limit is hereinafter, can then be effectively reduced interelectrode connection resistance.
" average grain diameter " of above-mentioned inorganic particulate indicates number average bead diameter.The average grain diameter of inorganic particulate can be by using electronics Microscope or arbitrary 50 inorganic particulates of optical microphotograph sem observation simultaneously calculate average value to acquire.
It states in use on the surface of core material in the case of the compound particle configured with inorganic particulate, above-mentioned compound particle Average diameter (average grain diameter) be preferably 0.0012 μm or more, more preferably 0.0502 μm or more, preferably 1.9 μm hereinafter, More preferably 1.2 μm or less.If the average diameter of above-mentioned compound particle be above-mentioned lower limit more than and the above-mentioned upper limit hereinafter, if can Enough it is effectively reduced interelectrode connection resistance.
" average diameter (average grain diameter) " of above-mentioned compound particle indicates number average diameter (number average bead diameter).Above-mentioned compound particle Average diameter by using arbitrary 50 compound particles of electron microscope or optical microphotograph sem observation and average value can be calculated It acquires.
[megohmite insulant]
The electroconductive particle of the present invention is preferably provided with the megohmite insulant being configured on above-mentioned conductive layer surface.In the situation Under, when electroconductive particle is used for interelectrode connection, adjacent interelectrode short circuit can be prevented.Specifically, multiple When electroconductive particle contacts, there are megohmite insulants between multiple electrodes, it is therefore possible to prevent laterally between upper adjacent electrode, Er Feishang Under interelectrode short circuit.It should be noted that when carrying out interelectrode connection, by using two electrodes to electroconductive particle It pressurizes, can easily exclude the megohmite insulant between the conductive layer of electroconductive particle and electrode.Since electroconductive particle exists There are multiple protrusions therefore can easily exclude exhausted between the conductive layer of electroconductive particle and electrode for the outer surface of conductive layer Edge substance.
When carrying out interelectrode pressing, above-mentioned megohmite insulant can be more easily excluded, therefore, above-mentioned megohmite insulant is preferred For insulating particle.
The concrete example of material, that is, insulative resin as above-mentioned megohmite insulant can enumerate polyolefins, (methyl) propylene Acid ester polymer, (methyl) acrylate copolymer, block polymer, thermoplastic resin, the cross-linking agent of thermoplastic resin, thermosetting Property resin and water-soluble resin etc..
As said polyolefins class, it is total that polyethylene, vinyl-vinyl acetate copolymer and ethylene-acrylate can be enumerated Polymers etc..As above-mentioned (methyl) acrylate polymer, poly- (methyl) methyl acrylate, poly- (methyl) acrylic acid second can be enumerated Ester and poly- (methyl) butyl acrylate etc..As above-mentioned block polymer, it is total that polystyrene, cinnamic acrylic ester can be enumerated Polymers, SB types styrene-butadiene block copolymer and SBS types styrene-butadiene block copolymer and these polymer Hydrogenation products etc..As above-mentioned thermoplastic resin, polyvinyl and ethylenic copolymer etc. can be enumerated.As above-mentioned heat Thermosetting resin can enumerate epoxy resin, phenolic resin and melmac etc..As above-mentioned water-soluble resin, can enumerate poly- Vinyl alcohol, polyacrylic acid, polyacrylamide, polyvinylpyrrolidone, polyethylene glycol oxide and methylcellulose etc..Wherein, excellent Select water-soluble resin, more preferable polyvinyl alcohol.
As the method for configuring megohmite insulant on the surface of above-mentioned conductive layer, chemical method and physics or machinery can be enumerated Method etc..As above-mentioned chemical method, can enumerate：Interfacial polymerization, suspension polymerization in the presence of particle and emulsion polymerization Method etc..As it is above-mentioned physically or mechanically, spray drying process, hydridization method, electrostatic adherence method, spray-on process, dipping can be enumerated Method and the method etc. for utilizing vacuum evaporation.It wherein, preferably will be above-mentioned exhausted by chemical bond since megohmite insulant is not easily disconnected from The method that edge substance is configured at the surface of above-mentioned conductive layer.
The average diameter (average grain diameter) of above-mentioned megohmite insulant can be according to the grain size of electroconductive particle and electroconductive particle Purposes etc. is suitable for selection.The average diameter (average grain diameter) of above-mentioned megohmite insulant is preferably 0.005 μm or more, more preferably 0.01 μm or more, preferably 1 μm hereinafter, more preferably 0.5 μm or less.If the average diameter of megohmite insulant is above-mentioned lower limit or more, When then electroconductive particle being made to be scattered in adhesive resin, the conductive layer in multiple electroconductive particles is not easy to contact each other.If The average diameter of insulating properties particle be the above-mentioned upper limit hereinafter, then between connection electrode when, without in order to exclude electrode and electric conductivity Megohmite insulant between particle and excessively improve pressure, need not also be heated to high temperature.
" average diameter (average grain diameter) " of above-mentioned megohmite insulant indicates number average diameter (number average bead diameter).Megohmite insulant is put down Equal diameter can utilize particle size distribution device etc. to acquire.
(conductive material)
The conductive material of the present invention contains above-mentioned electroconductive particle and adhesive resin.Above-mentioned electroconductive particle preferably disperses It is used as conductive material in adhesive resin.Above-mentioned conductive material is preferably anisotropic conductive material.
Above-mentioned adhesive resin is not particularly limited.As above-mentioned adhesive resin, well known insulative resin can be used.
As above-mentioned adhesive resin, such as can enumerate：Vinylite, thermoplastic resin, curable resin, thermoplasticity Block copolymer and elastomer etc..Above-mentioned adhesive resin can only use one kind, can also be applied in combination two or more.
As above-mentioned vinylite, for example,：Vinyl acetate resin, acrylic resin and styrene resin Deng.As above-mentioned thermoplastic resin, for example,：Vistanex, vinyl-vinyl acetate copolymer and polyamide resin Fat etc..As above-mentioned curable resin, for example,：Epoxy resin, polyurethane resin, polyimide resin and unsaturation Polyester resin etc..It should be noted that above-mentioned curable resin can be solid for normal temperature cured type resin, thermohardening type resin, light Change type resin or wet-cured type resin.Above-mentioned curable resin can be applied in combination with curing agent.As above-mentioned thermoplastic block Copolymer, for example,：Styrene-Butadiene-Styrene Block Copolymer, styrene-isoprene-phenylethene block Copolymer, the hydrogenation products of Styrene-Butadiene-Styrene Block Copolymer and styrene-isoprene-phenylethene block are total The hydrogenation products etc. of polymers.As above-mentioned elastomer, for example,：Styrene butadiene copolymers rubber and acrylonitrile- Styrene rubber etc..
In above-mentioned conductive material other than above-mentioned electroconductive particle and above-mentioned adhesive resin, it can also contain and for example fill out It is steady to fill agent, incremental agent, softening agent, plasticizer, polymerization catalyst, curing catalysts, colorant, antioxidant, heat stabilizer, light Determine the various additives such as agent, ultra-violet absorber, lubricant, antistatic agent and fire retardant.
The method that above-mentioned electroconductive particle is scattered in above-mentioned adhesive resin is set to use conventionally known dispersion side Method is not particularly limited.As making above-mentioned electroconductive particle be scattered in the method in above-mentioned adhesive resin, example can be enumerated Such as：After adding above-mentioned electroconductive particle in above-mentioned adhesive resin, carried out being kneaded the side for making it disperse with planetary mixer etc. Method；So that above-mentioned electroconductive particle is evenly dispersed in water or organic solvent using homogenizer etc., is then added to above-mentioned bonding In agent resin, planetary mixer etc. is used in combination to carry out being kneaded the method for making it disperse；And by above-mentioned adhesive resin water or have After solvent etc. is diluted, electroconductive particle is added, planetary mixer etc. is used in combination to carry out being kneaded the method etc. for making it disperse.
The conductive material of the present invention can be made into electroconductive paste or conductive film uses.It is conductive film in the conductive material of the present invention In the case of, the film of electroconductive particle can also be free of in the conductive film superimposed layer containing electroconductive particle.Above-mentioned electroconductive paste is excellent It is selected as anisotropic conductive paste.Above-mentioned conductive film is preferably anisotropic conductive film.
In 100 weight % of above-mentioned conductive material, the content of above-mentioned adhesive resin is preferably 10 weight % or more, more excellent It is selected as 30 weight % or more, further preferably 50 weight % or more, particularly preferably 70 weight % or more, preferably 99.99 Weight % is hereinafter, more preferably 99.9 weight % or less.If the content of above-mentioned adhesive resin be above-mentioned lower limit more than and on The upper limit is stated hereinafter, then electroconductive particle is efficiently configured between electrode, by the connection of the connecting object component of conductive material connection Reliability further increases.
In 100 weight % of above-mentioned conductive material, the content of above-mentioned electroconductive particle is preferably 0.01 weight % or more, more Preferably 0.1 weight % or more, preferably 40 weight % hereinafter, more preferably 20 weight % hereinafter, further preferably 10 weights Measure % or less.If the content of above-mentioned electroconductive particle be above-mentioned lower limit more than and the above-mentioned upper limit hereinafter, if interelectrode conducting Reliability further increases.
(connection structural bodies)
By using electroconductive particle of the invention or use the conduction containing the electroconductive particle and adhesive resin Material is attached connecting object component, can obtain connection structural bodies.
It is preferred that above-mentioned connection structural bodies have the first connecting object component, the second connecting object component and connection first, The interconnecting piece of second connecting object component, and the interconnecting piece is formed or by the electroconductive particle of the present invention by containing the conduction Property particle and adhesive resin conductive material (anisotropic conductive material etc.) formation.The case where using electroconductive particle Under, interconnecting piece sheet is as electroconductive particle.That is, the first, second connecting object component is connected by electroconductive particle.
The electroconductive particle for having used first embodiment of the invention is schematically shown in Fig. 4 with front section view Connection structural bodies.
Connection structural bodies 51 shown in Fig. 4 has the first connecting object component 52, the second connecting object component 53, Yi Jilian Connect the interconnecting piece 54 of the first, the second connecting object component 52,53.Interconnecting piece 54 is by making the conduction material containing electroconductive particle 1 Material is solidified to form.It should be noted that in Fig. 4, in order to illustrate conveniently, electroconductive particle 1 is indicated with schematic diagram.
First connecting object component 52 has multiple electrodes 52b in upper surface 52a (surface).Second connecting object component 53 In lower surface, 53a (surface) has multiple electrodes 53b.Electrode 52b and electrode 53b passes through 1 electricity of one or more electroconductive particles Connection.Therefore, the first, the second connecting object component 52,53 is electrically connected by electroconductive particle 1.
The manufacturing method of above-mentioned connection structural bodies is not particularly limited.One example of the manufacturing method as connection structural bodies Son can be enumerated：Above-mentioned conductive material is configured between the first connecting object component and the second connecting object component and obtains lamination After body, method etc. which is heated and pressurizeed.
The pressure of above-mentioned pressurization is 9.8 × 104~4.9 × 106Pa or so.The temperature of above-mentioned heating is 120~220 DEG C of left sides It is right.
As above-mentioned connecting object component, can specifically enumerate：The electronic units such as semiconductor chip, capacitor and diode, And electronic units such as circuit boards such as printed base plate, flexible printing substrate and glass substrate etc..Above-mentioned connecting object component is excellent It is selected as electronic unit.Above-mentioned electroconductive particle is preferred for the electrical connection of the electrode in electronic unit.
As the electrode for being set to above-mentioned connecting object component, can enumerate：Gold electrode, nickel electrode, tin electrode, aluminium electricity The metal electrodes such as pole, copper electrode, molybdenum electrode and tungsten electrode.In the case where above-mentioned connecting object component is flexible printing substrate, It is preferred that above-mentioned electrode is gold electrode, nickel electrode, tin electrode or copper electrode.The case where above-mentioned connecting object component is glass substrate Under, preferably above-mentioned electrode is aluminium electrode, copper electrode, molybdenum electrode or tungsten electrode.It should be noted that being aluminium electrode in above-mentioned electrode In the case of, can be the electrode only formed by aluminium, or made of the surface stack aluminium layer of metal oxide layer Electrode.As the material of above-mentioned metal oxide layer, can enumerate doped with the indium oxide of trivalent metallic element and doped with trivalent The zinc oxide etc. of metallic element.As above-mentioned trivalent metallic element, can enumerate：Sn, Al and Ga etc..
Hereinafter, enumerating Examples and Comparative Examples further illustrates the present invention.The present invention is not limited to reality below Apply example.
(embodiment 1)
(1) palladium adheres to process
Prepare divinylbenzene resin particle (ponding chemical industrial company system " the Micropearl SP- that grain size is 5.0 μm 205").The resin particle is etched, is washed.Then, in the palladium catalyst of the 100mL containing 8 weight % palladium catalysts Resin particle is added in liquid and is stirred.Then, it is filtered, cleans.In the dimethylamino for the 0.5 weight % that pH value is 6 Resin particle is added in borine liquid, obtains the resin particle for being attached with palladium.
(2) process for electroless nickel plating process
In order to form nickel-phosphor conductive layer, prepared the nickel sulfate containing 0.25mol/L, 0.25mol/L sodium hypophosphite, The nickel-plating liquid (pH8.0) of the sodium citrate of 0.15mol/L and the sodium molybdate of 0.01mol/L.
The resin particle of palladium is attached with obtained by addition in the pure water of 1000mL, is disperseed using ultrasonic disperser, Suspension has been obtained as a result,.Above-mentioned nickel-plating liquid is slowly added dropwise into suspension while 60 DEG C of stirring gained suspension, carries out Process for electroless nickel plating.Then, particle is isolated by being filtered to suspension, and is washed, is dried, use nickel-phosphor as a result, (the first resin-coated particle of conductive layer (thickness 5.2nm) of nickel-molybdenum-phosphorous layer (Ni-Mo-P layers) i.e., has obtained being formed with first layer The particle of conductive layer.
(3) core material attachment process and process for electroless nickel plating process
Prepare aluminium oxide (Al2O3) particle slurry (average grain diameter 100nm).Using be formed with the first conductive layer particle and Metallic slurry is coated.
In order to form nickel-phosphor conductive layer, prepared the nickel sulfate containing 0.25mol/L, 0.25mol/L sodium hypophosphite, The nickel-plating liquid (pH8.0) of the sodium citrate of 0.15mol/L and the sodium molybdate of 0.01mol/L.
In 60 DEG C of stirring gained suspension, while above-mentioned nickel-plating liquid being slowly added dropwise into suspension, carries out process for electroless nickel plating, Form the second conductive layer (nickel-molybdenum-phosphorous layer (Ni-Mo-P layers)) that thickness is 90nm.Then, by being filtered to suspension And particle is isolated, and washed, dried, result in electroconductive particle.Obtained electroconductive particle is in the second conduction The outer surface of layer has protrusion, and is configured with core material in the inside of the protrusion of the second conductive layer.In addition, in resin particle and The first conductive layer is configured between core material.
(embodiment 2)
In addition to by aluminium oxide (Al2O3) to be altered to silicon dioxide granule slurry (average for particle slurry (average grain diameter 100nm) Grain size 100nm) other than, implement similarly to Example 1, has obtained electroconductive particle.
(embodiment 3)
In addition to by aluminium oxide (Al2O3) to be altered to tungsten carbide (WC) particle slurry (flat for particle slurry (average grain diameter 100nm) Equal grain size 100nm) other than, implement similarly to Example 1, has obtained electroconductive particle.
(embodiment 4~8)
In addition to the thickness of i.e. the first conductive layer of layer of nickel-phosphorous is altered to it is following shown in other than value, similarly to Example 1 Implement, has obtained electroconductive particle.
The thickness of first conductive layer：
Embodiment 4：10μm
Embodiment 5：20μm
Embodiment 6：100μm
Embodiment 7：750μm
Embodiment 8：860μm
(embodiment 9)
(1) making of insulating properties particle
Four neck removable lids (4 Star mouth セ パ ラ Block Le カ バ ー), agitating paddle, triple valve, condenser pipe and temperature are being installed In the removable flask of the 1000mL of sensor, weigh containing methyl methacrylate 100mmol, N, N, N- trimethyls-N-2- The monomer composition of bis- (2- amidine propanes) the dihydrochloride 1mmol of methylacryoyloxyethyl ammonium chloride 1mmol and 2,2 '-azo In ion exchange water and the solid constituent point rate of the monomer composition is made to be then 5 weight % are stirred with 200rpm It mixes, has carried out polymerizeing for 24 hours in nitrogen atmosphere, at 70 DEG C.After reaction, it is freeze-dried, having obtained surface has Ammonium, average grain diameter are the insulating properties particle that 220nm and CV values are 10%.
So that insulating properties particle is dispersed in ion exchange water under ultrasonic activation, obtains 10 weight % of insulating properties particle Aqueous dispersions.
So that the electroconductive particle 10g obtained in embodiment 1 is scattered in 500mL ion exchange waters, adds insulating properties particle Aqueous dispersions 4g, be stirred at room temperature 6 hours.After 3 μm of granular membrane filtering, further cleaned with methanol, It is dry, obtain the electroconductive particle for being attached with insulating properties particle.
Using scanning electron microscope (SEM) observed as a result, the surface of electroconductive particle only form 1 layer by The clad that insulating properties particle is constituted.Cladding area (the i.e. grain of insulating properties particle of insulating properties particle is calculated using image analysis The projected area of diameter) relative to 2.5 μm of the center away from electroconductive particle area ratio, as a result, clad ratio 30%.
(embodiment 10)
In addition to divinylbenzene resin particle (the ponding chemical industrial company system " Micropearl for being 5.0 μm by grain size SP-205 ") it is altered to divinylbenzene resin particle (the ponding chemical industrial company for being 5.0 μm by coated with silica grain size Make " Micropearl SP-205 ") surface made of other than organic inorganic hybridization particle (5.1 μm of grain size), it is same with embodiment 1 Implement to sample, has obtained electroconductive particle.
(comparative example 1)
Other than the thickness of i.e. the first conductive layer of layer of nickel-phosphorous is altered to 4.5nm, implements similarly to Example 1, obtain Electroconductive particle is arrived.
(comparative example 2)
Prepare divinylbenzene resin particle (ponding chemical industrial company system " the Micropearl SP- that grain size is 5.0 μm 205").In addition, preparing aluminium oxide (Al2O3) particle slurry (average grain diameter 100nm).It is starched using resin particle and metallic Material, using the surface of the resin-coated particle of core material, has obtained suspension.
In order to form nickel-phosphor conductive layer, prepared the nickel sulfate containing 0.25mol/L, 0.25mol/L sodium hypophosphite, The nickel-plating liquid (pH8.0) of the sodium citrate of 0.15mol/L and the sodium molybdate of 0.01mol/L.
Above-mentioned nickel-plating liquid is slowly added dropwise into suspension while 60 DEG C of stirring gained suspension, carries out electroless plating Nickel forms the conductive layer that thickness is 100nm.Then, particle is isolated by being filtered to suspension, and carries out water It washes, dry, result in electroconductive particle.In obtained electroconductive particle, core material and base particle contact.
(embodiment 11)
(1) palladium adheres to process
The resin particle for being attached with palladium obtained in embodiment 1 is prepared.
(2) process for electroless nickel plating process
Prepare the sodium citrate of the nickel sulfate containing 0.23mol/L, the dimethylamino borine of 0.92mol/L, 0.5mol/L And the nickel-plating liquid (pH8.5) of the sodium tungstate of 0.01mol/L.
The resin particle of palladium is attached with obtained by addition in the pure water of 1000mL, is disperseed using ultrasonic disperser, Suspension has been obtained as a result,.Above-mentioned nickel-plating liquid is slowly added dropwise into suspension while 60 DEG C of stirring gained suspension, carries out Process for electroless nickel plating.Then, particle is isolated by being filtered to suspension, and is washed, is dried, use nickel-as a result, Tungsten-boron layer i.e. the first resin-coated particle of conductive layer (thickness 5.1nm), has obtained the particle for being formed with the first conductive layer.
(3) core material attachment process and process for electroless nickel plating process
Prepare aluminium oxide (Al2O3) particle slurry (average grain diameter 100nm).Using be formed with the first conductive layer particle and Metallic slurry is coated.
Prepare the sodium citrate of the nickel sulfate containing 0.23mol/L, the dimethylamino borine of 0.92mol/L, 0.5mol/L And the nickel-plating liquid (pH8.5) of the sodium tungstate of 0.01mol/L.
Above-mentioned nickel-plating liquid is slowly added dropwise into suspension while 60 DEG C of stirring gained suspension, carries out electroless plating Nickel forms the second conductive layer that thickness is 90nm.Then, particle is isolated by being filtered to suspension, and carried out Washing, drying, have obtained electroconductive particle as a result,.Obtained electroconductive particle has prominent in the outer surface of the second conductive layer It rises, and core material is configured in the inside of the protrusion of the second conductive layer.In addition, configured with the between resin particle and core material One conductive layer.
(embodiment 12)
It is real similarly to Example 11 other than the thickness of i.e. the first conductive layer of nickel-tungsten-boron layer is altered to 10nm It applies, has obtained electroconductive particle.
(embodiment 13)
It is real similarly to Example 11 other than the thickness of i.e. the first conductive layer of nickel-tungsten-boron layer is altered to 20nm It applies, has obtained electroconductive particle.
(embodiment 14)
Prepare 10 weight % aqueous dispersions of the insulating properties particle obtained in embodiment 9.Make what is obtained in embodiment 11 to lead Conductive particles 10g is scattered in 500mL ion exchange waters, adds the aqueous dispersions 4g of insulating properties particle, it is small to be stirred at room temperature 6 When.After 3 μm of granular membrane filtering, is further cleaned, dried with methanol, obtained being attached with insulating properties particle Electroconductive particle.
Using scanning electron microscope (SEM) observed as a result, the surface of electroconductive particle only form 1 layer by The clad that insulating properties particle is constituted.Cladding area (the i.e. grain of insulating properties particle of insulating properties particle is calculated using image analysis The projected area of diameter) relative to 2.5 μm of the center away from electroconductive particle area ratio, as a result, clad ratio 30%.
(comparative example 3)
Other than the thickness of i.e. the first conductive layer of nickel-tungsten-boron layer is altered to 3nm, implement similarly to Example 11, Electroconductive particle is obtained.
(comparative example 4)
Prepare divinylbenzene resin particle (ponding chemical industrial company system " the Micropearl SP- that grain size is 5.0 μm 205").In addition, preparing aluminium oxide (Al2O3) particle slurry (average grain diameter 100nm).It is starched using resin particle and metallic Material, using the surface of the resin-coated particle of core material, has obtained suspension.
Prepare the sodium citrate of the nickel sulfate containing 0.23mol/L, the dimethylamino borine of 0.92mol/L, 0.5mol/L And the nickel-plating liquid (pH8.5) of the sodium tungstate of 0.01mol/L.
Above-mentioned nickel-plating liquid is slowly added dropwise into suspension while 60 DEG C of stirring gained suspension, carries out electroless plating Nickel forms the conductive layer that thickness is 100nm.Then, particle is isolated by being filtered to suspension, and carries out water It washes, dry, result in electroconductive particle.In obtained electroconductive particle, core material and base particle contact.
(embodiment 15)
(1) palladium adheres to process
Prepare the resin particle for being attached with palladium obtained in embodiment 1.
(2) process for electroless nickel plating process
Prepare the sodium citrate of the nickel sulfate containing 0.23mol/L, the dimethylamino borine of 0.92mol/L, 0.5mol/L And the nickel-plating liquid (pH8.5) of the sodium tungstate of 0.01mol/L.
The resin particle of palladium is attached with obtained by addition in the pure water of 1000mL, is disperseed using ultrasonic disperser, Suspension is obtained.Above-mentioned nickel-plating liquid is slowly added dropwise into suspension while 60 DEG C of stirring gained suspension, carries out non-electrical Solve nickel plating.Then, particle is isolated by being filtered to suspension, and is washed, is dried, use nickel-tungsten-boron as a result, Layer is the resin-coated particle of the first conductive layer of thickness 10nm, has obtained the particle for being formed with the first conductive layer.
(3) core material attachment process and process for electroless nickel plating process
Prepare barium titanate (BaTiO3) particle slurry (average grain diameter 100nm).Use the particle for being formed with the first conductive layer With metallic slurry, the surface of the first conductive layer is coated with metallic, obtains suspension.
Prepare the nickel sulfate containing 0.23mol/L, the dimethylamino borine of 0.92mol/L and the sodium citrate of 0.5mol/L Nickel-plating liquid (pH7.0).
Above-mentioned nickel-plating liquid is slowly added dropwise into suspension while 60 DEG C of stirring gained suspension, carries out electroless plating Nickel forms the second conductive layer that thickness is 90nm.Then, particle is isolated by being filtered to suspension, and carried out Washing, drying, result in electroconductive particle.Obtained electroconductive particle has prominent in the outer surface of the second conductive layer It rises, core material is configured in the inside of the protrusion of the second conductive layer.In addition, being configured with first between resin particle and core material Conductive layer.
(embodiment 16)
It is real similarly to Example 15 other than the thickness of i.e. the first conductive layer of nickel-tungsten-boron layer is altered to 5.1nm It applies, has obtained electroconductive particle.
(embodiment 17)
It is real similarly to Example 15 other than the thickness of i.e. the first conductive layer of nickel-tungsten-boron layer is altered to 20nm It applies, has obtained electroconductive particle.
(embodiment 18)
In addition to by barium titanate (BaTiO3) particle slurry (average grain diameter 100nm) is altered to aluminium oxide (Al2O3) particle slurry Other than (average grain diameter 100nm), implement similarly to Example 15, has obtained electroconductive particle.
(embodiment 19)
In addition to by barium titanate (BaTiO3) particle slurry (average grain diameter 100nm) is altered to aluminium oxide (Al2O3) particle slurry Other than (average grain diameter 100nm), implement similarly to Example 16, has obtained electroconductive particle.
(embodiment 20)
In addition to by barium titanate (BaTiO3) particle slurry (average grain diameter 100nm) is altered to aluminium oxide (Al2O3) particle slurry Other than (average grain diameter 100nm), implement similarly to Example 17, has obtained electroconductive particle.
(embodiment 21)
Other than the sodium tungstate of additional 0.01mol/L in the nickel-plating liquid for being used to form the second conductive layer, with embodiment 15 similarly implement, and have obtained electroconductive particle.
(embodiment 22)
Prepare 10 weight % aqueous dispersions of the insulating properties particle obtained in embodiment 9.Make what is obtained in embodiment 15 to lead Conductive particles 10g is scattered in 500mL ion exchange waters, adds the aqueous dispersions 4g of insulating properties particle, it is small to be stirred at room temperature 6 When.After 3 μm of granular membrane filtering, is further cleaned, dried with methanol, obtained being attached with insulating properties particle Electroconductive particle.
Using scanning electron microscope (SEM) observed as a result, the surface of electroconductive particle only form 1 layer by The clad that insulating properties particle is constituted.Cladding area (the i.e. grain of insulating properties particle of insulating properties particle is calculated using image analysis The projected area of diameter) relative to 2.5 μm of the center away from electroconductive particle area ratio, as a result, clad ratio 30%.
(comparative example 5)
Prepare divinylbenzene resin particle (ponding chemical industrial company system " the Micropearl SP- that grain size is 5.0 μm 205").In addition, preparing barium titanate (BaTiO3) particle slurry (average grain diameter 100nm).It is starched using resin particle and metallic Material, using the surface of the resin-coated particle of core material, has obtained suspension.
Prepare the sodium citrate of the nickel sulfate containing 0.23mol/L, the dimethylamino borine of 0.92mol/L, 0.5mol/L And the nickel-plating liquid (pH8.5) of the sodium tungstate of 0.01mol/L.
Above-mentioned nickel-plating liquid is slowly added dropwise into suspension while 60 DEG C of stirring gained suspension, carries out electroless plating Nickel forms the conductive layer that thickness is 100nm.Then, particle is isolated by being filtered to suspension, and carries out water It washes, dry, result in electroconductive particle.In obtained electroconductive particle, core material and base particle contact.
(comparative example 6)
Other than the thickness of i.e. the first conductive layer of nickel-tungsten-boron layer is altered to 1nm, implement similarly to Example 18, Electroconductive particle is obtained.
(embodiment 23)
Prepare 10 weight % aqueous dispersions of the insulating properties particle obtained in embodiment 9.Make what is obtained in embodiment 18 to lead Conductive particles 10g is scattered in 500mL ion exchange waters, adds the aqueous dispersions 4g of insulating properties particle, it is small to be stirred at room temperature 6 When.After 3 μm of granular membrane filtering, is further cleaned, dried with methanol, obtained being attached with insulating properties particle Electroconductive particle.
Using scanning electron microscope (SEM) observed as a result, the surface of electroconductive particle only form 1 layer by The clad that insulating properties particle is constituted.Cladding area (the i.e. grain of insulating properties particle of insulating properties particle is calculated using image analysis The projected area of diameter) relative to 2.5 μm of the center away from electroconductive particle area ratio, as a result, clad ratio 30%.
(evaluation)
(1) average distance between the surface of base particle and the surface of core material
Cutting gained electroconductive particle simultaneously carries out section observation, thus determines the surface of base particle and multiple cores The distance between substance.The distance between the surface of base particle and the surface of core material measure as follows：Shooting is conductive Property particle multiple positions section and obtain image, by gained image making stereo-picture, obtained stereo-picture is used It is measured.The focused ion beam scanning electron microscope (FIBSEM) that the shooting of above-mentioned section is manufactured using Japanese FEI Co. Device name Helious NanoLab.650 are carried out.The cut film of electroconductive particle is made using focused ion beam, and is utilized and swept Retouch electron microscope observation section.By being repeated the operation 200 times and carrying out image analysis, the stereogram of particle has been obtained Picture.The distance between the surface of base particle and the surface of core material are found out by stereo-picture.
(2) in 100 weight % of the total number of core material, between the surface of base particle and the surface of core material Distance is more than the ratio (%) of the number of the core material of 5nm
In the same manner as the assessment item of above-mentioned (1), measure in the 100 weight % of total number of core material, basis material grain The surface of son and the distance between the surface of core material are more than the ratio (%) of the number of the core material of 5nm, and according to following bases Standard is judged.
[the distance between the surface of base particle and the surface of core material are more than the ratio of the number of the core material of 5nm The determinating reference of example (%)]
A：The ratio of above-mentioned number is more than 80%
B：The ratio of above-mentioned number is 80% or less
(3) resistance is connected
The making of connection structural bodies：
Mix bisphenol A type epoxy resin (Mitsubishi Chemical Ind's system " Epikote 1009 "), 40 parts by weight of 10 parts by weight Acrylic rubber (weight average molecular weight is about 800,000), the methyl ethyl ketone of 200 parts by weight, 50 parts by weight microcapsule-type solidification Agent (ASAHI KASEI CHEMICALS corporations " HX3941HP "), 2 parts by weight silane coupling agent (Dow Corning Toray Silicone corporations " SH6040 "), and adding electroconductive particle makes its content be 3 weight %, is disperseed, is obtained Resin combination.
Obtained resin combination is coated on single side, and to have passed through the PET that the thickness of demoulding processing is 50 μm (poly- to benzene two Formic acid glycol ester) film made anisotropic conductive film using 70 DEG C of heated-air drying 5 minutes.Obtained anisotropy is led The thickness of electrolemma is 12 μm.
Obtained anisotropic conductive film is cut into the size of 5mm × 5mm.The anisotropic conductive film that will be cut It is fitted in the aluminium electricity for the glass substrate (width 3cm, length 3cm) for being provided with aluminium electrode (0.2 μm, L/S=20 μm/20 μm of height) The substantial middle of pole side, wherein the aluminium electrode is the electrode that side has resistance measurement lead.Then, will have identical The two-layer flexible printed base plate (width 2cm, length 1cm) of aluminium electrode is bonded after being aligned in such a way that electrode overlaps each other. Hot pressing is carried out to the laminated body of the glass substrate and two-layer flexible printed base plate with the pressing condition of 10N, 180 DEG C and 20 seconds It closes, has obtained connection structural bodies.Wherein, the two-layer flexible printing that aluminium electrode is formed directly on polyimide film is used Substrate.
Connect the measurement of resistance：
As four-end method determine obtained by connection structural bodies opposite interelectrode connection resistance.In addition, with following bases Standard determined connection resistance.
[determinating reference of connection resistance]
○○：Connection resistance is 2.0 Ω or less
○：Connection resistance is more than 2.0 Ω and is 3.0 Ω or less
△：Connection resistance is more than 3.0 Ω and is 5.0 Ω or less
×：It is more than 5.0 Ω to connect resistance
(4) impact resistance
So that the connection structural bodies obtained in the evaluation that above-mentioned (3) connect resistance is fallen from the position of height 70cm, confirms Conducting, has thus carried out the evaluation of impact resistance.According to the climbing of the resistance value relative to initial stage resistance value, according to following bases Standard determined impact resistance.
[determinating reference of impact resistance]
○○：The climbing of resistance value relative to initial stage resistance value is 20% or less
○：The climbing of resistance value relative to initial stage resistance value is more than 20% and is 35% or less
△：The climbing of resistance value relative to initial stage resistance value is more than 35% and is 50% or less
×：The climbing of resistance value relative to initial stage resistance value is more than 50%
(5) state of impression
Using differential interference microscope, the glass of the connection structural bodies obtained from the evaluation that above-mentioned (3) connect resistance Substrate-side observes the electrode for being set to glass substrate, has on the electrode contacted to electroconductive particle according to following determinating references No impression formation is evaluated.It should be noted that about whether there is or not impressions to be formed on electrode, it is 0.02mm to make electrode area2, It is observed, has been calculated in every 0.02mm using differential interference microscope2Impression number on electrode area.It is micro- using differential interference Arbitrary 10 positions of sem observation have been calculated per 0.02mm2The average value of impression number on electrode area.
[determinating reference of impression state]
○：Per 0.02mm2The average value of impression number on electrode area is 20 or more
△：Per 0.02mm2The average value of impression number on electrode area is 5 or more and less than 20
×：Per 0.02mm2The average value of impression number on electrode area is less than 5
As a result as shown in following table 1~3.It should be noted that shown in following table 1~3 first, second conductive layer and The Mohs' hardness of core material.In addition, in following table 1~3, "-" expression is not evaluated.
[table 2]

Claims (11)

1. a kind of electroconductive particle, has：
Base particle,
Coat described matrix material particles conductive layer and
The multiple core materials being embedded in the conductive layer,
The surface of the conductive layer on the outside has multiple protrusions, is configured in the inside of the protrusion of the conductive layer described Core material,
The conductive layer, the surface of described matrix material particles are configured between described matrix material particles and the core material Separated by a distance with the surface of the core material, being averaged between the surface of described matrix material particles and the surface of the core material Distance is more than 5nm.
2. electroconductive particle according to claim 1, wherein
Average distance between the surface of described matrix material particles and the surface of the core material be more than 5nm and for 800nm with Under.
3. electroconductive particle according to claim 1 or 2, wherein
In the total number 100% of the core material, between the surface of described matrix material particles and the surface of the core material Distance be more than 5nm core material number ratio be more than 80% and be 100% or less.
4. electroconductive particle described in any one of claim 1 to 3, wherein
The most metallic element of the content metallic element most with content in the conductive layer is identical in the core material.
5. electroconductive particle according to any one of claims 1 to 4, wherein
The conductive layer has the first conductive layer and cladding first conductive layer and described of cladding described matrix material particles Second conductive layer of core material,
The core material is configured on the surface of first conductive layer, and is embedded in second conductive layer,
The surface of second conductive layer on the outside has multiple protrusions,
It is configured with the core material in the inside of the protrusion of second conductive layer,
First conductive layer is configured between described matrix material particles and the core material.
6. electroconductive particle according to claim 5, wherein
The most metallic element of the content metallic element most with content in second conductive layer is identical in the core material.
7. electroconductive particle according to any one of claims 1 to 4, wherein
The conductive layer is the conductive layer of single layer.
8. electroconductive particle according to any one of claims 1 to 7, wherein
The core material is metallic.
9. according to electroconductive particle according to any one of claims 1 to 8, it is also equipped with the surface for being attached to the conductive layer Megohmite insulant.
10. a kind of conductive material contains electroconductive particle according to any one of claims 1 to 9 and adhesive resin.
11. a kind of connecting structure body, has：
First connecting object component,
Second connecting object component and
The interconnecting piece of the first, second connecting object component is connected,
The interconnecting piece is formed by electroconductive particle according to any one of claims 1 to 9 or by containing the electric conductivity The conductive material of particle and adhesive resin is formed.
CN201810695985.2A 2011-12-21 2012-12-19 Conductive particle, conductive material, and connection structure Active CN108806824B (en)

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