CN103748637A - Conductive particles, conductive material and connection structure - Google Patents

Conductive particles, conductive material and connection structure Download PDF

Info

Publication number
CN103748637A
CN103748637A CN201380002679.1A CN201380002679A CN103748637A CN 103748637 A CN103748637 A CN 103748637A CN 201380002679 A CN201380002679 A CN 201380002679A CN 103748637 A CN103748637 A CN 103748637A
Authority
CN
China
Prior art keywords
particle
mentioned
conductive layer
electroconductive particle
inorganic particulate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201380002679.1A
Other languages
Chinese (zh)
Other versions
CN103748637B (en
Inventor
西冈敬三
大塚真弘
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sekisui Chemical Co Ltd
Original Assignee
Sekisui Chemical Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sekisui Chemical Co Ltd filed Critical Sekisui Chemical Co Ltd
Publication of CN103748637A publication Critical patent/CN103748637A/en
Application granted granted Critical
Publication of CN103748637B publication Critical patent/CN103748637B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R13/00—Details of coupling devices of the kinds covered by groups H01R12/70 or H01R24/00 - H01R33/00
    • H01R13/02—Contact members
    • H01R13/03—Contact members characterised by the material, e.g. plating, or coating materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/001—Conductive additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R4/00—Electrically-conductive connections between two or more conductive members in direct contact, i.e. touching one another; Means for effecting or maintaining such contact; Electrically-conductive connections having two or more spaced connecting locations for conductors and using contact members penetrating insulation
    • H01R4/04—Electrically-conductive connections between two or more conductive members in direct contact, i.e. touching one another; Means for effecting or maintaining such contact; Electrically-conductive connections having two or more spaced connecting locations for conductors and using contact members penetrating insulation using electrically conductive adhesives

Abstract

Provided are conductive particles which are capable of lowering the connection resistance between electrodes in cases where the conductive particles are used for the connection between the electrodes. A conductive particle (21) of the present invention comprises: a base particle (2); a conductive layer (22) that is arranged on the surface of the base particle (2) and has a plurality of projections (22a) on the outer surface; and a plurality of inorganic particles (23) that are embedded in the conductive layer (22). The inorganic particles (23) are arranged within the projections (22a) on the outer surface of the conductive layer (22). At least some of the plurality of inorganic particles (23) are out of contact with the surface of the base particle (2).

Description

Electroconductive particle, electric conducting material and syndeton body
Technical field
The present invention relates to can be used for the electroconductive particle of for example interelectrode electrical connection, more specifically, relate to a kind of electroconductive particle that disposes conductive layer and there are multiple projections at the outer surface of this conductive layer on the surface of basis material particle.In addition, electric conducting material and the syndeton body of above-mentioned electroconductive particle have been the present invention relates to use.
Background technology
The anisotropic conductive materials such as anisotropic conductive paste and anisotropic conductive film are by well-known.For these anisotropic conductive materials, in adhesive resin, be dispersed with multiple electroconductive particles.
Above-mentioned anisotropic conductive material has been used to connection and the IC chip between IC chip and flexible printed wiring board and has had connection between the circuit substrate of ITO electrode etc.For example, can, by configure anisotropic conductive material between the electrode of IC chip and the electrode of circuit substrate after, heat and pressurize, realizing the electrical connection between these electrodes.
As an example of above-mentioned electroconductive particle, the electroconductive particle that possesses compound particle and cover the coat of metal of this compound particle is disclosed in following patent documentation 1.Above-mentioned compound particle has plastics nucleome and by chemical bond, is adsorbed in the non-conductive inorganic particulate of this plastics nucleome.In the electroconductive particle that patent documentation 1 is recorded, the above-mentioned coat of metal has the surface that forms jut.In addition, above-mentioned non-conductive inorganic particulate is harder than the above-mentioned coat of metal.
In following patent documentation 2, disclose a kind of electroconductive particle, on the basis of its electroconductive particle of recording at patent documentation 1, further possessed the second non-conductive inorganic particulate that is adsorbed in metal coating surface.
Prior art document
Patent documentation
Patent documentation 1:(Japan) JP 2011-29179 communique
Patent documentation 2:(Japan) JP 2011-29180 communique
Summary of the invention
The problem that invention will solve
In the case of using between the electroconductive particle connecting electrode of recording in patent documentation 1,2, can reduce to a certain extent interelectrode contact resistance.But, even if use the electroconductive particle of recording in patent documentation 1,2, sometimes can not fully reduce interelectrode contact resistance.
In addition, in order to reduce interelectrode contact resistance, expect to develop the new electroconductive particle different from the electroconductive particle of recording in patent documentation 1,2.
The object of the present invention is to provide and a kind ofly when for interelectrode connection, can reduce the electroconductive particle of interelectrode contact resistance and use electric conducting material and the syndeton body of this electroconductive particle.The method of dealing with problems
According to wide in range aspect of the present invention, a kind of electroconductive particle can be provided, it possesses: basis material particle, be disposed on the surface of this basis material particle and have the conductive layer of multiple projections and imbed the multiple inorganic particulates in this conductive layer at outer surface, inner side in the described projection of the outer surface of described conductive layer disposes described inorganic particulate, described at least a portion in described multiple inorganic particulates inorganic particulate not with the Surface Contact of described basis material particle.
In certain particular aspects of electroconductive particle of the present invention, in the inner side of 1 described projection of the outer surface of described conductive layer, dispose multiple described inorganic particulates.
In another particular aspects of electroconductive particle of the present invention, in total number of described multiple inorganic particulates more than 20% not with the Surface Contact of described basis material particle.
In other particular aspects of electroconductive particle of the present invention, the distance not and between the inorganic particulate of the Surface Contact of described basis material particle and described basis material particle is more than 5nm.
In another particular aspects of electroconductive particle of the present invention, this electroconductive particle further possesses multiple core materials of imbedding in described conductive layer.
In another particular aspects of electroconductive particle of the present invention, inner side in the described projection of the outer surface of described conductive layer disposes described core material, in 1 described projection of the outer surface of described conductive layer be disposed between the described core material of this projection inner side and dispose described inorganic particulate.
In another other particular aspects of electroconductive particle of the present invention, multiple described inorganic particulates contact with described core material.
In other particular aspects of electroconductive particle of the present invention, on the surface of described core material, be attached with described inorganic particulate, by described core material and described inorganic particulate, form complex.
In another other particular aspects of electroconductive particle of the present invention, described core material is metallic.
In another particular aspects of electroconductive particle of the present invention, multiple described inorganic particulates are at the skewness of inner surface side and the outer surface side of described conductive layer, its outside the amount of face side higher than the amount in inner surface side.
In other particular aspects of electroconductive particle of the present invention, this electroconductive particle further possesses the surperficial megohmite insulant that is attached to described conductive layer.
Electric conducting material of the present invention contains adhesive resin and above-mentioned electroconductive particle.
Syndeton body of the present invention possesses: the first connecting object parts, the second connecting object parts and connect the connecting portion of these first, second connecting object parts, described connecting portion is formed by above-mentioned electroconductive particle or formed by the electric conducting material that contains this electroconductive particle and adhesive resin.
The effect of invention
Electroconductive particle of the present invention possesses: basis material particle, be disposed on the surface of this basis material particle and have the conductive layer of multiple projections and imbed the multiple inorganic particulates in this conductive layer at outer surface, inner side in the described projection of the outer surface of described conductive layer disposes described inorganic particulate, described at least a portion in described multiple inorganic particulate inorganic particulate not with the Surface Contact of described basis material particle, therefore, when electroconductive particle is used for to interelectrode connection, can reduce contact resistance.
Accompanying drawing explanation
Fig. 1 is the cutaway view that represents the electroconductive particle of first embodiment of the invention;
Fig. 2 is the cutaway view that represents the electroconductive particle of second embodiment of the invention;
Fig. 3 is the cutaway view that represents the electroconductive particle of third embodiment of the invention;
Fig. 4 is front section view, schematically shows the syndeton body that has used the electroconductive particle shown in Fig. 3.
Symbol description
1 ... electroconductive particle
2 ... basis material particle
3 ... conductive layer
3a ... projection
4 ... core material
5 ... inorganic particulate
6 ... megohmite insulant
11 ... electroconductive particle
12 ... conductive layer
12a ... projection
13 ... core material
14 ... inorganic particulate
21 ... electroconductive particle
22 ... conductive layer
22a ... projection
23 ... inorganic particulate
51 ... syndeton body
52 ... the first connecting object parts
52a ... upper surface
52b ... electrode
53 ... the second connecting object parts
53a ... lower surface
53b ... electrode
54 ... connecting portion
Embodiment
Below, the present invention is described in detail.
Electroconductive particle of the present invention possesses: basis material particle, be disposed on the surface of this basis material particle and have on the outer surface the conductive layer of multiple projections and imbed the multiple inorganic particulates in this conductive layer.
In electroconductive particle of the present invention, above-mentioned conductive layer has multiple projections on the outer surface.On the surface of the electrode being connected by electroconductive particle, be mostly formed with oxide film thereon.In addition, at the outer surface of above-mentioned conductive layer, be mostly formed with oxide film thereon.Above-mentioned conductive layer has multiple projections on the outer surface, thus, by carry out pressing after electroconductive particle is disposed between electrode, can utilize projection effectively to get rid of oxide film thereon.Thus, can make electrode effectively contact with electroconductive particle, can reduce interelectrode contact resistance.And then, utilize above-mentioned projection, can effectively get rid of adhesive resin, megohmite insulant between electroconductive particle and electrode.Therefore can improve interelectrode conducting reliability.
In addition, in electroconductive particle of the present invention, in the inner side of the above-mentioned projection of above-mentioned conductive layer outer surface, dispose above-mentioned inorganic particulate.In addition, the above-mentioned inorganic particulate of at least a portion in above-mentioned multiple inorganic particulate not with the Surface Contact of above-mentioned basis material particle.The above-mentioned inorganic particulate of at least a portion and above-mentioned basis material particle partition distance.With compared with the above-mentioned inorganic particulate of the Surface Contact of above-mentioned basis material particle, be not disposed at the position of the outer surface of more close conductive layer with the above-mentioned inorganic particulate of the Surface Contact of above-mentioned basis material particle.
Electroconductive particle of the present invention is by taking above-mentioned formation, particularly, by configuring above-mentioned inorganic particulate in the inner side of above-mentioned projection, and then due to the existence of the above-mentioned inorganic particulate not contacting with above-mentioned basis material particle surface, can effectively strengthen by above-mentioned inorganic particulate the hardness of the jut of electroconductive particle, reduce the interelectrode contact resistance being connected by electroconductive particle.For example, when carrying out interelectrode pressing, due to the existence of harder above-mentioned inorganic particulate, easily make electrode strongly press conductive layer, therefore, contact resistance reduces.In addition, thus while connecting, also may on electrode, form suitable impression between compression conductive particle is by electrode.It should be noted that, the impression forming on electrode is electroconductive particle extruding electrode and the recess of the electrode that produces.And then, in the case of by the electric conducting material (anisotropic conductive material etc.) that is dispersed with electroconductive particle in adhesive resin for interelectrode pressing, can effectively get rid of the adhesive resin between conductive layer and electrode.By effectively getting rid of adhesive resin, also can reduce interelectrode contact resistance.
In addition, in the present invention, can be near the outer surface side of conductive layer with the above-mentioned inorganic particulate of the Surface Contact of above-mentioned basis material particle.When inorganic particulate is during near the outer surface side of conductive layer, can more effectively improve the hardness of the jut of electroconductive particle, thereby effectively reduce interelectrode contact resistance.In addition, do not form chemical bond with above-mentioned basis material particle with the above-mentioned inorganic particulate of the Surface Contact of above-mentioned basis material particle.And, preferably do not form chemical bond with above-mentioned basis material particle with the above-mentioned inorganic particulate of the Surface Contact of above-mentioned basis material particle.By making inorganic particulate not form chemical bond with basis material particle, can be not to the surface of inorganic particulate or the surface of basis material particle import for making inorganic particulate and basis material particle form the functional group of chemical bond.So, without the new material of preparing for importing functional group, can unreally use to import the operation of functional group, therefore can improve the production efficiency of electroconductive particle.Preferred above-mentioned electroconductive particle contains the inorganic particulate that is not adsorbed in above-mentioned basis material particle by chemical bond.Preferred above-mentioned inorganic particulate is not adsorbed in above-mentioned basis material particle by chemical bond.
Preferred electroconductive particle of the present invention further possesses multiple core materials of imbedding in above-mentioned conductive layer.But electroconductive particle of the present invention is also also nonessential possesses core material.Utilize above-mentioned core material, can easily at the outer surface of conductive layer, form projection, and easily make the outer surface side of inorganic particulate near conductive layer.Inorganic particulate during near the outer surface side of conductive layer, can effectively improve the hardness of the jut of electroconductive particle, thereby effectively reduce interelectrode contact resistance.
Preferably in the inner side of 1 above-mentioned projection of the outer surface of above-mentioned conductive layer, dispose multiple above-mentioned inorganic particulates, preferred disposition has 5 above above-mentioned inorganic particulates.Further, preferably in the inner side of the above-mentioned projection of the outer surface of above-mentioned conductive layer, dispose above-mentioned core material, and in 1 above-mentioned projection of the outer surface of above-mentioned conductive layer be disposed between the above-mentioned core material of this projection inner side and dispose above-mentioned inorganic particulate, more preferably dispose multiple above-mentioned inorganic particulates, preferred disposition has 5 above above-mentioned inorganic particulates.In these cases, the hardness of the jut of above-mentioned electroconductive particle uprises effectively.Therefore, when carrying out interelectrode pressing, owing to being disposed at the existence of above-mentioned inorganic particulate of projection inner side, can make electrode more strongly press conductive layer, therefore can effectively reduce interelectrode contact resistance.
Preferably multiple above-mentioned inorganic particulates exist unevenly with existing more than the mode of inner surface side of the outer surface side at above-mentioned conductive layer.In this case, when carrying out interelectrode pressing, utilize near the above-mentioned inorganic particulate of outer surface that is disposed at projection inner side and conductive layer, can make electrode more strongly press conductive layer, therefore can further reduce interelectrode contact resistance.
Preferably between the surface of the above-mentioned inorganic particulate of at least a portion and the surface of above-mentioned basis material particle, configure above-mentioned conductive layer.In addition, preferably between the surface of the above-mentioned inorganic particulate of at least a portion and the surface of above-mentioned basis material particle, configure above-mentioned conductive layer or above-mentioned core material, the above-mentioned core material of preferred disposition.Further, preferably between the surface of the inorganic particulate of more than 20% (preferably more than 50%) in total number of inorganic particulate and the surface of above-mentioned basis material particle, configure above-mentioned conductive layer or above-mentioned core material, the above-mentioned conductive layer of preferred disposition.Preferably the inorganic particulate of more than 20% (preferably more than 50%) in total number of inorganic particulate does not contact with above-mentioned basis material particle, preferably with above-mentioned basis material particle partition distance.In these cases, while carrying out interelectrode pressing, due to the existence of inorganic particulate, can more effectively make electrode strongly press conductive layer, therefore can further reduce interelectrode contact resistance.
In addition, preferred above-mentioned inorganic particulate is harder than above-mentioned conductive layer.In this case, while carrying out interelectrode pressing, due to the existence of inorganic particulate, can more effectively make electrode press conductive layer, therefore can further reduce interelectrode contact resistance.
Distance X not and between the inorganic particulate of the Surface Contact of above-mentioned basis material particle and above-mentioned basis material particle more preferably exceedes 5nm more than being preferably 5nm, more preferably more than 10nm, is preferably below 1 μ m, more preferably below 0.3 μ m.It should be noted that, in the case of only not existing 1 with the inorganic particulate of the Surface Contact of above-mentioned basis material particle, above-mentioned distance X represents the beeline between 1 inorganic particulate and above-mentioned basis material particle.In the case of not with the inorganic particulate of the Surface Contact of above-mentioned basis material particle exist multiple, above-mentioned distance X can be obtained by the mean value of measuring respectively the beeline between 1 inorganic particulate and above-mentioned basis material particle and calculating this beeline.In the case of not existing more than 10 with the inorganic particulate of the Surface Contact of above-mentioned basis material particle, above-mentioned distance X is preferably obtained by the mean value of measuring the beeline between whole inorganic particulates and above-mentioned basis material particle and calculating whole beelines, but also can obtain by the beeline between 10 inorganic particulates of 10 Site Determinations and above-mentioned basis material particle respectively the mean value that calculates the beeline at 10 positions.Above-mentioned distance X can be below 9/10 of conductive layer thickness, can be also below 4/5, can be also below 1/2, can be also below 1/3.
From more effectively get rid of electrode and electroconductive particle surface oxide film thereon, further improve the viewpoint of interelectrode conducting reliability, in total number 100% of above-mentioned core material, beeline between above-mentioned inorganic particulate and above-mentioned basis material particle is that the number ratio of inorganic particulate more than 5nm is preferably more than 50%, more preferably exceedes below 80% and 100%.Also can be in above-mentioned whole inorganic particulates, more than the beeline between above-mentioned inorganic particulate and above-mentioned basis material particle is 5nm.In total number 100% of above-mentioned inorganic particulate, the beeline between above-mentioned inorganic particulate and above-mentioned basis material particle is that the number ratio of inorganic particulate more than 10nm is preferably more than 50%, more preferably exceedes below 80% and 100%.Also can be in above-mentioned whole inorganic particulates, more than the beeline between above-mentioned inorganic particulate and above-mentioned basis material particle is 10nm.
Beeline between above-mentioned inorganic particulate and above-mentioned basis material particle can obtain image by the section at multiple positions of shooting electroconductive particle, by gained image, makes stereo-picture, and uses the stereo-picture obtaining to measure exactly.The shooting of above-mentioned section can be used focused ion beam scanning electron microscopy (FIBSEM) etc. to carry out.For example, use focused ion beam, make the cut film of electroconductive particle, and utilize sem observation section.By this operation being repeated hundreds of times and carrying out image analysis, can obtain the stereo-picture of particle.
About the details of said determination method, by cutting gained electroconductive particle carry out profile view and examine, can measure the distance between surface and multiple inorganic particulates of basis material particle.Distance between the surface of basis material particle and the surface of core material can obtain image by the section at multiple positions of taking electroconductive particle, by gained image, makes stereo-picture, and measures with the stereo-picture obtaining.The shooting of above-mentioned section can be used focused ion beam scanning electron microscopy (FIBSEM) the device name Helious NanoLab.650 that Japanese FEI Co. manufactures etc. to carry out.Use focused ion beam, make the cut film of electroconductive particle, and utilize sem observation section.By this operation being repeated 200 times and carrying out image analysis, can obtain the stereo-picture of particle.By stereo-picture, can obtain the distance between basis material particle surface and surface of inorganic particles, and obtain in total number 100 % by weight of inorganic particulate, the distance between the surface of basis material particle and the surface of inorganic particulate meets the ratio (%) of the number of the inorganic particulate of particular value.
Below, the details of electroconductive particle, electric conducting material and syndeton body are described.
(electroconductive particle)
Fig. 1 is the cutaway view that represents the electroconductive particle of first embodiment of the invention.Fig. 2 is the cutaway view that represents the electroconductive particle of second embodiment of the invention.Fig. 3 is the cutaway view that represents the electroconductive particle of third embodiment of the invention.
First, the electroconductive particle 1 shown in Fig. 3 is described.Electroconductive particle 1 shown in Fig. 3 possesses: basis material particle 2, conductive layer 3, multiple core material 4, multiple inorganic particulate 5 and megohmite insulant 6.Conductive layer 3 is disposed on the surface of basis material particle 2.Conductive layer 3 has multiple projection 3a at outer surface.Multiple core materials 4 are disposed on the surface of basis material particle 2, and imbed in conductive layer 3.Core material 4 is disposed at the inner side of projection 3a.Multiple inorganic particulates 5 are disposed on the surface of basis material particle 2, and imbed in conductive layer 3.Megohmite insulant 6 is disposed on the surface of conductive layer 3.
Megohmite insulant 6 is insulating particle.Megohmite insulant 6 is formed by the material with insulating properties.Electroconductive particle also not necessarily possesses megohmite insulant.In addition, as megohmite insulant, the insulating barrier that electroconductive particle also can possess the outer surface of coated with conductive layer replaces insulating particle.
In electroconductive particle 1, in the inner side of 1 projection 3a of conductive layer 3 outer surfaces, dispose multiple inorganic particulates 5.At 1 projection 3a of conductive layer 3 outer surfaces be disposed between the core material 4 of this projection 3a inner side and dispose multiple inorganic particulates 5.In addition, between the surface of at least a portion inorganic particulate 5 and the surface of basis material particle 2, dispose conductive layer 3 or core material 4.At least a portion inorganic particulate 5 does not contact with basis material particle 2, but with basis material particle 2 partition distance.In addition, multiple inorganic particulates 5 contact with core material 4.Multiple inorganic particulates 5 are attached to core material 4.Multiple inorganic particulates 5 do not form chemical bond with basis material particle 2, by chemical bond, are not adsorbed in basis material particle 2.The inorganic particulate 5 not contacting with basis material particle 2 does not form chemical bond with basis material particle 2.Inorganic particulate 5 is harder than conductive layer 3.The Mohs' hardness of inorganic particulate 5 is higher than the Mohs' hardness of conductive layer 3.
In electroconductive particle 1, at least a portion inorganic particulate 5 contacts with basis material particle 2.Electroconductive particle 1 comprises the inorganic particulate 5 contacting with basis material particle 2.The inorganic particulate 5 contacting with basis material particle 2 does not form chemical bond with basis material particle 2.Electroconductive particle 1 also comprises the inorganic particulate 5 not contacting with basis material particle 2.In addition, in electroconductive particle 1, basis material particle 2 does not contact with core material 4.Basis material particle 2 also can contact with core material 4.
Electroconductive particle 11 shown in Fig. 2 possesses: basis material particle 2, conductive layer 12, multiple core material 13, multiple inorganic particulate 14 and insulating particle 6.Conductive layer 12 is disposed on the surface of basis material particle 2.Conductive layer 12 has multiple projection 12a at outer surface.Multiple core materials 13 are imbedded in conductive layer 12.Core material 13 is disposed at the inner side of projection 12a.Multiple inorganic particulates 14 are imbedded in conductive layer 12.Insulating particle 6 is disposed on the surface of conductive layer 12.
In electroconductive particle 11, core material 13 does not contact with inorganic particulate 14.Like this, core material 13 also can not contact with inorganic particulate 14.
In electroconductive particle 11, in the inner side of 1 projection 12a of conductive layer 12 outer surfaces, dispose multiple inorganic particulates 14.Inorganic particulate 14 does not contact with basis material particle 2.In addition, in electroconductive particle 11, multiple inorganic particulates 14 exist unevenly with existing more than the mode of inner surface side of the outer surface side at conductive layer 12.Its result, can utilize inorganic particulate 14 and effectively improve the hardness of the projection 12a part of electroconductive particle 11.Therefore,, by using electroconductive particle 11, interelectrode contact resistance further reduces.
In electroconductive particle 11, compared with the region of the thickness 1/2 of the inner surface side of conductive layer 12, multiple inorganic particulates 14 are present in the region of the thickness 1/2 of the outer surface of conductive layer 12 more.It should be noted that, in electroconductive particle 21 described later, compared with the region of the thickness 1/2 of the inner surface side of conductive layer 22, multiple inorganic particulates 23 are present in the region of the thickness 1/2 of the outer surface of conductive layer 22 more.For example, in total number 100% of multiple inorganic particulates 14,23, exceed 50%, preferably more than 60%, more preferably more than 70% inorganic particulate 14,23 is present in the region of thickness 1/2 of the outer surface side of conductive layer 12,22.It should be noted that, multiple inorganic particulates the 14, the 23rd, are present in the region of thickness 1/2 of the inner surface side of conductive layer 12,22 or are present in the region of thickness 1/2 of the outer surface side of conductive layer 12,22, can judge take the central point of inorganic particulate 14,23 as benchmark.
In addition, in electroconductive particle 11, numerous inorganic particulates 14 does not contact, does not adhere to core material 13.Like this, inorganic particulate also not necessarily contacts with core material.
Electroconductive particle 21 shown in Fig. 1 possesses: basis material particle 2, conductive layer 22, multiple inorganic particulate 23 and insulating particle 6.Conductive layer 22 is disposed on the surface of basis material particle 2.Conductive layer 22 has multiple projection 22a at outer surface.Multiple inorganic particulates 23 are imbedded in conductive layer 22.Insulating particle 6 is disposed on the surface of conductive layer 22.Electroconductive particle 21 does not possess core material.Like this, electroconductive particle also may not necessarily possess core material.
In electroconductive particle 21, in the inner side of 1 projection 22a of conductive layer 22 outer surfaces, dispose multiple inorganic particulates 23.Inorganic particulate 23 does not contact with basis material particle 2.In addition, in electroconductive particle 21, the same with electroconductive particle 11, multiple inorganic particulates 23 exist unevenly with existing more than the mode of inner surface side of the outer surface side at conductive layer 22.Its result, can utilize inorganic particulate 23 and effectively improve the hardness of the jut of electroconductive particle 21.Therefore,, by using electroconductive particle 21, interelectrode contact resistance further reduces.
In electroconductive particle 1,11,21, preferably electroconductive particle 21.The comparison of electroconductive particle 21 is easy.
[basis material particle]
As above-mentioned basis material particle, can enumerate: resin particle, the inorganic particulate except metal, organic inorganic hybridization particle and metallic etc.Above-mentioned basis material particle is preferably the basis material particle except metallic, more preferably resin particle, the inorganic particulate except metal or organic inorganic hybridization particle.
Above-mentioned basis material particle is preferably the resin particle being formed by resin.While stating in the use between electroconductive particle connecting electrode, after above-mentioned electroconductive particle is disposed between electrode, carry out pressing, make thus above-mentioned electroconductive particle compression.If basis material particle is resin particle,, when carrying out above-mentioned pressing, above-mentioned electroconductive particle is easily deformable, and it is large that the contact area of electroconductive particle and electrode becomes.Therefore, interelectrode conducting reliability uprises.
As the resin that is used to form above-mentioned resin particle, can preferably use various organic substances.As the resin that is used to form above-mentioned resin particle, for example can enumerate: the vistanexes such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, Vingon, polypropylene, polyisobutene, polybutadiene, the acrylic resin such as polymethyl methacrylate, polymethyl acrylate, polyalkylene terephthalates, Merlon, polyamide, phenol formaldehyde resin, melamine resin, benzoguanamin formaldehyde resin, urea-formaldehyde resin, phenolic resins, melmac, benzoguanamine resin, Lauxite, epoxy resin, unsaturated polyester resin, saturated polyester resin, polysulfones, polyphenylene oxide, polyacetals, polyimides, polyamidoimide, polyether-ether-ketone, polyether sulfone, and the polymer that obtains through polymerization of the various polymerizable monomers that there is ethylenically unsaturated group by one or more etc.Owing to can designing and synthesize the resin particle of the physical property arbitrarily with when compression that is suitable for electric conducting material, and can easily the hardness of basis material particle be controlled to suitable scope, therefore the resin that, is used to form above-mentioned resin particle is preferably the polymer that the polymerizable monomer that has multiple ethylenically unsaturated groups by one or more is polymerized.
In the case of making the monomer with ethylenically unsaturated group carry out polymerization and obtain above-mentioned resin particle, as the above-mentioned monomer with ethylenically unsaturated group, can enumerate the monomer of non-crosslinked and the monomer of bridging property.
As the monomer of above-mentioned non-crosslinked, for example, can enumerate: the styrene monomers such as styrene, AMS; The carboxyl group-containing monomers such as (methyl) acrylic acid, maleic acid, maleic anhydride; (methyl) alkyl-acrylates such as (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) 2-EHA, (methyl) lauryl acrylate, (methyl) aliphatic acrylate, (methyl) stearyl acrylate ester, (methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate; (methyl) esters of acrylic acid that (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid glyceride, polyoxyethylene (methyl) acrylate, (methyl) glycidyl acrylate etc. contain oxygen atom; (methyl) acrylonitrile etc. are containing nitrile monomer; The vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether; The vinyl acetate classes such as vinyl acetate, vinyl butyrate, vinyl laurate, stearic acid vinyl ester; The unsaturated hydrocarbons such as ethene, propylene, isoprene, butadiene; The halogen containing monomers such as (methyl) acrylic acid trifluoro methyl esters, (methyl) acrylic acid five fluorine ethyl esters, vinyl chloride, PVF, chlorostyrene etc.
As the monomer of above-mentioned bridging property, for example can enumerate: tetramethylol methane four (methyl) acrylate, tetramethylol methane three (methyl) acrylate, tetramethylol methane two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, dipentaerythritol six (methyl) acrylate, dipentaerythritol five (methyl) acrylate, glycerine three (methyl) acrylate, glycerine two (methyl) acrylate, (gathering) ethylene glycol bisthioglycolate (methyl) acrylate, (gathering) propylene glycol two (methyl) acrylate, (gathering) tetramethylene two (methyl) acrylate, 1, multifunctional (methyl) esters of acrylic acids such as 4-butanediol two (methyl) acrylate, (different) triallyl cyanurate, trimellitic acid triallyl, divinylbenzene, dially phthalate, diallyl acrylamide, diallyl ether, γ-(methyl) acryloxy propyl trimethoxy silicane, trimethoxysilyl styrene, vinyltrimethoxy silane etc. contain silane monomer etc.
By utilizing known method to make the above-mentioned polymerizable monomer polymerization with ethylenically unsaturated group, can obtain above-mentioned resin particle.As the method, for example, can enumerate and under the existence of radical polymerization initiator, carry out the method for suspension polymerisation and use noncrosslinking kind of particle to make monomer swell together with radical polymerization initiator and method of polymerization etc.
Above-mentioned basis material particle is in the situation of inorganic particulate except metallic or organic inorganic hybridization particle, as the inorganic matter that is used to form above-mentioned basis material particle, can enumerate silicon dioxide and carbon black etc.As the particle being formed by above-mentioned silicon dioxide, be not particularly limited, for example can enumerate by the silicon compound with 2 above water-disintegrable alkoxyls is hydrolyzed and is formed after cross-linking polymer particle, fire as required and the particle that obtains.As above-mentioned organic inorganic hybridization particle, for example, can enumerate organic inorganic hybridization particle being formed by the alkoxysilyl polymer being cross-linked and acrylic resin etc.
In the situation that above-mentioned basis material particle is metallic, as the metal that is used to form this metallic, can enumerate silver, copper, nickel, silicon, gold and titanium etc., still, preferred substrate material particle is not metallic.
More than the particle diameter of above-mentioned basis material particle is preferably 0.1 μ m, more preferably more than 0.5 μ m, more preferably more than 1 μ m, more than being more preferably 1.5 μ m, more than being particularly preferably 2 μ m, be preferably below 1000 μ m, more preferably below 500 μ m, more preferably below 300 μ m, be more preferably below 50 μ m, further be preferably below 30 μ m, be particularly preferably below 5 μ m, most preferably be below 3 μ m.If the particle diameter of basis material particle is more than above-mentioned lower limit, the contact area of electroconductive particle and electrode becomes large, therefore, can further improve interelectrode conducting reliability, further reduces the interelectrode contact resistance connecting via electroconductive particle.In addition, by electroless plating, at basis material particle surface, forming during conductive layer, difficult cohesion, is difficult for forming the electroconductive particle of cohesion.If particle diameter is below the above-mentioned upper limit, electroconductive particle is easily fully compressed, and interelectrode contact resistance further reduces, and can further dwindle interelectrode interval.With regard to the particle diameter of above-mentioned basis material particle, at basis material particle, for just spherical in the situation that, represent diameter, at basis material particle, be not just spherical in the situation that, represent maximum gauge.
More than the particle diameter of above-mentioned basis material particle is particularly preferably 0.1 μ m and below 5 μ m.The particle diameter of above-mentioned basis material particle in the scope of 0.1～5 μ m time, can dwindle interelectrode interval, even and increase the thickness of conductive layer, also can obtain less electroconductive particle.Even if also can obtain the viewpoint of less electroconductive particle when increasing the thickness of conductive layer from can further dwindling interelectrode interval, more than the particle diameter of above-mentioned basis material particle is preferably 0.5 μ m, more preferably more than 2 μ m, be preferably below 3 μ m.
[conductive layer]
The metal that is used to form above-mentioned conductive layer is not particularly limited.And, at electroconductive particle, be that the metallic of entirety for conductive layer, the metal that is used to form this metallic is not particularly limited.As this metal, for example, can enumerate: gold, silver, copper, palladium, platinum, zinc, iron, tin, lead, aluminium, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, thallium, germanium, cadmium, silicon, tungsten, molybdenum and their alloy etc.In addition, as above-mentioned metal, can enumerate: tin-doped indium oxide (ITO) and scolding tin etc.Wherein, owing to can further reducing interelectrode contact resistance, therefore, preferably contain alloy, nickel, palladium, copper or the gold of tin, more preferably nickel or palladium.The metal that forms above-mentioned conductive layer preferably contains nickel.Above-mentioned conductive layer preferably contains at least a kind that is selected from nickel, tungsten, molybdenum, palladium, phosphorus and boron, more preferably contains nickel and contains phosphorus or boron.The material that forms above-mentioned conductive layer can be also the alloy that contains phosphorus and boron etc.In above-mentioned conductive layer, nickel and tungsten or molybdenum also can form alloy.
In the situation that above-mentioned conductive layer contains phosphorus or boron, in above-mentioned conductive layer 100 % by weight, preferably the total content of phosphorus and boron is below 4 % by weight.If the total content of phosphorus and boron is below the above-mentioned upper limit, the content of the metal such as nickel relatively increases, and therefore, interelectrode contact resistance further reduces.In above-mentioned conductive layer 100 % by weight, preferably the total content of phosphorus and boron is more than 0.1 % by weight, more preferably more than 0.5 % by weight.
Above-mentioned conductive layer can form by 1 layer, also can be formed by multilayer.That is, conductive layer can be individual layer, also can have two-layer above stepped construction.In the situation that conductive layer is formed by multilayer, preferably outermost layer is gold layer, nickel dam, palladium layer, copper layer or contains tin and the alloy-layer of silver, and more preferably gold layer or palladium layer, is particularly preferably gold layer.In the situation that outermost layer is these preferred conductive layers, interelectrode contact resistance further reduces.In addition, in the situation that outermost layer is gold layer, corrosion resistance further improves.
The method that forms conductive layer on the surface of above-mentioned basis material particle is not particularly limited.As forming the method for conductive layer, for example, can enumerate: utilize electroless plating method, utilize electric plating method, utilize the method for physical vapor deposition and will contain metal dust or contain metal dust and the thickener of adhesive is coated on the method etc. of basis material particle surface.Wherein, because the formation of conductive layer is simple, therefore, preferably utilize the method for electroless plating.As the above-mentioned method of utilizing physical vapor deposition, can enumerate: the methods such as vacuum evaporation, ion plating and ion sputtering.
More than the average grain diameter of above-mentioned electroconductive particle is preferably 0.11 μ m, more preferably more than 0.5 μ m, more preferably more than 0.51 μ m, more than being particularly preferably 1 μ m, be preferably below 100 μ m, more preferably, below 20 μ m, more preferably, below 5.6 μ m, be particularly preferably below 3.6 μ m.If the average grain diameter of electroconductive particle is more than above-mentioned lower limit and below the above-mentioned upper limit, in the situation that using between electroconductive particle connecting electrode, can fully increase the contact area between electroconductive particle and electrode, and when forming conductive layer, be difficult for forming the electroconductive particle of cohesion.In addition, the interelectrode interval connecting via electroconductive particle can not become excessive, and conductive layer is difficult for the sur-face peeling from basis material particle.
" average grain diameter " of above-mentioned electroconductive particle represents number average bead diameter.The average grain diameter of electroconductive particle can be by with electron microscope or any 50 electroconductive particles of observation by light microscope and calculate mean value and try to achieve.
More than the thickness of above-mentioned conductive layer is preferably 0.005 μ m, more preferably more than 0.01 μ m, be preferably below 1 μ m, more preferably below 0.3 μ m.If to be above-mentioned lower limit above and below the above-mentioned upper limit, can obtain sufficient conductivity for the thickness of conductive layer, and electroconductive particle can not become really up to the mark, and while connecting between by electrode, electroconductive particle can be out of shape fully.
In the situation that above-mentioned conductive layer is formed by multilayer, the thickness of outermost conductive layer, more than particularly when outermost layer is gold layer, the thickness of gold layer is preferably 0.001 μ m, more preferably more than 0.01 μ m, be preferably below 0.5 μ m, more preferably below 0.1 μ m.If the thickness of above-mentioned outermost conductive layer is more than above-mentioned lower limit and below the above-mentioned upper limit, can make the evenly coated of outermost conductive layer, corrosion resistance can be fully improved, and interelectrode contact resistance can be fully reduced.
The thickness of above-mentioned conductive layer can be by being used for example transmission electron microscope (TEM) to observe to measure to the section of electroconductive particle.
The projection of the above-mentioned conductive layer outer surface of each above-mentioned electroconductive particle is preferably more than 3, more preferably more than 5.The upper limit of above-mentioned projection quantity is not particularly limited.The upper limit of projection quantity can be considered the average grain diameter of electroconductive particle etc. and suitably select.
More than the average height of multiple above-mentioned projections is preferably 0.001 μ m, more preferably more than 0.05 μ m, be preferably below 0.9 μ m, more preferably below 0.2 μ m.If the average height of above-mentioned projection is more than above-mentioned lower limit and below the above-mentioned upper limit, can effectively reduce interelectrode contact resistance.
[core material]
By above-mentioned core material is embedded in above-mentioned conductive layer, can easily make above-mentioned conductive layer there are multiple projections at outer surface.
As the method that forms above-mentioned projection, can enumerate: core material is attached to behind the surface of basis material particle, by electroless plating, form the method for conductive layer; And forming after conductive layer on the surface of basis material particle by electroless plating, core material is adhered to, and then by electroless plating, form method of conductive layer etc.
As the method that configures core material on the surface at above-mentioned basis material particle, for example, can enumerate: to the conductive material that is added to core material in the dispersion liquid of basis material particle, make core material by for example Van der Waals force, gather and be attached to the surperficial method of basis material particle or metallic; And add core material to having added in the container of basis material particle or metallic, by the mechanism of the generations such as container rotation, make core material be attached to surperficial method of basis material particle or metallic etc.Wherein, owing to being easy to control the amount of accompanying core material, therefore, preferably making core material gather and be attached to basis material particle in dispersion liquid or the surperficial method of metallic.
As the material that forms above-mentioned core material, can enumerate conductive material and non-conductive material.As above-mentioned conductive material, for example, 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-conductive material, can enumerate: silicon dioxide, aluminium oxide and zirconia etc.Wherein, owing to can improving conductivity and then can effectively reducing contact resistance, therefore, preferable alloy.Above-mentioned core material is preferably metallic.
As above-mentioned metal, for example, can enumerate: the alloy that the metals such as gold, silver, copper, platinum, zinc, iron, lead, tin, aluminium, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, germanium and cadmium and tin-lead alloy, tin-copper alloy, tin-silver alloy, tin-lead-silver alloy and tungsten carbide etc. are formed by two or more metals etc.Wherein, preferred nickel, copper, silver or golden.The metal of above-mentioned formation core material can be identical with the metal of above-mentioned formation conductive layer, also can be different.The metal of above-mentioned formation core material preferably comprises the metal of above-mentioned formation conductive layer.The metal of above-mentioned formation core material preferably comprises nickel.The metal of above-mentioned formation core material preferably comprises nickel.
The shape of above-mentioned core material is not particularly limited.The shape of core material is preferably bulk.As core material, for example, can enumerate: emboliform, multiple fine particle condense the cohesion piece that forms and unbodied etc.Preferred above-mentioned core material is particle shape, and above-mentioned core material is core particle.
More than the average diameter (average grain diameter) of above-mentioned core material is preferably 0.001 μ m, more preferably more than 0.05 μ m, be preferably below 0.9 μ m, more preferably below 0.2 μ m.If the average diameter of above-mentioned core material is more than above-mentioned lower limit and below the above-mentioned upper limit, can effectively reduce interelectrode contact resistance.
" average diameter (average grain diameter) " of above-mentioned core material represents number average diameter (number average bead diameter).The average diameter of core material can be by with electron microscope or any 50 core materials of observation by light microscope and calculate its mean value and try to achieve.
[inorganic particulate]
Preferably imbed above-mentioned inorganic particulate in above-mentioned conductive layer harder than above-mentioned conductive layer.In this case, due to the existence of inorganic particulate, can make the further hardening of hardness of the jut of electroconductive particle, thereby can reduce the interelectrode contact resistance being connected by electroconductive particle.
As above-mentioned inorganic particulate, can enumerate: silicon dioxide (silicon dioxide, Mohs' hardness 6～7), zirconia (Mohs' hardness 8～9), aluminium oxide (Mohs' hardness 9), tungsten carbide (Mohs' hardness 9) and diamond (Mohs' hardness 10) etc.Above-mentioned inorganic particulate is preferably silicon dioxide, zirconia, aluminium oxide, tungsten carbide or diamond, is also preferably silicon dioxide, zirconia, aluminium oxide or diamond.The Mohs' hardness of above-mentioned inorganic particulate is preferably more than 5, more preferably more than 6.The Mohs' hardness of preferred above-mentioned inorganic particulate is greater than the Mohs' hardness of above-mentioned conductive layer.The absolute value of the difference of the Mohs' hardness of above-mentioned inorganic particulate and the Mohs' hardness of above-mentioned conductive layer is preferably more than 0.1, more preferably more than 0.2, more preferably more than 0.5, is particularly preferably more than 1.In addition, in the situation that conductive layer is formed by multilayer, when inorganic particulate is all hard than the whole metals that form multiple layers, can more effectively give play to the reduction effect of contact resistance.
Multiple above-mentioned inorganic particulates also can contact with above-mentioned core material.Above-mentioned inorganic particulate also can be attached to the surface of above-mentioned core material.Also can use surface attachment to have the above-mentioned core material of above-mentioned inorganic particulate, thereby on the surface of above-mentioned basis material particle, configure above-mentioned core material and above-mentioned inorganic particulate.
More than the average grain diameter of above-mentioned inorganic particulate is preferably 0.0001 μ m, more preferably more than 0.005 μ m, be preferably below 0.5 μ m, more preferably below 0.1 μ m.If the average grain diameter of above-mentioned inorganic particulate is more than above-mentioned lower limit and below the above-mentioned upper limit, can effectively reduce interelectrode contact resistance.
" average grain diameter " of above-mentioned inorganic particulate represents number average bead diameter.The average grain diameter of inorganic particulate can be tried to achieve by utilizing any 50 inorganic particulates of electron microscope or observation by light microscope and calculating mean value.
In the electroconductive particle 1 shown in Fig. 3, multiple inorganic particulates 5 contact with core material 4.In addition, inorganic particulate 5 is optionally disposed at the inner side of the projection 3a of conductive layer 3 outer surfaces.Preferably compared with the inner side of the unpolarized outer surface part of above-mentioned conductive layer, multiple above-mentioned inorganic particulates exist unevenly in the mode of inner side of the projection that is present in more above-mentioned conductive layer outer surface.Like this, as the method that inorganic particulate is optionally disposed to projection inner side, can enumerate the method that makes inorganic particulate be attached to core material, particularly, can enumerate following method,, inorganic particulate is attached to behind the surface of core material, the core material that is attached with inorganic particulate is configured on the surface of basis material particle, then, utilizes the coated basis material particle of conductive layer and the core material that is attached with inorganic particulate.Also can use the method method in addition.
Electroconductive particle 11,22 as shown in Fig. 2,1, preferably multiple above-mentioned inorganic particulates 14,23 exist unevenly with existing more than the mode of inner surface side of the outer surface side at above-mentioned conductive layer 12,22.As the method that makes in this wise inorganic particulate exist unevenly, can enumerate: form conductive layer by multiple layers, and make to contain in the conductive layer in outside than the method for more inorganic particulate in the conductive layer of inner side; And when forming conductive layer by electroless plating, than the initial stage of electroless plating, make method that contains more inorganic particulate in the electroless plating liquid of follow-up phase etc.Also can use these methods method in addition.
From effectively improve above-mentioned electroconductive particle jut hardness, further reduce the viewpoint of interelectrode contact resistance, preferably on the surface of above-mentioned core material, adhere to above-mentioned inorganic particulate, by above-mentioned core material and above-mentioned inorganic particulate, form complex.By prepare to be attached with the complex of inorganic particulate on the surface of above-mentioned core material, and when forming conductive layer, this complex is imbedded in conductive layer, can be obtained possessing the electroconductive particle of above-mentioned complex.By using above-mentioned complex, can be easily core material and inorganic particulate are imbedded in conductive layer and make at least a portion inorganic particulate in multiple inorganic particulates not with the Surface Contact of basis material particle.
With respect to above-mentioned core material, above-mentioned inorganic particulate can adhere to by chemical bonding, also can adhere to by mechanism or physical action.
More than the average diameter (average grain diameter) of above-mentioned complex is preferably 0.0012 μ m, more preferably more than 0.0502 μ m, be preferably below 1.9 μ m, more preferably below 1.2 μ m.If the average diameter of above-mentioned complex is more than above-mentioned lower limit and below the above-mentioned upper limit, can effectively reduce interelectrode contact resistance.
" average diameter (average grain diameter) " of above-mentioned complex represents number average bead diameter (number average bead diameter).The average diameter of above-mentioned complex can be tried to achieve by utilizing any 50 core materials of electron microscope or observation by light microscope and calculating mean value.
[megohmite insulant]
Electroconductive particle of the present invention preferably possesses the megohmite insulant being disposed on above-mentioned conductive layer surface.In this case, when electroconductive particle is used for to interelectrode connection, can prevent the interelectrode short circuit of adjacency.Particularly, when the contact of multiple electroconductive particles, owing to there is megohmite insulant between multiple electrodes, therefore can prevent between transversely adjacent electrode but not short circuit between upper/lower electrode.It should be noted that, when carrying out interelectrode connection, by utilizing two electrode pair electroconductive particles to pressurize, can easily get rid of the megohmite insulant between conductive layer and the electrode of electroconductive particle.Because electroconductive particle has multiple projections at the outer surface of conductive layer, therefore, can easily get rid of the megohmite insulant between conductive layer and the electrode of electroconductive particle.
When carrying out interelectrode pressing, can more easily get rid of above-mentioned megohmite insulant, therefore, above-mentioned megohmite insulant is preferably insulating particle.
As the material of above-mentioned megohmite insulant, be the concrete example of insulative resin, can enumerate cross-linking agent, thermosetting resin and the water-soluble resin etc. of TPO, (methyl) acrylate polymer, (methyl) acrylate copolymer, block polymer, thermoplastic resin, thermoplastic resin.
As said polyolefins class, can enumerate: polyethylene, vinyl-vinyl acetate copolymer and vinyl-acrylate copolymer etc.As above-mentioned (methyl) acrylate polymer, can enumerate: poly-(methyl) methyl acrylate, poly-(methyl) ethyl acrylate and poly-(methyl) butyl acrylate etc.As above-mentioned block polymer, can enumerate the hydrogenation products of polystyrene, copolymer in cinnamic acrylic ester, SB type styrene-butadiene block copolymer and SBS type styrene-butadiene block copolymer and these polymer etc.As above-mentioned thermoplastic resin, can enumerate polyvinyl and ethylenic copolymer etc.As above-mentioned thermosetting resin, can enumerate epoxy resin, phenolic resins and melmac etc.As above-mentioned water-soluble resin, can enumerate polyvinyl alcohol, polyacrylic acid, polyacrylamide, PVP, polyoxyethylene and methylcellulose etc.Wherein, be preferably water-soluble resin, more preferably polyvinyl alcohol.
As the method that configures megohmite insulant on the surface of above-mentioned conductive layer, can enumerate chemical method and physics or mechanical means etc.As above-mentioned chemical method, for example can enumerate: interfacial polymerization, the suspension polymerization under particle exists and emulsion polymerization etc.As above-mentioned physics or mechanical means, can enumerate spray drying process, hydridization method, electrostatic adherence method, spray-on process, infusion process and utilize method of vacuum evaporation etc.Wherein, because megohmite insulant is difficult for departing from, therefore preferably by chemical bond, make above-mentioned megohmite insulant be attached to the surperficial method of above-mentioned conductive layer.
The average diameter (average grain diameter of insulating particle) of above-mentioned megohmite insulant can be according to suitable selections such as the purposes of the particle diameter of electroconductive particle and electroconductive particle.More than the average diameter (average grain diameter of insulating particle) of above-mentioned megohmite insulant is preferably 0.005 μ m, more preferably more than 0.01 μ m, be preferably below 1 μ m, more preferably below 0.5 μ m.If the average diameter of megohmite insulant is more than above-mentioned lower limit, while making electroconductive particle be scattered in adhesive resin, between the conductive layer of multiple electroconductive particles, be difficult for coming in contact.If the average diameter of insulating properties particle (average grain diameter) is below the above-mentioned upper limit, while connecting, without excessively improving pressure in order to get rid of the megohmite insulant between electrode and electroconductive particle, do not need to be heated to high temperature between by electrode yet.
" average diameter (average grain diameter) " of above-mentioned megohmite insulant represents number average diameter (number average bead diameter).The average diameter of megohmite insulant can utilize particle size distribution device etc. to try to achieve.
(electric conducting material)
Electric conducting material of the present invention contains above-mentioned electroconductive particle and adhesive resin.Above-mentioned electroconductive particle is preferably scattered in adhesive resin and makes electric conducting material and use.Above-mentioned electric conducting material is preferably anisotropic conductive material.
Above-mentioned adhesive resin is not particularly limited.As above-mentioned adhesive resin, can use known insulative resin.
In above-mentioned electric conducting material, except above-mentioned electroconductive particle and above-mentioned adhesive resin, can also contain the various additives such as such as filler, extender, softening agent, plasticizer, polymerization catalyst, curing catalysts, colouring agent, antioxidant, heat stabilizer, light stabilizer, ultra-violet absorber, lubricant, antistatic agent and fire retardant.
The method that above-mentioned electroconductive particle is scattered in above-mentioned adhesive resin can be used existing known process for dispersing, is not particularly limited.As making above-mentioned electroconductive particle be scattered in the method in above-mentioned adhesive resin, for example, can enumerate: after in above-mentioned adhesive resin, carry out mixing so that the method for its dispersion with planet mixer etc.; Use homogenizer etc. that above-mentioned electroconductive particle is evenly dispersed in water or organic solvent, then make an addition in above-mentioned adhesive resin, carry out mixing so that the method for its dispersion with planet mixer etc.; And after above-mentioned adhesive resin water or organic solvent etc. are diluted, add electroconductive particle, with planet mixer etc., carry out mixing so that the method for its dispersion etc.
Electric conducting material of the present invention can be made into the uses such as electroconductive paste or conducting film.In the situation that electric conducting material of the present invention is conducting film, also can be on the conducting film that contains electroconductive particle stacked not containing the film of electroconductive particle.Above-mentioned electroconductive paste is preferably anisotropic conductive and sticks with paste.Above-mentioned conducting film is preferably anisotropic conductive film.
In above-mentioned electric conducting material 100 % by weight, more than the content of above-mentioned adhesive resin is preferably 10 % by weight, more preferably more than 30 % by weight, more preferably more than 50 % by weight, more than being particularly preferably 70 % by weight, be preferably below 99.99 % by weight, more preferably below 99.9 % by weight.If the content of above-mentioned adhesive resin is that more than above-mentioned lower limit and below the above-mentioned upper limit, electroconductive particle is disposed between electrode effectively, the connection reliability of the connecting object parts that connected by electric conducting material further improves.
In above-mentioned electric conducting material 100 % by weight, more than the content of above-mentioned electroconductive particle is preferably 0.01 % by weight, more preferably more than 0.1 % by weight, be preferably below 40 % by weight, more preferably below 20 % by weight, more preferably below 10 % by weight.If the content of above-mentioned electroconductive particle is that more than above-mentioned lower limit and below the above-mentioned upper limit, interelectrode conducting reliability further improves.
(syndeton body)
The electric conducting material that the electroconductive particle of the application of the invention or use contain this electroconductive particle and adhesive resin is connected connecting object parts, can obtain syndeton body.
Above-mentioned syndeton body possesses the first connecting object parts, the second connecting object parts and the connecting portion by first, second connecting object parts electrical connection, and this connecting portion is preferably the syndeton body being formed by electroconductive particle of the present invention or the syndeton body being formed by the electric conducting material that contains this electroconductive particle and adhesive resin (anisotropic conductive material etc.).In the situation that using electroconductive particle, connecting portion is originally as electroconductive particle.That is, first, second connecting object parts are connected by electroconductive particle.
Fig. 4 schematically shows the syndeton body of the electroconductive particle that has used an embodiment of the present invention with front section view.
Syndeton body 51 shown in Fig. 4 possesses the first connecting object parts 52, the second connecting object parts 53 and connects the connecting portion 54 of first, second connecting object parts 52,53.Connecting portion 54 is by being solidified to form the electric conducting material that contains electroconductive particle 1.To it should be noted that, in Fig. 4, in order illustrating conveniently, with sketch, to show electroconductive particle 1.Also can use the replacement electroconductive particles 1 such as electroconductive particle 11,21.
The first connecting object parts 52 have multiple electrode 52b at upper surface 52a (surface).The second connecting object parts 53 have multiple electrode 53b at lower surface 53a (surface).Electrode 52b and electrode 53b are electrically connected by one or more electroconductive particles 1.Thus, first, second connecting object parts 52,53 are electrically connected by electroconductive particle 1.
The manufacture method of above-mentioned syndeton body is not particularly limited.As an example of the manufacture method of syndeton body, can enumerate: between the first connecting object parts and the second connecting object parts, configure above-mentioned electric conducting material and obtain after duplexer, this duplexer is heated and the method for pressurizeing etc.
The pressure of above-mentioned pressurization is 9.8 × 10 4～4.9 × 10 6pa left and right.The temperature of above-mentioned heating is 120～220 ℃ of left and right.
As above-mentioned connecting object parts, specifically can enumerate: the electronic units such as circuit substrate such as the electronic units such as semiconductor chip, capacitor and diode and printed base plate, flexible printing substrate and glass substrate etc.Above-mentioned connecting object parts are preferably electronic unit.Above-mentioned electroconductive particle is preferred for the electrical connection of the electrode of electronic unit.
As the electrode that is arranged at above-mentioned connecting object parts, can enumerate: the metal electrodes such as gold electrode, nickel electrode, tin electrode, aluminium electrode, copper electrode, molybdenum electrode and tungsten electrode.In the situation that above-mentioned connecting object parts are flexible printing substrate, preferred above-mentioned electrode is gold electrode, nickel electrode, tin electrode or copper electrode.In the situation that above-mentioned connecting object parts are glass substrate, preferred above-mentioned electrode is aluminium electrode, copper electrode, molybdenum electrode or tungsten electrode.It should be noted that, in the situation that above-mentioned electrode is aluminium electrode, can be the electrode only being formed by aluminium, can be also the electrode forming at the stacked aluminium lamination in the surface of metal oxide layer.As the material of above-mentioned metal oxide layer, can enumerate doped with the indium oxide of 3 valency metallic elements and doped with zinc oxide of 3 valency metallic elements etc.As 3 above-mentioned valency metallic elements, can enumerate: Sn, Al and Ga etc.In addition, above-mentioned electrode is preferably ITO electrode, IZO electrode, AZO electrode, GZO electrode or ZnO electrode.These electrode surfaces are harder.In electroconductive particle of the present invention, because the hardness of jut is harder, therefore can make conductive layer effectively contact with harder electrode, thereby can effectively reduce interelectrode contact resistance.
Below, in conjunction with the embodiments and comparative example be described more specifically the present invention.The present invention is not only defined in following embodiment.
(embodiment 1)
(1) palladium adheres to operation
Preparing particle diameter is the divinyl benzene copolymer resin particle (ponding chemical industrial company system " Micropearl SP-203 ") of 3.0 μ m.
After using in aqueous slkali 100 weight portions that ultrasonic disperser is scattered in the above-mentioned resin particle of 10 weight portions to contain 5 % by weight palladium catalyst liquid, filtering solution, extracts resin particle thus.Then, resin particle is added in the dimethylamino borine 1 % by weight solution of 100 weight portions, make the surface active of resin particle.After the resin particle that surface is activated is fully washed, add 500 weight portions distilled water and make it disperse, thus, obtained being attached with the resin particle of palladium.
(2) process for electroless nickel plating operation
To being attached with the ion exchange water that adds 1000mL in the resin particle of palladium, use ultrasonic processor to make it abundant dispersion, obtain suspension.The nickel-plating liquid (pH6.5) of the natrium citricum of the nickelous sulfate that preparation contains 0.23mol/L, the sodium hypophosphite of 0.5mol/L and 0.5mol/L.When stirring above-mentioned suspension for 30 ℃, slowly drip above-mentioned nickel-plating liquid (pH6.5), carry out process for electroless nickel plating, formed the first nickel coating of thick 5nm.After the foaming of confirmation hydrogen stops, the alumina slurry (average grain diameter 50nm) that adds 1g also makes it to disperse after 10 minutes, has obtained being attached with the nickel plating particle 1 of inorganic particulate.
To being attached with the ion exchange water that adds 1000mL in the nickel plating particle 1 of inorganic particulate, use ultrasonic processor to make it abundant dispersion, obtained suspension.The nickel-plating liquid (pH8.5) of the natrium citricum of the nickelous sulfate that preparation contains 0.23mol/L, the sodium hypophosphite of 0.5mol/L and 0.5mol/L.When stirring above-mentioned suspension for 30 ℃, slowly drip above-mentioned nickel-plating liquid (pH8.5), be attached with the process for electroless nickel plating of the nickel plating particle 1 of inorganic particulate, formed the second nickel coating of thick 95nm.After the foaming of confirming hydrogen stops, filtering out particle and carried out washing, alcohol displacement, then carry out vacuumize, obtained the bossed electroconductive particle of surperficial tool at nickel coating.
It should be noted that, in the electroconductive particle obtaining, inorganic particulate is harder than conductive layer, and the Mohs' hardness of inorganic particulate is greater than the Mohs' hardness of conductive layer.In addition, in the electroconductive particle obtaining, 100% (more than 20%) in total number of multiple inorganic particulates is not with the Surface Contact of the above-mentioned resin particle as basis material particle but partition distance.
(embodiment 2)
Except alumina slurry (average grain diameter 50nm) is altered to zirconia slurry (average grain diameter 60nm), implement similarly to Example 1, obtained electroconductive particle.
It should be noted that, in the electroconductive particle obtaining, inorganic particulate is harder than conductive layer, and the Mohs' hardness of inorganic particulate is greater than the Mohs' hardness of conductive layer.In addition, in the electroconductive particle obtaining, 100% (more than 20%) in total number of multiple inorganic particulates is not with the Surface Contact of the above-mentioned resin particle as basis material particle but partition distance.
(embodiment 3)
Except alumina slurry (average grain diameter 50nm) is altered to silica slurry (average grain diameter 20nm), implement similarly to Example 1, obtained electroconductive particle.
It should be noted that, in the electroconductive particle obtaining, inorganic particulate is harder than conductive layer, and the Mohs' hardness of inorganic particulate is greater than the Mohs' hardness of conductive layer.In addition, in the electroconductive particle obtaining, 100% (more than 20%) in total number of multiple inorganic particulates is not with the Surface Contact of the above-mentioned resin particle as basis material particle but partition distance.
(embodiment 4)
(1) core material adheres to operation
The resin particle that is attached with palladium of having prepared to obtain in embodiment 1.This resin particle that is attached with palladium is stirred and within 3 minutes, makes it to disperse in the ion exchange water of 300mL, obtained dispersion liquid.Then, through 3 minutes, the metallic nickel particle slurry (average grain diameter 250nm) of 1g is added in above-mentioned dispersion liquid, obtained being attached with the resin particle of core material.
(2) process for electroless nickel plating operation
To being attached with the ion exchange water that adds 1000mL in the resin particle of core material, use ultrasonic processor to make it abundant dispersion, obtained suspension.The nickel-plating liquid (pH8.0) of the natrium citricum of the nickelous sulfate that preparation contains 0.25mol/L, the sodium hypophosphite of 0.25mol/L and 0.5mol/L.When stirring above-mentioned suspension for 30 ℃, slowly drip above-mentioned nickel-plating liquid (pH8.0), carry out the process for electroless nickel plating of the above-mentioned resin particle that is attached with core material, formed the first nickel coating of thick 5nm.After the foaming of confirming hydrogen stops, adding the alumina slurry (average grain diameter 50nm) of 1g and make it to disperse after 10 minutes, obtained being attached with the nickel plating particle 1 of inorganic particulate.
To being attached with the ion exchange water that adds 1000mL in the nickel plating particle 1 of inorganic particulate, use ultrasonic processor to make it abundant dispersion, obtained suspension.The nickel-plating liquid (pH8.0) of the natrium citricum of the nickelous sulfate that preparation contains 0.25mol/L, the sodium hypophosphite of 0.25mol/L and 0.5mol/L.When stirring above-mentioned suspension for 30 ℃, slowly drip above-mentioned nickel-plating liquid (pH8.0), be attached with the process for electroless nickel plating of the nickel plating particle 1 of inorganic particulate, formed the second nickel coating of thick 95nm.After the foaming of confirming hydrogen stops, filtering out particle and carried out washing, alcohol displacement, then carry out vacuumize, obtained the bossed electroconductive particle of outer surface tool at nickel coating.
It should be noted that, in the electroconductive particle obtaining, inorganic particulate is harder than conductive layer, and the Mohs' hardness of inorganic particulate is greater than the Mohs' hardness of conductive layer.In addition, in the electroconductive particle obtaining, 100% (more than 20%) in total number of multiple inorganic particulates is not with the Surface Contact of the above-mentioned resin particle as basis material particle but partition distance.
(comparative example 1)
(1) palladium adheres to operation
Having prepared particle diameter is the divinyl benzene copolymer resin particle (ponding chemical industrial company system " Micropearl SP-203 ") of 3.0 μ m.
After using in aqueous slkali 100 weight portions that ultrasonic disperser is scattered in the above-mentioned resin particle of 10 weight portions to contain 5 % by weight palladium catalyst liquid, filtering solution, extracts resin particle thus.Then, resin particle is added in the dimethylamino borine 1 % by weight solution of 100 weight portions, make the surface active of resin particle.After the resin particle that surface is activated is fully washed, add 500 weight portions distilled water and make it disperse, thus, obtained being attached with the resin particle of palladium.
(2) inorganic particulate adheres to operation
The resin particle that is attached with palladium stirred 3 minutes in the ion exchange water of 300mL and make it to disperse, having obtained dispersion liquid.Then, through 3 minutes, the alumina slurry of 1g (average grain diameter 50nm) is added in above-mentioned dispersion liquid, obtained being attached with the resin particle of inorganic particulate.In the resin particle that is attached with inorganic particulate obtaining, inorganic particulate all contacts with resin particle.
(3) process for electroless nickel plating operation
The nickel-plating liquid (pH8.0) of the natrium citricum of the nickelous sulfate that preparation contains 0.25mol/L, the sodium hypophosphite of 0.25mol/L and 0.5mol/L.The above-mentioned particle slurry liquid that is attached with inorganic particulate, when stirring for 60 ℃, is slowly dripped to above-mentioned nickel-plating liquid (pH8.0), carry out process for electroless nickel plating, formed the nickel coating of thick 100nm.After the foaming of confirming hydrogen stops, filtering out particle and carried out washing, alcohol displacement, then carry out vacuumize, obtained the bossed electroconductive particle of surperficial tool at nickel coating.
(embodiment 5)
(1) palladium adheres to operation
Preparing particle diameter is the divinyl benzene copolymer resin particle (ponding chemical industrial company system " Micropearl SP-203 ") of 3.0 μ m.
After using in aqueous slkali 100 weight portions that ultrasonic disperser is scattered in the above-mentioned resin particle of 10 weight portions to contain 5 % by weight palladium catalyst liquid, filtering solution, extracts resin particle thus.Then, resin particle is added in the dimethylamino borine 1 % by weight solution of 100 weight portions, make the surface active of resin particle.After the resin particle that surface is activated is fully washed, add 500 weight portions distilled water and make it disperse, thus, obtained the dispersion liquid that contains the resin particle that is attached with palladium.
(2) core material adheres to operation
Through 3 minutes, the metallic nickel particle slurry (average grain diameter 250nm) of 1g is added in aqueous dispersions, then add the alumina slurry (average grain diameter 50nm) of 1g and make it to disperse 10 minutes, having obtained being attached with the metallic nickel particle 1 of aluminium oxide.Then, metallic nickel particle 1 is added in the dispersion liquid that contains the resin particle that is attached with palladium, obtained the slurry that contains the particle that is attached with core material.
(3) process for electroless nickel plating operation
The nickel-plating liquid (pH8.0) of the natrium citricum of the nickelous sulfate that preparation contains 0.25mol/L, the sodium hypophosphite of 0.25mol/L and 0.5mol/L.The slurry that contains the above-mentioned particle that is attached with core material, when stirring for 60 ℃, is slowly added drop-wise to above-mentioned nickel-plating liquid (pH8.0) in above-mentioned slurry, carries out process for electroless nickel plating.After the foaming of confirming hydrogen stops, filtering out particle and carried out washing, alcohol displacement, then carry out vacuumize, obtained the bossed electroconductive particle of outer surface tool at the nickel coating of thick 100nm.
It should be noted that, in the electroconductive particle obtaining, inorganic particulate is harder than conductive layer, and the Mohs' hardness of inorganic particulate is greater than the Mohs' hardness of conductive layer.In addition, in the electroconductive particle obtaining, in total number of multiple inorganic particulates more than 20% not with the Surface Contact of the above-mentioned resin particle as basis material particle but partition distance.
(embodiment 6)
Except alumina slurry (average grain diameter 50nm) is altered to zirconia slurry (average grain diameter 60nm), implement similarly to Example 5, obtained electroconductive particle.
It should be noted that, in the electroconductive particle obtaining, inorganic particulate is harder than conductive layer, and the Mohs' hardness of inorganic particulate is greater than the Mohs' hardness of conductive layer.In addition, in the electroconductive particle obtaining, in total number of multiple inorganic particulates more than 20% not with the Surface Contact of the above-mentioned resin particle as basis material particle but partition distance.
(embodiment 7)
Except alumina slurry (average grain diameter 50nm) is altered to silica slurry (average grain diameter 20nm), implement similarly to Example 5, obtained electroconductive particle.
It should be noted that, in the electroconductive particle obtaining, inorganic particulate is harder than conductive layer, and the Mohs' hardness of inorganic particulate is greater than the Mohs' hardness of conductive layer.In addition, in the electroconductive particle obtaining, in total number of multiple inorganic particulates more than 20% not with the Surface Contact of the above-mentioned resin particle as basis material particle but partition distance.
(embodiment 8)
(1) making of insulating particle
Four neck removable lid (4 Star mouth セ パ ラ Block Le カ バ ー) are being installed, paddle, triple valve, in the removable flask of the 1000mL of condenser pipe and temperature sensor, take and contain methyl methacrylate 100mmol, N, N, N-trimethyl-N-2-methylacryoyloxyethyl ammonium chloride 1mmol and 2, the monomer composition of two (2-amidine propane) the dihydrochloride 1mmol of 2 '-azo is in ion exchange water, and to make the solid constituent point rate of described monomer composition be 5 % by weight, then, with 200rpm, stir, in nitrogen atmosphere, at 70 ℃, carried out polymerization in 24 hours.Reaction finish after, carry out freeze drying, obtained surface there is ammonium, average grain diameter is the insulating particle that 220nm and CV value are 10%.
Insulating particle is dispersed in ion exchange water under ultrasonic vibration, obtains 10 % by weight aqueous dispersions of insulating particle.
The electroconductive particle 10g obtaining in embodiment 1 is scattered in ion exchange water 500mL, adds the aqueous dispersions 4g of insulating particle, and in stirring at room 6 hours.Utilize after the granular membrane filtration of 3 μ m, further with methyl alcohol, clean, be dried, obtained being attached with the electroconductive particle of insulating properties particle.
Utilize scanning electron microscopy (SEM) to observe, result has only formed 1 layer of coating layer consisting of insulating particle on the surface of electroconductive particle.Utilize image analysis to calculate the coated area (being the projected area of the particle diameter of insulating particle) of insulating particle with respect to the ratio of the area apart from electroconductive particle center 2.5 μ m, result, clad ratio is 30%.
(embodiment 9～14)
Except the electroconductive particle obtaining in embodiment 1 being altered to the electroconductive particle obtaining in the following embodiments, implement similarly to Example 8, obtained being attached with the electroconductive particle of insulating particle.
Embodiment 9: be altered to the electroconductive particle obtaining in embodiment 2
Embodiment 10: be altered to the electroconductive particle obtaining in embodiment 3
Embodiment 11: be altered to the electroconductive particle obtaining in embodiment 4
Embodiment 12: be altered to the electroconductive particle obtaining in embodiment 5
Embodiment 13: be altered to the electroconductive particle obtaining in embodiment 6
Embodiment 14: be altered to the electroconductive particle obtaining in embodiment 7
(evaluation)
(1) making of syndeton body
Mix the bisphenol A type epoxy resin (Mitsubishi Chemical Ind's system " Epikote1009 ") of 10 weight portions, the acrylic rubber (weight average molecular weight is about 800,000) of 40 weight portions, methyl ethyl ketone, the microcapsule-type curing agent (ASAHI KASEI CHEMICALS company's system " HX3941HP ") of 50 weight portions and the silane coupler (Dow Corning Toray Silicone system " SH6040 ") of 2 weight portions of 200 weight portions, add electroconductive particle and make its content reach 3 % by weight, disperse, obtained resin combination.
It is PET (PETG) film of 50 μ m that the resin combination obtaining is coated to the thickness that one side passed through demoulding processing, utilizes the heated-air drying 5 minutes of 70 ℃, has made anisotropic conductive film.The thickness of the anisotropic conductive film obtaining is 12 μ m.
The anisotropic conductive film obtaining is cut into the size of 5mm × 5mm.By cut the anisotropic conductive film obtaining be fitted in be provided with aluminium electrode (height 0.2 μ m, L/S=20 μ m/20 μ glass substrate (width 3cm m), length 3cm) the substantial middle of aluminium electrode side, wherein, described aluminium electrode is that a side has the electrode of resistance measurement with lead-in wire.Then the mode, the two-layer flexible printed base plate (width 2cm, length 1cm) with identical aluminium electrode being overlapped each other with electrode is fitted after aliging.Pressing condition with 10N, 180 ℃ and 20 seconds is carried out hot pressing to the duplexer of this glass substrate and two-layer flexible printed base plate, has obtained syndeton body.Wherein, use is the two-layer flexible printed base plate that is directly formed with aluminium electrode on polyimide film.
(2) contact resistance
By four-end method, measured the contact resistance between the comparative electrode of the syndeton body obtaining in the making of above-mentioned (1) syndeton body.And, with following standard, contact resistance is judged.
[criterion of contact resistance]
Zero: contact resistance is below 3.0 Ω
△: contact resistance exceedes 3.0 Ω and is below 5.0 Ω
×: contact resistance exceedes 5.0 Ω
Result is as follows.
[result of determination of contact resistance]
Embodiment 1: zero
Embodiment 2: zero
Embodiment 3: zero
Embodiment 4: zero
Comparative example 1: ×
Embodiment 5: zero
Embodiment 6: zero
Embodiment 7: zero
Embodiment 8: zero
Embodiment 9: zero
Embodiment 10: zero
Embodiment 11: zero
Embodiment 12: zero
Embodiment 13: zero
Embodiment 14: zero
It should be noted that, in the electroconductive particle obtaining, in the inner side of 1 projection of conductive layer outer surface, all with 5, dispose above multiple inorganic particulates in all embodiment.In addition, in embodiment 5～7,12～14, in the inner side of 1 projection of conductive layer outer surface, dispose 1 core material, in 1 projection of conductive layer outer surface be disposed between the core material of this projection inner side, with 5, dispose above multiple inorganic particulates.In addition, in embodiment 5～7,12～14, between the surface of numerous inorganic particulates and the surface of basis material particle, dispose conductive layer and dispose core material.In addition, in embodiment 5～7,12～14, because core material has been used the complex that is attached with inorganic particulate, therefore, numerous inorganic particulates contact with core material.In addition, in embodiment 1～4,8～11, compared with the inner side of the unpolarized outer surface part of conductive layer, multiple inorganic particulates exist unevenly in the mode of inner side of the projection that is present in more conductive layer outer surface.

Claims (13)

1. an electroconductive particle, it possesses:
Basis material particle,
Be disposed on the surface of described basis material particle and outer surface have multiple projections conductive layer and
Imbed the multiple inorganic particulates in described conductive layer,
Wherein,
Inner side in the described projection of the outer surface of described conductive layer disposes described inorganic particulate,
Described at least a portion in described multiple inorganic particulate inorganic particulate not with the Surface Contact of described basis material particle.
2. electroconductive particle according to claim 1, wherein,
Inner side in a described projection of the outer surface of described conductive layer disposes multiple described inorganic particulates.
3. electroconductive particle according to claim 1 and 2, wherein,
In total number of described multiple inorganic particulates more than 20% not with the Surface Contact of described basis material particle.
4. according to the electroconductive particle described in any one in claim 1～3, wherein,
Described basis material particle and the distance not and between the inorganic particulate of the Surface Contact of described basis material particle are below 5nm.
5. according to the electroconductive particle described in any one in claim 1～4, it also possesses multiple core materials of imbedding in described conductive layer.
6. electroconductive particle according to claim 5, wherein,
Inner side in the described projection of the outer surface of described conductive layer disposes described core material,
In a described projection of the outer surface of described conductive layer be disposed between the described core material of inner side of described projection and dispose described inorganic particulate.
7. according to the electroconductive particle described in claim 5 or 6, wherein,
Multiple described inorganic particulates contact with described core material.
8. according to the electroconductive particle described in any one in claim 5～7, wherein,
On the surface of described core material, be attached with described inorganic particulate,
Described core material and described inorganic particulate form complex.
9. according to the electroconductive particle described in any one in claim 5～8, wherein,
Described core material is metallic.
10. according to the electroconductive particle described in any one in claim 1～9, wherein,
Multiple described inorganic particulates are at the skewness of inner surface side and the outer surface side of described conductive layer, its outside the amount of face side higher than the amount in inner surface side.
11. according to the electroconductive particle described in any one in claim 1～10, and it also possesses the surperficial megohmite insulant that is attached to described conductive layer.
12. 1 kinds of electric conducting materials, it contains the electroconductive particle described in any one in adhesive resin and claim 1～11.
13. 1 kinds of syndeton bodies, it possesses:
The 1st connecting object parts,
The 2nd connecting object parts and
Connect connecting portions described the 1st, the 2nd connecting object parts,
Wherein, described connecting portion is formed by the electroconductive particle described in any one in claim 1～11 or is formed by the electric conducting material that contains described electroconductive particle and adhesive resin.
CN201380002679.1A 2012-01-19 2013-01-15 Electroconductive particle, conductive material and connection structural bodies Active CN103748637B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2012009177 2012-01-19
JP2012-009177 2012-01-19
PCT/JP2013/050537 WO2013108740A1 (en) 2012-01-19 2013-01-15 Conductive particles, conductive material and connection structure

Publications (2)

Publication Number Publication Date
CN103748637A true CN103748637A (en) 2014-04-23
CN103748637B CN103748637B (en) 2017-09-29

Family

ID=48799165

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201380002679.1A Active CN103748637B (en) 2012-01-19 2013-01-15 Electroconductive particle, conductive material and connection structural bodies

Country Status (5)

Country Link
JP (2) JP6333552B2 (en)
KR (1) KR101987509B1 (en)
CN (1) CN103748637B (en)
TW (1) TWI601158B (en)
WO (1) WO2013108740A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113993962A (en) * 2019-03-25 2022-01-28 斯皮拉技术有限公司 Multicomponent system and method for producing a multicomponent system, in particular for microelectronic applications

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI561542B (en) * 2013-09-25 2016-12-11 Eternal Materials Co Ltd Polymer particles and the manufacturing process and uses thereof
JP6345075B2 (en) * 2013-10-23 2018-06-20 積水化学工業株式会社 Conductive particles, conductive materials, and connection structures
JP6739894B2 (en) * 2013-11-18 2020-08-12 積水化学工業株式会社 Conductive particles, conductive material and connection structure
JP6577723B2 (en) * 2014-03-10 2019-09-18 積水化学工業株式会社 Conductive particles with insulating particles, conductive material, and connection structure
WO2015174195A1 (en) * 2014-05-12 2015-11-19 積水化学工業株式会社 Electroconductive particles, conductive material, and connection structure
CN112863732B (en) * 2014-10-29 2023-01-17 迪睿合株式会社 Method for manufacturing connection structure, and conductive material
CN107615403B (en) * 2015-09-24 2021-12-24 积水化学工业株式会社 Conductive particle, conductive material, and connection structure
CN108701508B (en) * 2016-02-10 2020-03-24 日立化成株式会社 Conductive particle, insulation-coated conductive particle, anisotropic conductive adhesive, connection structure, and method for producing conductive particle
JP7077963B2 (en) * 2017-01-27 2022-05-31 昭和電工マテリアルズ株式会社 Insulation coated conductive particles, anisotropic conductive film, method for manufacturing anisotropic conductive film, connection structure and method for manufacturing connection structure

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006216388A (en) * 2005-02-03 2006-08-17 Sekisui Chem Co Ltd Conductive fine particle and anisotropic conductive material
JP2006228474A (en) * 2005-02-15 2006-08-31 Sekisui Chem Co Ltd Conductive fine particles and anisotropic conductive material
CN1954393A (en) * 2004-05-12 2007-04-25 第一毛织株式会社 Insulated conductive particles and anisotropic conductive adhesive film containing the particles
CN101006525A (en) * 2004-08-20 2007-07-25 积水化学工业株式会社 Conductive fine particles and anisotropic conductive material
JP2007242307A (en) * 2006-03-06 2007-09-20 Sekisui Chem Co Ltd Conductive particulate and anisotropic conductive material
CN101309993A (en) * 2005-11-18 2008-11-19 日立化成工业株式会社 Adhesive composition, circuit connecting material, connecting structure and circuit member connecting method
WO2011002084A1 (en) * 2009-07-02 2011-01-06 日立化成工業株式会社 Conductive particle

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9822822D0 (en) * 1998-10-19 1998-12-16 Dyno Particles As Particles
JP4860163B2 (en) * 2005-02-15 2012-01-25 積水化学工業株式会社 Method for producing conductive fine particles
JP4746116B2 (en) * 2008-10-14 2011-08-10 日本化学工業株式会社 Conductive powder, conductive material containing the same, and method for producing conductive particles
JP4640532B2 (en) 2009-07-02 2011-03-02 日立化成工業株式会社 Coated conductive particles
JP4640531B2 (en) 2009-07-02 2011-03-02 日立化成工業株式会社 Conductive particles
WO2012014925A1 (en) * 2010-07-28 2012-02-02 積水化学工業株式会社 Insulating-particle-adhered electrically conductive particle, process for producing insulating-particle-adhered electrically conductive particle, anisotropic conductive material, and connected structure
JP5184612B2 (en) * 2010-11-22 2013-04-17 日本化学工業株式会社 Conductive powder, conductive material containing the same, and method for producing the same
JP5323147B2 (en) * 2011-08-10 2013-10-23 積水化学工業株式会社 Conductive fine particles and anisotropic conductive materials

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1954393A (en) * 2004-05-12 2007-04-25 第一毛织株式会社 Insulated conductive particles and anisotropic conductive adhesive film containing the particles
CN101006525A (en) * 2004-08-20 2007-07-25 积水化学工业株式会社 Conductive fine particles and anisotropic conductive material
JP2006216388A (en) * 2005-02-03 2006-08-17 Sekisui Chem Co Ltd Conductive fine particle and anisotropic conductive material
JP2006228474A (en) * 2005-02-15 2006-08-31 Sekisui Chem Co Ltd Conductive fine particles and anisotropic conductive material
CN101309993A (en) * 2005-11-18 2008-11-19 日立化成工业株式会社 Adhesive composition, circuit connecting material, connecting structure and circuit member connecting method
JP2007242307A (en) * 2006-03-06 2007-09-20 Sekisui Chem Co Ltd Conductive particulate and anisotropic conductive material
WO2011002084A1 (en) * 2009-07-02 2011-01-06 日立化成工業株式会社 Conductive particle

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113993962A (en) * 2019-03-25 2022-01-28 斯皮拉技术有限公司 Multicomponent system and method for producing a multicomponent system, in particular for microelectronic applications

Also Published As

Publication number Publication date
WO2013108740A1 (en) 2013-07-25
TW201337957A (en) 2013-09-16
CN103748637B (en) 2017-09-29
KR20140113628A (en) 2014-09-24
JP2018056138A (en) 2018-04-05
TWI601158B (en) 2017-10-01
KR101987509B1 (en) 2019-06-10
JP6333552B2 (en) 2018-05-30
JPWO2013108740A1 (en) 2015-05-11

Similar Documents

Publication Publication Date Title
CN103748637A (en) Conductive particles, conductive material and connection structure
CN103748636A (en) Conductive particles, conductive material, and connection structure
CN104380392B (en) The electroconductive particle of tape insulation particle, conductive material and connection structural bodies
CN103650063B (en) Electroconductive particle, electric conducting material and connection structural bodies
CN103124999B (en) Conductive particles, anisotropic conductive material and connection structure
TWI498405B (en) An electrically conductive particles having an insulating particle, an anisotropic conductive material, and a connecting structure
JP6034177B2 (en) Conductive particles, conductive materials, and connection structures
CN104380393A (en) Conductive particle, resin particle, conductive material, and connection structure
CN103765527B (en) Electroconductive particle, conductive material and connection structural bodies
CN104471650A (en) Conductive particle, conductive material and connecting structure
CN105210157A (en) Conductive particles, conducting material, and connection structure
JP6577698B2 (en) Conductive film and connection structure
CN103782351B (en) Electroconductive particle, conductive material and connection structural bodies
CN103748635B (en) Electroconductive particle, conductive material and connection structural bodies
CN104584141B (en) Conductive particle with insulating particles, conductive material and connection structure
CN106605273A (en) Conductive particles, conductive material and connection structure
CN107615403A (en) Electroconductive particle, conductive material and connection structural bodies
KR20190008828A (en) Conductive particles, a conductive material, and a connection structure

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant