CN107077915A - Conductive material and connecting structure body - Google Patents
Conductive material and connecting structure body Download PDFInfo
- Publication number
- CN107077915A CN107077915A CN201680003614.2A CN201680003614A CN107077915A CN 107077915 A CN107077915 A CN 107077915A CN 201680003614 A CN201680003614 A CN 201680003614A CN 107077915 A CN107077915 A CN 107077915A
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- Prior art keywords
- mentioned
- electrode
- solder
- electroconductive particle
- particle
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
-
- 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
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/16—Non-insulated conductors or conductive bodies characterised by their form comprising conductive material in insulating or poorly conductive material, e.g. conductive rubber
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
- H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L24/10—Bump connectors ; Manufacturing methods related thereto
- H01L24/12—Structure, shape, material or disposition of the bump connectors prior to the connecting process
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
- H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
- H05K3/34—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
- H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
- H05K3/34—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering
- H05K3/3457—Solder materials or compositions; Methods of application thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
- H01L2224/732—Location after the connecting process
- H01L2224/73201—Location after the connecting process on the same surface
- H01L2224/73203—Bump and layer connectors
- H01L2224/73204—Bump and layer connectors the bump connector being embedded into the layer connector
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
- H01L2224/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
- H01L2224/838—Bonding techniques
- H01L2224/83886—Involving a self-assembly process, e.g. self-agglomeration of a material dispersed in a fluid
Abstract
There is provided the electroconductive particle in a kind of conductive material dispersiveness it is higher, can efficiently be configured on electrode the solder in electroconductive particle and improve it is interelectrode conducting reliability conductive material.The conductive material of the present invention includes multiple electroconductive particles, Thermocurable compound and thermal curing agents, above-mentioned electroconductive particle has solder in the outer surface part of conductive part, and above-mentioned electroconductive particle has O-Si keys in the outer surface of the above-mentioned solder of above-mentioned conductive part.
Description
Technical field
The present invention relates to a kind of conductive material, the conductive material includes the electroconductive particle with solder.In addition, of the invention
It has been directed to use with the connecting structure body of above-mentioned conductive material.
Background technology
The anisotropic conductive material such as anisotropic conductive paste and anisotropic conductive film is well known.With regard to above-mentioned
For anisotropic conductive material, electroconductive particle is dispersed with bonding agent.
In order to obtain various connecting structure bodies, above-mentioned anisotropic conductive material be for example used in flexible printing substrate with
Connection (COF (the Chip on of the connection (FOG (Film on Glass)) of glass substrate, semiconductor chip and flexible printing substrate
Film)), the connection (COG (Chip on Glass)) of semiconductor chip and glass substrate and flexible printing substrate and glass
Connection (FOB (Film on Board)) of epoxy substrate etc..
Utilizing electricity of the above-mentioned anisotropic conductive material to such as electrode of flexible printing substrate and glass epoxy substrate
When pole is electrically connected, configuration includes the anisotropic conductive material of electroconductive particle on glass epoxy substrate.Next, layer
Folded flexible printing substrate, is heated and is pressurizeed.Thus, solidify anisotropic conductive material, via electroconductive particle pair
It is electrically connected between electrode, obtains connecting structure body.
As an example of above-mentioned anisotropic conductive material, following patent documents 1 describes a kind of comprising conduction
Property particle and will not the electroconductive particle fusing point complete solidification resin component anisotropic conductive material.As above-mentioned
Electroconductive particle, specifically, can enumerate tin (Sn), indium (In), bismuth (Bi), silver-colored (Ag), copper (Cu), zinc (Zn), lead (Pb), cadmium
(Cd), the alloy of gallium (Ga), the silver-colored metal such as (Ag) and thallium (Tl) or these metals.
In patent document 1, describing will electrically connect via resin heating stepses and resin component curing schedule between electrode,
In the resin heating stepses, anisotropic conductive resin is heated to higher than the fusing point of above-mentioned electroconductive particle and will not
Above-mentioned resin component is completed the temperature of solidification, in the resin component curing schedule, solidify above-mentioned resin component.In addition,
Record and installed with the temperature curve shown in Fig. 8 of patent document 1 in patent document 1.In patent document 1, not
Completed with the temperature for heating anisotropic conductive resin in the resin component of solidification, electroconductive particle melting.
The following Patent Document 2 discloses a kind of jointing tape, the jointing tape, which is included, has heat-curing resin
Resin bed, solder powder and curing agent, above-mentioned solder powder and above-mentioned curing agent are present in above-mentioned resin bed.The bonded adhesives
Band is membranaceous, not paste-like.
In addition, in patent document 2, disclosing the adhering method using above-mentioned jointing tape.Specifically, from below according to
It is secondary to be laminated first substrate, jointing tape, second substrate, jointing tape and the 3rd substrate and obtain layered product.Now, make to set
First electrode in the surface of first substrate and the second electrode on the surface located at second substrate are opposed.In addition, making to be located at second
The surface of substrate point second electrode and the 3rd electrode contraposition located at the surface of the 3rd substrate.Then, heated with defined temperature
Layered product and be bonded.Thus, connecting structure body is obtained.
In addition, in following patent documents 3, disclosing a kind of by semiconductor chip and tool with multiple connection terminals
The circuit board for having multiple electrodes terminal is opposed to arrange and by the above-mentioned electrode terminal of above-mentioned circuit board and above-mentioned semiconductor
What the above-mentioned connection terminal of chip was electrically connected is flip-chip mounted method.This is flip-chip mounted method and included：(1) to above-mentioned circuit board
The process of the resin of solder powder and convection current additive, (2) are supplied on surface with above-mentioned electrode terminal makes above-mentioned semiconductor
Chip is connected to the work that above-mentioned circuit board is heated to the temperature of above-mentioned solder powder melting by the process of above-mentioned resin surface, (3)
Sequence and (4) make the process of above-mentioned resin solidification after above-mentioned heating process.In the heating process (3) of above-mentioned circuit board
In, the connector for electrically connecting above-mentioned electrode terminal with above-mentioned connection terminal is formed, in addition, in the curing process of above-mentioned resin
(4) in, above-mentioned semiconductor chip is fixed on above-mentioned circuit board.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2004-260131 publications
Patent document 2：WO2008/023452A1
Patent document 3：Japanese Unexamined Patent Publication 2006-114865 publications
The content of the invention
In the anisotropic conductive paste of the electroconductive particle containing conventional solder powder or surface with solder layer, have
Solder powder or electroconductive particle are efficiently configured on electrode (line) by Shi Weineng.In conventional solder powder or electric conductivity grain
In son, solder powder or electroconductive particle are slower to the translational speed on electrode sometimes.
If in addition, using the anisotropic conductive material described in patent document 1, in the method described in patent document 1
It will electrically connect, then the electroconductive particle comprising solder can not be efficiently configured on electrode (line) sometimes between electrode.In addition,
In the embodiment of patent document 1, in order to make solder fully move at a temperature of more than the fusing point of solder, constant temperature is remained
Degree, the manufacture efficiency reduction of connecting structure body.If being installed with the temperature curve shown in Fig. 8 of patent document 1, structure is connected
Make the manufacture efficiency reduction of body.
In patent document 2, the electroconductive particle on being used in anisotropic conductive material is not recorded specifically.
In the embodiment of patent document 3, use and layers of copper is formed with the surface of resin particle and is formed on the surface of the layers of copper
There is the electroconductive particle of solder layer.The core of the electroconductive particle is made up of resin particle.If in addition, using patent document
2nd, the anisotropic conductive material described in 3, then be difficult on electrode (line) efficiently configure electroconductive particle sometimes, and producing should
Interelectrode position skew above and below connection.
In addition, in conventional anisotropic conductive material, the dispersiveness of electroconductive particle is sometimes relatively low.Therefore, if
Used after keeping anisotropic conductive material, then electroconductive particle is more difficult to configuration on electrode (line) sometimes.
It is an object of the present invention to provide a kind of dispersiveness of electroconductive particle in conductive material it is higher, can be in electricity
The solder in electroconductive particle is efficiently configured on extremely and the conductive material of interelectrode conducting reliability is improved.In addition, this hair
Bright purpose is that there is provided a kind of connecting structure body for having used above-mentioned conductive material.
Means for solving the problems
According to the wide in range aspect of the present invention there is provided a kind of conductive material, multiple electroconductive particles, Thermocurable chemical combination are included
Thing and thermal curing agents, above-mentioned electroconductive particle have solder in the outer surface part of conductive part, and above-mentioned electroconductive particle is upper
Stating the outer surface of the above-mentioned solder of conductive part has O-Si keys.
In some particular aspects of the conductive material of the present invention, above-mentioned solder of the above-mentioned electroconductive particle in above-mentioned conductive part
Outer surface there is Sn-O-Si keys.
It is the surface treatment based on silane coupler in some particular aspects of the conductive material of the present invention.
In some particular aspects of the conductive material of the present invention, above-mentioned solder of the above-mentioned electroconductive particle in above-mentioned conductive part
Outer surface there is amino.
In some particular aspects of the conductive material of the present invention, above-mentioned solder of the above-mentioned electroconductive particle in above-mentioned conductive part
Outer surface have via Sn-O-Si keys and wrap carboxylic group.
In some particular aspects of the conductive material of the present invention, above-mentioned electroconductive particle is semiconductor particles.
In some particular aspects of the conductive material of the present invention, the average grain diameter of above-mentioned electroconductive particle for more than 1 μm and
Less than 60 μm.
In some particular aspects of the conductive material of the present invention, in the weight % of conductive material 100, above-mentioned electric conductivity grain
The content of son is more than 10 weight % and below 80 weight %.
According to the wide in range aspect of the present invention there is provided a kind of connecting structure body, possess：First connecting object part, it is in table
Face has first electrode；Second connecting object part, it has second electrode on surface；And connecting portion, it is by above-mentioned first
Connecting object part is connected with above-mentioned second connecting object part, and the material of above-mentioned connecting portion is above-mentioned conductive material, and above-mentioned
One electrode utilizes the solder in above-mentioned electroconductive particle to electrically connect with above-mentioned second electrode.
Invention effect
The conductive material of the present invention includes multiple electroconductive particles, Thermocurable compound and thermal curing agents, above-mentioned to lead
Conductive particles have a solder in the outer surface part of conductive part, above-mentioned electroconductive particle above-mentioned conductive part above-mentioned solder it is outer
Surface has O-Si keys, therefore the dispersiveness of the electroconductive particle in conductive material is higher, can efficiently be configured on electrode
Solder in electroconductive particle, and interelectrode conducting reliability can be improved.
Brief description of the drawings
Fig. 1 is to show schematically cuing open for the connecting structure body obtained using the conductive material of one embodiment of the present invention
Face figure.
Fig. 2 (a)~(c) is for illustrating to manufacture connecting structure body using the conductive material of one embodiment of the present invention
Method an example each operation profile.
Fig. 3 is the profile for the variation for representing connecting structure body.
Fig. 4 is to represent that the profile of the first case of the electroconductive particle of conductive material can be used in.
Fig. 5 is to represent that the profile of the second case of the electroconductive particle of conductive material can be used in.
Fig. 6 is to represent that the profile of the 3rd of the electroconductive particle of conductive material can be used in.
Embodiment
Hereinafter, the details of the present invention is illustrated.
(conductive material)
The conductive material of the present invention includes multiple electroconductive particles, Thermocurable compound and thermal curing agents.It is above-mentioned to lead
Conductive particles have conductive part.Above-mentioned electroconductive particle has solder in the outer surface part of conductive part.Solder is included in conduction
It is some or all of conductive part in portion.
In the conductive material of the present invention, above-mentioned electroconductive particle has in the outer surface of the above-mentioned solder of above-mentioned conductive part
O-Si keys.
In the present invention, due to including specific electroconductive particle in conductive material, therefore solder can be suppressed well
Corrosion.In the present invention, due to possessing above-mentioned composition, therefore in the case where will be electrically connected between electrode, electroconductive particle
In solder easily concentrate on above and below opposed electrode between, can efficiently by electroconductive particle solder configure in electrode
On (line).In addition, a part for the solder in electroconductive particle is difficult to be configured at the region for being formed without electrode (space), can
Rather reduce the amount for the solder for being configured at the region for being formed without electrode.In the present invention, it can make to be not located at opposed electrode
Between electroconductive particle be efficiently moved between opposed electrode.Therefore, it is possible to improve interelectrode conducting reliability.Also,
The interelectrode electrical connection adjacent in the horizontal that can not be connected can be prevented, it is possible to increase insulating reliability.
Moreover, in the present invention, the dispersiveness of the electroconductive particle in conductive material is higher, the preservation of conductive material is stable
Property is excellent.In addition, in the present invention, the corrosion of the solder in electroconductive particle is also difficult to.Therefore, either conductive material
Keeping before or keeping after in the case of, can efficiently by electroconductive particle solder configure on electrode, can
Improve interelectrode conducting reliability.
Also, it in the present invention, can prevent interelectrode position from offseting.In the present invention, the second connecting object is made
When part coincides with the first connecting object part that conductive material is configured with upper surface, even in the first connecting object part
Electrode and the second connecting object part electrode alignment occur deviation in the state of, make the first connecting object part and second
In the case that connecting object part is overlapped, the deviation can be also corrected, and connects the electrode of the first connecting object part and second
Connect the electrode connection (self-aligning effect) of object Part.
For the viewpoint for the configuration precision for effectively improving dispersiveness and solder, preferably above-mentioned electroconductive particle exists
The outer surface of the above-mentioned solder of above-mentioned conductive part has Sn-O-Si keys.
For the viewpoint for the configuration precision for effectively improving dispersiveness and solder, above-mentioned electroconductive particle is preferably logical
Cross the surface treatment for having used silane coupler and obtain, above-mentioned electroconductive particle has carried out table preferably by silane coupler
Face is handled.That is, above-mentioned electroconductive particle is preferably based on the surface treatment of silane coupler.
Above-mentioned electroconductive particle can also be semiconductor particles.Above-mentioned semiconductor particles are formed by solder.Above-mentioned semiconductor particles exist
The outer surface part of conductive part has solder.The core of above-mentioned semiconductor particles and the outer surface part of conductive part are by weldering
Material is formed, and the outer surface part of core and conductive part is particle as solder.Above-mentioned electroconductive particle also may be used
With the conductive part with substrate particle and configuration on the surface of the substrate particle.In this case, above-mentioned electroconductive particle
There is solder in the outer surface part of conductive part.
In addition, compared with using the situation for the electroconductive particle for possessing above-mentioned semiconductor particles, do not utilized using possessing
In the case of the electroconductive particle of solder portion of the substrate particle of solder formation with configuration on the surface of substrate particle, electric conductivity
Particle is difficult to be collected on electrode, and the mutual solder zygosity of electroconductive particle is relatively low, therefore the electric conductivity moved on electrode
There is the trend easily moved to outside electrode in particle, there is also the trend of reduction for the effect of the interelectrode position skew of suppression.Cause
This, the semiconductor particles that above-mentioned electroconductive particle is formed preferably with solder.
In order to which further efficiently by solder configuration on electrode, viscosity (η 25) of the above-mentioned conductive material at 25 DEG C is excellent
Choosing is more than 10Pas, more preferably more than 50Pas, more preferably more than 100Pas, and preferably
Below 800Pas, more preferably below 600Pas, more preferably below 500Pas.
Above-mentioned viscosity (η 25) can suitably adjust according to the species and use level of gradation composition.In addition, by filling out
The use of material, can make viscosity of a relatively high.
Above-mentioned viscosity (η 25) can use such as E types viscosimeter (Toki Sangyo Co., Ltd. manufacture " TVE22L ")
It is measured under conditions of 25 DEG C and 5rpm.
Above-mentioned conductive material is used as conductive paste and conducting film etc..Above-mentioned conductive paste is preferably anisotropy
Conductive paste, above-mentioned conducting film is preferably anisotropic conductive film.For further efficiently by the weldering in electroconductive particle
Viewpoint of the material configuration on electrode, above-mentioned conductive material is preferably anisotropic conductive paste.Above-mentioned conductive material is adapted to use
In the electrical connection of electrode.Above-mentioned conductive material is preferably circuit connection material.
Hereinafter, each composition that above-mentioned conductive material is included is illustrated.
(electroconductive particle)
Above-mentioned electroconductive particle will be electrically connected between the electrode of connecting object part.Above-mentioned electroconductive particle is in the outer of conductive part
Surface portion has solder.Above-mentioned electroconductive particle has O-Si keys in the outer surface of the above-mentioned solder of above-mentioned conductive part.On
The O-Si keys existed in the outer surface of the above-mentioned solder of above-mentioned conductive part, the composition atom of solder (constitute) of such as solder with
The oxygen atom key of O-Si keys.Above-mentioned electroconductive particle for example has (solder in the outer surface of the above-mentioned solder of above-mentioned conductive part
Composition)-O-Si keys ((atom for constituting solder)-O-Si keys).
For the further dispersiveness for improving electroconductive particle, solder is more efficiently configured on electrode, and further press down
The viewpoint of interelectrode position skew is made, preferably above-mentioned electroconductive particle is in the outer surface of the above-mentioned solder of above-mentioned conductive part
With Sn-O-Si keys.
Can be reacted hydroxyl of the silane coupler on the surface of solder.By making silane coupler in the table of solder
The hydroxyl in face is reacted, and can form O-Si keys.
Preferably, surface treatment row is carried out by using silane coupler, obtained in the outer surface of the solder of conductive part
Electroconductive particle with Sn-O-Si keys, afterwards, the electroconductive particle, Thermocurable compound and thermal curing agents are entered
Row mixing, is derived from above-mentioned conductive material.
For the further dispersiveness for improving electroconductive particle, further efficiently by solder configuration on electrode, go forward side by side
One step suppresses the viewpoint of interelectrode position skew, and above-mentioned electroconductive particle is preferably the above-mentioned solder in above-mentioned conductive part
Outer surface has amino.
For the further dispersiveness for improving electroconductive particle, further efficiently by solder configuration on electrode, go forward side by side
One step suppresses the viewpoint of interelectrode position skew, and above-mentioned electroconductive particle is preferably the above-mentioned solder in above-mentioned conductive part
Outer surface has via O-Si keys wraps carboxylic group, is more preferably in the outer surface of the above-mentioned solder of above-mentioned conductive part
Have via Sn-O-Si keys and wrap carboxylic group.Especially since the presence of carboxylic group is wrapped, the cohesion of solder
Performance is rather improved.
For the further dispersiveness for improving electroconductive particle, further efficiently by solder configuration on electrode, go forward side by side
One step suppresses the viewpoint of interelectrode position skew, and above-mentioned electroconductive particle is carried out at surface preferably with silane coupler
Obtained after reason, by importing the carboxylic group of bag.The residue having for silane coupler, can be imported comprising carboxylic
The group of base.Above-mentioned electroconductive particle is preferably with the base from silane coupler and containing carboxyl, and solder is with including carboxylic
The group of base preferably links via the base from silane coupler.
Above-mentioned silane coupler preferably has organic functional base and alkoxy in 1 molecule, and the organic functional base is excellent
Choosing is can be reacted with the compound with the carboxylic group of bag.As above-mentioned alkoxy, can enumerate methoxyl group with
And ethyoxyl etc..As above-mentioned silane coupler, the silane coupler with epoxy radicals can be enumerated, with the silane coupled of amino
Agent and silane coupler with NCO etc..Exist for further efficiently the solder in electroconductive particle is configured
Viewpoint on electrode, above-mentioned silane coupler is preferably the silane coupler with amino.Above-mentioned silane coupler can be only
, can also be simultaneously using two or more using one kind.In addition, above-mentioned electroconductive particle above-mentioned conductive part above-mentioned solder
In the case that outer surface has amino, the amino from the silane coupler with the amino may not be.
As the silane coupler with above-mentioned epoxy radicals, can enumerate the making of KCC of SHIN-ETSU HANTOTAI KBM-303,
KBM-402, KBM-403, KBE-402 and KBE-403 etc..As the silane coupler with above-mentioned amino, it can enumerate
KBM-602 and KBM-603, KBM-903 etc..As the silane coupler with above-mentioned NCO, it can enumerate
KBE-9007 etc..
As the compound for importing the carboxylic group of above-mentioned bag, can enumerate levulic acid, glutaric acid, glycolic,
Butanedioic acid, malic acid, oxalic acid, malonic acid, adipic acid, 5- oxos caproic acid, 3- hydracrylic acids, 4-Aminobutanoicacid, 3- sulfydryls
Propionic acid, 3- mercaptoisobutyric acids, 3- methylpropanethioates, 3- benzenpropanoic acids, 3- phenylisobutyrics, 4-phenylbutyrate, capric acid,
Laurate, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, 9- unrighted acids, Heptadecanoic acide, palmitic acid, oleic acid, 18 carbon
Olefin(e) acid, linoleic acid, (9,12,15)-leukotrienes, nonadecylic acid, arachic acid, decanedioic acid and dodecanedioic acid etc..It is preferred that
It is glutaric acid, adipic acid or glycolic.One kind can be both used only in compound for importing the carboxylic group of above-mentioned bag,
Can also be simultaneously using two or more.
The specific method for having the electroconductive particle of O-Si keys in the outer surface of solder as obtaining, can be set forth in first
Electroconductive particle and silane coupler are put into the solvent of the low polarity of benzene etc. and method of dealcoholization etc. is carried out.
Next, on one side referring to the drawings, while the concrete example of explanation electroconductive particle.
Fig. 4 is to represent that the profile of the first case of the electroconductive particle of conductive material can be used in.
Electroconductive particle 21 shown in Fig. 4 is semiconductor particles.Electroconductive particle 21 is overall to be formed by solder.Electroconductive particle
21 be not the core shell particle in core with substrate particle.The core of electroconductive particle 21 and the outer surface portion of conductive part
Divide and formed by solder.
Fig. 5 is to represent that the profile of the second case of the electroconductive particle of conductive material can be used in.
Electroconductive particle 31 shown in Fig. 5 possesses the conductive part of substrate particle 32 and configuration on the surface of substrate particle 32
33.Conductive part 33 covers the surface of substrate particle 32.Electroconductive particle 31 is that the surface of substrate particle 32 is covered by conductive part 33
The covering particle of lid.
Conductive part 33 has the second conductive part 33A and solder portion 33B (the first conductive part).Electroconductive particle 31 is in base material grain
Possesses the second conductive part 33A between 32 and solder portion 33B of son.Therefore, electroconductive particle 31 possesses substrate particle 32, configured in base
The solder portion 33B of the second conductive part 33A and configuration on the second conductive part 33A outer surface on the surface of material particle 32.
Fig. 6 is to represent that the profile of the 3rd of the electroconductive particle of conductive material can be used in.
As described above, the conductive part 33 in electroconductive particle 31 has double-layer structural.Electroconductive particle 41 shown in Fig. 6
With conductive part of the solder portion 42 as individual layer.Electroconductive particle 41 possesses the table of substrate particle 32 and configuration in substrate particle 32
Solder portion 42 on face.
As above-mentioned substrate particle, resin particle, the inorganic particulate in addition to metallic, organic inorganic hybridization can be enumerated
Particle and metallic etc..Above-mentioned substrate particle is preferably the substrate particle in addition to metal, and preferably resin particle
Son, the inorganic particulate in addition to metallic or organic inorganic hybridization particle.Above-mentioned substrate particle can also be copper particle.On
The shell of core and configuration on the surface of the core can also be had by stating substrate particle, can also be core shell particle.Above-mentioned core can also
It is to have movement, above-mentioned shell can also be inorganic shell.
As the resin for forming above-mentioned resin particle, preferably using various organic matters.As above-mentioned for being formed
The resin of resin particle, can for example enumerate polyethylene, polypropylene, polystyrene, polyvinyl chloride, Vingon, polyisobutene,
The vistanexes such as polybutadiene；The acrylic resins such as polymethyl methacrylate, PMA；Makrolon, polyamides
Amine, phenol formaldehyde resin, melamine resin, benzoguanamin formaldehyde resin, urea-formaldehyde resin, phenolic resin, trimerization
It is melamine resin, benzoguanamine resin, Lauxite, epoxy resin, unsaturated polyester resin, saturated polyester resin, poly- to benzene two
Formic acid glycol ester, polysulfones, polyphenylene oxide, polyacetals, polyimides, polyamidoimide, polyether-ether-ketone, polyether sulfone, divinyl
Base benzene polymer and divinylbenzene analog copolymer etc..As above-mentioned divinylbenzene analog copolymer etc., divinyl can be enumerated
Base benzene-benzene ethylene copolymer and divinylbenzene-(methyl) acrylate copolymer etc..Due to can easily will be above-mentioned
The hardness of resin particle is controlled in appropriate scope, thus be accordingly used in the resin to form above-mentioned resin particle preferably for by one
The polymer that kind or the two or more polymerizable monomers with olefinic unsaturated group are polymerized.
In the case of obtaining above-mentioned resin particle, tool is used as polymerizeing the polymerizable monomer with olefinic unsaturated group
There is the polymerizable monomer of the olefinic unsaturated group, the monomer of non-crosslinked property and the monomer of bridging property can be enumerated.
As the monomer of above-mentioned non-crosslinked property, for example, it can enumerate：The styrene monomers such as styrene, α-methylstyrene；
The carboxyl group-containing monomers such as (methyl) acrylic acid, maleic acid, maleic anhydride；(methyl) methyl acrylate, (methyl) ethyl acrylate,
(methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) 2-EHA, (methyl) lauryl acrylate,
(methyl) aliphatic acrylate, (methyl) stearyl acrylate ester, (methyl) cyclohexyl acrylate, the different ice of (methyl) acrylic acid
Piece ester etc. (methyl) alkyl-acrylates；(methyl) acrylic acid 2- hydroxy methacrylates, (methyl) glycerol acrylate, polyoxyethylene
(methyl) esters of acrylic acid containing oxygen atom such as (methyl) acrylate, (methyl) glycidyl acrylate；(methyl) third
Alkene nitrile etc. contains nitrile monomer；The vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether；Vinyl acetate,
The vinyl acetate class such as vinyl butyrate, vinyl laurate, stearic acid vinyl ester；Ethene, propylene, isoprene, butadiene etc.
Unsaturated hydrocarbons；(methyl) acrylic acid trifluoromethyl ester, the fluorine ethyl ester of (methyl) acrylic acid five, vinyl chloride, PVF, chlorostyrene etc. contain
Halogen monomer etc..
As the monomer of above-mentioned bridging property, for example, it can enumerate：Tetramethylol methane four (methyl) acrylate, tetra methylol
Methane three (methyl) acrylate, tetramethylol methane two (methyl) acrylate, trimethylolpropane tris (methyl) acrylic acid
Ester, dipentaerythritol six (methyl) acrylate, dipentaerythritol five (methyl) acrylate, glycerine three (methyl) acrylic acid
Ester, glycerine two (methyl) acrylate, (poly-) ethylene glycol two (methyl) acrylate, (poly-) propane diols two (methyl) acrylic acid
Multifunctional (methyl) propylene such as ester, (poly-) tetramethylene two (methyl) acrylate, 1,4- butanediols two (methyl) acrylate
Esters of gallic acid；(different) triallyl cyanurate, triallyltrimelitate, divinylbenzene, dially phthalate, two allyls
Base acrylamide, diallyl ether, γ-(methyl) acryloxypropyl trimethoxy silane, trimethoxysilyl benzene
Silane-containing monomer such as ethene, vinyltrimethoxy silane etc..
It polymerize the above-mentioned polymerizable monomer with ethylenically unsaturated group by using known method, can obtains
State resin particle.As this method, can for example enumerate carried out in the presence of radical polymerization initiator suspension polymerisation method,
And the method for making monomer swell together with radical polymerization initiator using noncrosslinking kind of particle and polymerizeing etc..
In the case that above-mentioned base particle is the inorganic particulate or organic inorganic hybridization particle in addition to metal, as
Inorganic matter for forming above-mentioned base particle, can enumerate silica, aluminum oxide, barium titanate, zirconium oxide and carbon black
Deng.Above-mentioned inorganic matter is not preferably metal.Although it is not specifically limited using the particle of above-mentioned silica formation, but for example
It can enumerate to be formed to be crosslinked by the way that the silicon compound with the water-disintegrable alkoxysilyl of two or more is hydrolyzed and gather
After polymer particle, particle obtained from being fired as needed.As above-mentioned organic inorganic hybridization particle, for example, it can enumerate
Organic inorganic hybridization particle formed by the alkoxysilyl polymer and acrylic resin that are crosslinked etc..
Above-mentioned organic inorganic hybridization particle is preferably the core-shell-type of the shell on the surface of the core with core and configuration
Organic inorganic hybridization particle.Above-mentioned core has been preferably movement.Above-mentioned shell is preferably inorganic shell.For being effectively reduced electrode
Between connection resistance viewpoint, above-mentioned substrate particle preferably have movement and configure on the above-mentioned surface for having movement
The organic inorganic hybridization particle of inorganic shell.
As for forming the above-mentioned material for having a movement, the resin etc. for forming above-mentioned resin particle can be enumerated.
As the material for forming above-mentioned inorganic shell, the inorganic matter for forming above-mentioned substrate particle can be enumerated.With
Silica is preferably in the material for forming above-mentioned inorganic shell.Above-mentioned inorganic shell is preferably utilized on the surface of above-mentioned core
Sol-gal process make metal alkoxides turn into husk after, make the husk sinter and formed.Above-mentioned metal alkoxides are preferred
Be alkoxy silane.Above-mentioned inorganic shell is preferably formed by alkoxy silane.
The particle diameter of above-mentioned core is preferably more than 0.5 μm, more preferably more than 1 μm, and preferably less than 100 μm,
More preferably less than 60 μm, more preferably less than 30 μm, particularly preferably less than 15 μm, most preferably 10 μm with
Under.If the particle diameter of above-mentioned core is more than above-mentioned lower limit and below the above-mentioned upper limit, it can obtain and be more suitable for interelectrode electrical connection
Electroconductive particle, can suitably by substrate particle be applied to electroconductive particle purposes.If for example, the particle diameter of above-mentioned core is
More than above-mentioned lower limit and below the above-mentioned upper limit, then in the case where using between above-mentioned electroconductive particle connection electrode, electric conductivity
The contact area of particle and electrode fully becomes big, and is difficult to the electroconductive particle to form cohesion when forming conductive layer.In addition,
The interelectrode interval connected via electroconductive particle will not become too much, and conductive layer is difficult to the surface stripping from substrate particle
From.
The particle diameter of above-mentioned core in above-mentioned core to mean diameter in the case of just spherical, in above-mentioned core for beyond just spherical
Maximum gauge is meant in the case of shape.In addition, the particle diameter of core is meant determines core using arbitrary particle size determination device
Obtained by average grain diameter.The principle such as can utilize and use the graphical analysis after laser light scattering, resistance change, shooting
Particle size distribution machine.
The thickness of above-mentioned shell is preferably more than 100nm, more preferably more than 200nm, and preferably less than 5 μm,
More preferably less than 3 μm.If the thickness of above-mentioned shell is more than above-mentioned lower limit and below the above-mentioned upper limit, it can be more suitable for
Substrate particle, can be suitably used in the purposes of electroconductive particle by the electroconductive particle of interelectrode electrical connection.Above-mentioned shell
Thickness be each substrate particle average thickness.By the control of sol-gal process, the thickness of above-mentioned shell can be controlled.
In the case where above-mentioned substrate particle is metallic, as the metal for forming the metallic, it can enumerate
Silver, copper, nickel, silicon, gold and titanium etc..In the case where above-mentioned substrate particle is metallic, the metallic is preferably copper
Particle.Wherein, above-mentioned substrate particle is not preferably metallic.
The particle diameter of above-mentioned substrate particle is preferably more than 0.1 μm, more preferably more than 1 μm, more preferably 1.5
More than μm, particularly preferably more than 2 μm, and preferably less than 100 μm, more preferably less than 60 μm, further preferably
Be less than 30 μm, more preferably less than 20 μm, it is even furthermore preferable that less than 10 μm, particularly preferably 5 μm with
Under, most preferably less than 3 μm.If the particle diameter of above-mentioned substrate particle is more than above-mentioned lower limit, electroconductive particle and electrode
Contact area becomes big, therefore, it is possible to further improve interelectrode conducting reliability, and can further reduce via electric conductivity
The interelectrode connection resistance of particle connection.If the particle diameter of above-mentioned substrate particle is below the above-mentioned upper limit, it is easy to fully press
Contracting electroconductive particle, can further reduce interelectrode connection resistance, and can further reduce interelectrode interval.
The particle diameter of above-mentioned substrate particle, to represent diameter in the case of just spherical, is not just in substrate particle in substrate particle
Maximum gauge is represented in the case of spherical.
The particle diameter of above-mentioned substrate particle is particularly preferably more than 2 μm, less than 5 μm.If at the particle diameter of above-mentioned substrate particle
In in more than 2 μm, less than 5 μm of scope, then can further reduce interelectrode interval, even and if thicken conductive layer thickness
Degree also results in less electroconductive particle.
On the surface of above-mentioned substrate particle formed conductive part method and on the surface of above-mentioned substrate particle or
The method that solder portion is formed on the surface of above-mentioned second conductive part is not specifically limited.As forming above-mentioned conductive part and above-mentioned
The method of solder portion, for example, can enumerate the method based on electroless plating, the side based on electric plating method, based on physical collision
Method, the method based on mechanico-chemical reaction, method based on physical evaporation or physical absorption and by metal dust or
Paste coating comprising metal dust and bonding agent is in the method on the surface of substrate particle etc..These, it is preferred to electroless plating,
Method under plating or physical collision.As the above-mentioned method based on physical evaporation, vacuum evaporation, ion can be enumerated
The method such as plating and ion sputtering.In addition, in the above-mentioned method based on physical collision, can be used for example
ThetaComposer (moral longevity work institute Co. Ltd. system) etc..
The fusing point of above-mentioned substrate particle is preferably higher than the fusing point of above-mentioned conductive part and above-mentioned solder portion.Above-mentioned base material
The fusing point of particle is preferably more than 160 DEG C, especially excellent more preferably more than 400 DEG C more preferably more than 300 DEG C
Choosing is more than 450 DEG C.In addition, the fusing point of above-mentioned substrate particle might be less that 400 DEG C.The fusing point of above-mentioned substrate particle also may be used
To be less than 160 DEG C.The softening point of above-mentioned substrate particle is preferably more than 260 DEG C.The softening point of above-mentioned substrate particle also may be used
With less than 260 DEG C.
Above-mentioned electroconductive particle can also have the solder portion of individual layer.Above-mentioned electroconductive particle can also have leading for multilayer
Electric portion's (solder portion, the second conductive part).That is, can also stacked bi-layer above conductive part in above-mentioned electroconductive particle.Above-mentioned
In the case that conductive part is the double-deck above, above-mentioned electroconductive particle preferably has solder in the outer surface part of conductive part.
Above-mentioned solder is preferably the metal (low-melting-point metal) that fusing point is less than 450 DEG C.Above-mentioned solder portion is preferably
Fusing point is less than 450 DEG C of metal level (low-melting-point metal layer).Above-mentioned low-melting-point metal layer is the layer for including low-melting-point metal.On
State the solder in electroconductive particle and be preferably the metallic (low-melting-point metal particle) that fusing point is less than 450 DEG C.It is above-mentioned low
Melting point metals particle is the particle for including low-melting-point metal.The low-melting-point metal represents the metal that fusing point is less than 450 DEG C.Eutectic
The fusing point of point metal is preferably less than 300 DEG C, more preferably less than 160 DEG C.In addition, the solder in above-mentioned electroconductive particle
Preferably include tin.Solder in the weight % of metal 100 that above-mentioned solder portion is included and in above-mentioned electroconductive particle
Comprising the weight % of metal 100 in, the content of tin is preferably more than 30 weight %, more preferably more than 40 weight %,
More preferably more than 70 weight %, particularly preferably more than 90 weight %.If the solder institute in above-mentioned electroconductive particle
Comprising tin content for more than above-mentioned lower limit, then the conducting reliability of electroconductive particle and electrode is further improved.
In addition, the content of above-mentioned tin can use high-frequency inductive coupling plasma body emission spectrographic analysis device (strain formula meeting
Society's hole makes made " ICP-AES ") or fluorescent X-ray section analysis apparatus (Shimadzu Scisakusho Ltd system " EDX-
800HS ") etc. be measured.
There is the electroconductive particle of above-mentioned solder, melt solder by using the outer surface part in conductive part and be engaged in
Electrode, and solder makes conducting between electrode.For example, solder and electrode easily carry out face contact and simultaneously non-dots is contacted, therefore connection electricity
Resistance reduction.In addition, there is the electroconductive particle of solder by using the outer surface part in conductive part, the engagement of solder and electrode
Intensity is uprised, as a result, is more difficult to produce the stripping of solder and electrode, can be effectively improved conducting reliability.
The low-melting-point metal for constituting above-mentioned solder portion and above-mentioned semiconductor particles is not specifically limited.The low-melting-point metal is excellent
Choosing is tin or the alloy comprising tin.The alloy can enumerate tin-silver alloy, tin-copper alloy, tin-silver-copper alloy,
Tin-bismuth alloy electroplating, tin-zinc alloy, Sn-In alloy etc..Wherein, because the wetability to electrode is excellent, therefore above-mentioned low melting point
Metal is preferably tin, tin-silver alloy, tin-silver-copper alloy, tin-bismuth alloy electroplating, Sn-In alloy.More preferably tin-
Bismuth alloy, Sn-In alloy.
The material for constituting above-mentioned solder (solder portion) is preferably based on JISZ3001：Welding terminology, liquidus curve is 450 DEG C
Following filling metal.As the composition of above-mentioned solder, the gold such as comprising zinc, gold, silver, lead, copper, tin, bismuth, indium can be enumerated
Category composition.These, it is preferred to be used as low melting point and (139 DEG C of unleaded tin-indium class (117 DEG C of eutectics) or Sn-Bi class
Eutectic).That is, above-mentioned solder does not include lead preferably, and the preferably solder comprising tin and indium or comprising tin and bismuth
Solder.
It can be included to further improve the solder in the bond strength of above-mentioned solder and electrode, above-mentioned electroconductive particle
The metals such as nickel, copper, antimony, aluminium, zinc, iron, gold, titanium, phosphorus, germanium, tellurium, cobalt, bismuth, manganese, chromium, molybdenum, palladium.In addition, for further raising
Solder in the viewpoint of the bond strength of solder and electrode, above-mentioned electroconductive particle preferably comprising nickel, copper, antimony aluminium or
Zinc.For the viewpoint of the further solder improved in solder portion or electroconductive particle and the bond strength of electrode, for improving
In the weight % of solder 100 of the content of these metals of bond strength in above-mentioned electroconductive particle, preferably 0.0001 weight
Measure more than %, and preferably below 1 weight %.
The fusing point of above-mentioned second conductive part is preferably higher than the fusing point of above-mentioned solder portion.The fusing point of above-mentioned second conductive part
Preferably more than 160 DEG C, more preferably more than 300 DEG C, more preferably more than 400 DEG C, it is even furthermore preferable that
More than 450 DEG C, particularly preferably more than 500 DEG C, most preferably more than 600 DEG C.Above-mentioned solder portion is relatively low due to fusing point, because
This is melted when being conductively connected.Above-mentioned second conductive part is not melted preferably when being conductively connected.Above-mentioned electroconductive particle is excellent
Choosing is to make melt solder and use, and above-mentioned solder portion is melted and is used, and preferably makes above-mentioned solder portion
Melt and above-mentioned second conductive part is melted and is used.By making the fusing point of above-mentioned second conductive part than above-mentioned solder portion
Fusing point is high, so as to when being conductively connected, can not melt above-mentioned second conductive part and only melt above-mentioned solder portion.
The absolute value of the difference of the fusing point of the fusing point of above-mentioned solder portion and above-mentioned second conductive part is more than 0 DEG C, preferably 5 DEG C
More than, more preferably more than 10 DEG C, more preferably more than 30 DEG C, particularly preferably more than 50 DEG C, most preferably
More than 100 DEG C.
Above-mentioned second conductive part preferably includes metal.The metal for constituting above-mentioned second conductive part is not specifically limited.
As the metal, can for example enumerate gold, silver, copper, platinum, palladium, zinc, lead, aluminium, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, germanium and cadmium and
Their alloy etc..In addition, as above-mentioned metal, the indium oxide (ITO) for mixing tin can also be used.Above-mentioned metal both can only make
With one kind, it can also use two or more simultaneously.
Above-mentioned second conductive part is preferably nickel dam, palladium layers, layers of copper or layer gold, more preferably nickel dam or layer gold,
More preferably layers of copper.Electroconductive particle preferably has nickel dam, palladium layers, layers of copper or layer gold, more preferably has
Nickel dam or layer gold, more with preferably layers of copper.By these being had the electroconductive particle of preferred conductive part use
In interelectrode connection, so as to further reduce interelectrode connection resistance.In addition, can these preferred conductive parts table
Face is further readily formed solder portion.
The thickness of above-mentioned solder portion is preferably more than 0.005 μm, more preferably more than 0.01 μm, and preferably 10
Below μm, more preferably less than 1 μm, more preferably less than 0.3 μm.If the thickness of solder portion be above-mentioned lower limit more than with
And below the above-mentioned upper limit, then sufficient electric conductivity can be obtained, and electroconductive particle will not become really up to the mark, in interelectrode connection
When electroconductive particle is fully deformed.
The average grain diameter of above-mentioned electroconductive particle is preferably more than 0.5 μm, more preferably more than 1 μm, more preferably
Be more than 3 μm, particularly preferably more than 5 μm, and preferably less than 100 μm, more preferably less than 60 μm, further
Preferably less than 40 μm, more preferably less than 30 μm, it is even furthermore preferable that less than 20 μm, particularly preferably 15
Below μm, most preferably less than 10 μm.If the average grain diameter of above-mentioned electroconductive particle be above-mentioned lower limit more than and it is above-mentioned on
Limit is following, then can be further efficiently by electroconductive particle configuration on electrode.The average grain diameter of above-mentioned electroconductive particle
Particularly preferably more than 3 μm, less than 30 μm.
" average grain diameter " of above-mentioned electroconductive particle represents number average particle diameter.The average grain diameter of electroconductive particle for example passes through
With electron microscope or the arbitrary electroconductive particle of observation by light microscope 50 and calculate average value or carry out swash light ー spread out
Formula particle size distribution is penetrated to obtain.
The coefficient of alteration of the particle diameter of above-mentioned electroconductive particle is preferably more than 5%, should be preferably more than 10%, and excellent
Choosing is less than 40%, more preferably less than 30%.If the coefficient of alteration of above-mentioned particle diameter is more than above-mentioned lower limit and above-mentioned
Below the upper limit, then solder further can be efficiently configured on electrode.Wherein, the variation of the particle diameter of above-mentioned electroconductive particle
Coefficient might be less that 5%.
Above-mentioned coefficient of alteration (CV values) passes through following formula subrepresentation.
CV values (%)=(ρ/Dn) × 100
ρ：The standard deviation of the particle diameter of electroconductive particle
Dn：The average value of the particle diameter of electroconductive particle
The shape of above-mentioned electroconductive particle is not specifically limited.The shape of above-mentioned electroconductive particle both can be it is spherical,
Shape that can be with flat etc. in addition to spherical shape.
In the above-mentioned weight % of conductive material 100, the content of above-mentioned electroconductive particle is preferably more than 1 weight %, more
Preferably more than 2 weight %, more preferably more than 10 weight %, particularly preferably more than 20 weight %, most preferably
Be more than 30 weight %, and preferably below 80 weight %, more preferably below 60 weight %, more preferably 50
Below weight %.If the content of above-mentioned electroconductive particle is more than above-mentioned lower limit and below the above-mentioned upper limit, it can more enter one
Step efficiently configures electroconductive particle on electrode, electroconductive particle easily can be more configured between electrode, conducting can
Further improved by property.For the further viewpoint for improving conducting reliability, the content of preferably above-mentioned electroconductive particle compared with
It is many.
(Thermocurable compound：Thermocurable composition)
Above-mentioned Thermocurable compound is can be by the compound that is heating and curing.As above-mentioned Thermocurable compound,
It can enumerate：Oxetane compound, epoxide, episulfide compound, (methyl) acyclic compound, phenol chemical combination
Thing, amino-compound, unsaturated polyester compound, urethanes, polysiloxane compound and polyimide compound etc..
Wherein, it is excellent for making the curability and viscosity of conductive material further good and further improving the viewpoint of connection reliability
Choosing is epoxide.One kind can be used only in above-mentioned Thermocurable compound, can also be simultaneously using two or more.
As above-mentioned epoxide, aromatic epoxy compound can be enumerated.These, it is preferred to resorcinol type epoxy
The crystallinity epoxy compounds such as compound, naphthalene type epoxide, biphenyl type epoxy compound, diphenyl ketone type epoxide
Thing.Preferably normal temperature (23 DEG C) be solid and melting temperature be below the fusing point of solder epoxide.Melting temperature
Preferably less than 100 DEG C of degree, more preferably less than 80 DEG C, and preferably more than 40 DEG C.By using above-mentioned preferred
Epoxide, make connecting object part fit stage viscosity it is higher, by convey etc. impact assign acceleration
When, the position skew of the first connecting object part and the second connecting object part can be suppressed, in addition, utilizing heat when solidifying
Amount, can be greatly lowered the viscosity of conductive material, so as to make the cohesion of semiconductor particles efficiently carry out.
In the above-mentioned weight % of conductive material 100, the content of above-mentioned Thermocurable compound be preferably 20 weight % with
On, more preferably more than 40 weight %, more preferably more than 50 weight %, and preferably below 99 weight %, more
Preferably below 98 weight %, more preferably below 90 weight %, particularly preferably below 80 weight %.For entering
One step improves the viewpoint of impact resistance, and the content of preferably above-mentioned Thermocurable compound is more.
(thermal curing agents：Thermocurable composition)
Above-mentioned thermal curing agents make above-mentioned Thermocurable compound heat cure.As above-mentioned thermal curing agents, it can enumerate：Imidazoles is consolidated
The polythiol hardeners such as agent, amine hardener, phenol cured agent, polythiol curing agent, acid anhydrides, hot cationic initiator (heat sun from
Sub- curing agent) and hot radical producing agent etc..One kind can also be used alone in above-mentioned thermal curing agents, can also be applied in combination two kinds
More than.
Conductive material can be made further promptly to solidify in low temperature, it is therefore preferable that imidazole curing agent, polythiol hardener
Or amine hardener.In addition, when mixing Thermocurable compound and above-mentioned thermal curing agents, storage stability is improved, it is therefore preferable that
Latent curing agent.Latent curing agent is preferably that latency imidazole curing agent, latency polythiol hardener or latency amine are solid
Agent.In addition, above-mentioned thermal curing agents can also be coated by the polymer substance of polyurethane resin or polyester resin etc..
It is not particularly limited, can enumerates as above-mentioned imidazole curing agent：2-methylimidazole, 2-ethyl-4-methylimidazole,
1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-phenylimidazole trimellitic acid salt, 2,4- diaminourea -6- [2'- methylimidazoles
Base-(1')]-ethyl-s-triazine and 2,4- diaminourea -6- [2'- methylimidazolyls-(1']-ethyl-s-triazine isocyanuric acid adds
Into thing etc..
It is not particularly limited, can includes as above-mentioned polythiol curing agent：Trimethylolpropane tris -3- mercaptopropionic acids
Ester, six -3-thiopropionate of four -3-thiopropionate of pentaerythrite and dipentaerythritol etc..
It is not particularly limited, can enumerates as above-mentioned amine hardener：Hexamethylene diamine, eight methylene diamines, ten methylenes
Double (3- aminopropyls) -2,4,8,10- tetra- spiral shell [5.5] hendecanes of base diamines, 3,9-, double (4- aminocyclohexyls) methane,
Phenylenediamine and diamino diphenyl sulfone etc. are lifted.
As above-mentioned hot cationic initiator, iodine cationoid curing agent (hot cation curing agent), oxygen can be enumerated
Cationoid curing agent and sulphur cationoid curing agent etc..As above-mentioned iodine cationoid curing agent, double (uncles 4_ can be enumerated
Butyl phenyl) iodine hexafluorophosphate etc..As above-mentioned oxygen cationoid curing agent, trimethyl oxygen tetrafluoro boric acid can be enumerated
Salt etc..As above-mentioned sulphur cationoid curing agent, it can enumerate three-p- tolyl sulphur hexafluorophosphate etc..
As above-mentioned hot radical producing agent, it is not particularly limited, azo-compound and organic peroxide etc. can be enumerated.
As above-mentioned azo-compound, azodiisobutyronitrile (AIBN) etc. can be enumerated.As above-mentioned organic peroxide, it can enumerate two-
Tert-butyl peroxide and methyl-ethyl-ketone peroxide etc..
The reaction start temperature of above-mentioned thermal curing agents is preferably more than 50 DEG C, more preferably more than 70 DEG C, more excellent
Choosing is more than 80 DEG C, and preferably less than 250 DEG C, more preferably less than 200 DEG C, more preferably less than 150 DEG C,
Particularly preferably less than 140 DEG C.If the reaction start temperature of above-mentioned thermal curing agents is more than above-mentioned lower limit and the above-mentioned upper limit
Hereinafter, then can be further efficiently by solder configuration on electrode.The reaction start temperature of above-mentioned thermal curing agents is particularly preferred
It is more than 80 DEG C, less than 140 DEG C.
For viewpoint further efficiently by solder configuration on electrode, the reaction start temperature of above-mentioned thermal curing agents
Fusing point preferably than above-mentioned solder is high, more preferably high more than 5 DEG C, more preferably high more than 10 DEG C.
The reaction start temperature of above-mentioned thermal curing agents means the temperature begun to ramp up of the heating peak value in DSC.
The content of above-mentioned thermal curing agents is not specifically limited.It is above-mentioned relative to the above-mentioned parts by weight of Thermocurable compound 100
The content of thermal curing agents is preferably more than 0.01 parts by weight, more than more preferably 1 parts by weight, and preferably 200 weight
Below part, below more preferably 100 parts by weight, below more preferably 75 parts by weight.If the content of thermal curing agents is upper
State more than lower limit, then easily cure sufficiently conductive material.If the content of thermal curing agents is below the above-mentioned upper limit, after solidification
The unnecessary thermal curing agents for being not used for solidification are difficult to remain, and further improve the heat resistance of solidfied material.
(fluxing agent)
Above-mentioned conductive material preferably includes fluxing agent.By the use of fluxing agent, can further effectively will
Solder is configured on electrode.In addition, by the discovery of fluxing agent effect, interelectrode connection resistance is further reduced.It is above-mentioned to help
Flux is not specifically limited.As fluxing agent, the fluxing agent being generally used in solder engagement etc. can be used.Helped as above-mentioned
Flux, can be enumerated for example：Zinc chloride, the mixture of zinc chloride and inorganic halides, the mixture of zinc chloride and inorganic acid, melting
Salt, phosphoric acid, the derivative of phosphoric acid, organohalogen compounds, hydrazine, organic acid and rosin etc..Above-mentioned fluxing agent can be used alone one kind,
It can also be applied in combination two or more.
As above-mentioned fuse salt, ammonium chloride etc. can be enumerated.As above-mentioned organic acid, lactic acid, citric acid, tristearin can be enumerated
Acid, glutamic acid and glutaric acid etc..As above-mentioned rosin, activation rosin and disactivation rosin etc. can be enumerated.Above-mentioned fluxing agent is preferred
For organic acid and rosin containing two or more carboxyl.Above-mentioned fluxing agent can be the organic acid containing more than two carboxyls,
Can also be rosin.By the use of the organic acid with two or more carboxyl, rosin, interelectrode conducting is further improved
Reliability.
Above-mentioned rosin is the rosin using rosin acid as principal component.Fluxing agent is preferably rosin, more preferably rosin acid.
By the use of the preferred fluxing agent, interelectrode conducting reliability is further improved.
The active temperature (fusing point) of above-mentioned fluxing agent is preferably more than 50 DEG C, more preferably more than 70 DEG C, more excellent
Choosing is more than 80 DEG C, and preferably less than 200 DEG C, more preferably less than 190 DEG C, it is further preferred that 160 DEG C with
Under, more preferably less than 150 DEG C, it is even furthermore preferable that less than 140 DEG C.If the active temperature of above-mentioned fluxing agent is upper
State more than lower limit and below the above-mentioned upper limit, then can effectively further play fluxing agent effect, further will efficiently can weld
Material configuration is on electrode.The active temperature (fusing point) of above-mentioned fluxing agent is preferably more than 80 DEG C, less than 190 DEG C.It is above-mentioned fluxing
The active temperature (fusing point) of agent is particularly preferably more than 80 DEG C, less than 140 DEG C.
As the above-mentioned fluxing agent that the active temperature (fusing point) of net fluxing agent is more than 80 DEG C, less than 190 DEG C, amber can be enumerated
Amber acid (186 DEG C of fusing point), glutaric acid (96 DEG C of fusing point), adipic acid (152 DEG C of fusing point), pimelic acid (104 DEG C of fusing point), suberic acid
Dicarboxylic acids, benzoic acid (122 DEG C of fusing point), the malic acid (130 DEG C of fusing point) of (142 DEG C of fusing point) etc. etc..
In addition, the boiling point of above-mentioned fluxing agent is preferably less than 200 DEG C.
For solder efficiently further is configured into the viewpoint on electrode, the fusing point of above-mentioned fluxing agent is preferably than upper
The fusing point for stating solder is high, more preferably high more than 5 DEG C, more preferably high more than 10 DEG C.
For solder efficiently further is configured into the viewpoint on electrode, the fusing point of above-mentioned fluxing agent is preferably than upper
The reaction start temperature for stating thermal curing agents is high, more preferably high more than 5 DEG C, more preferably high more than 10 DEG C.
Above-mentioned fluxing agent can be both dispersed in conductive material, can also be attached on the surface of electroconductive particle.
Above-mentioned fluxing agent discharges the fluxing agent of cation preferably by heating.By using by heating release cation
Fluxing agent, can further efficiently by solder configuration on electrode.
As the fluxing agent that cation is discharged by above-mentioned heating, above-mentioned hot cationic initiator (hot cation can be enumerated
Curing agent).
In the above-mentioned weight % of conductive material 100, the content of above-mentioned fluxing agent is preferably more than 0.5 weight %, and excellent
Choosing is more preferably below 25 weight % below 30 weight %.Above-mentioned conductive material can also not include fluxing agent.If helping
The content of flux is that then oxide film thereon is more difficult to the surface in solder and electrode more than above-mentioned lower limit and below the above-mentioned upper limit
Formed, moreover, the oxide film thereon on the surface for being formed at solder and electrode can be removed effectively further.
(filler)
Filler can be added in above-mentioned conductive material.Filler both can be organic filler or inorganic filler.Pass through
The addition of filler, can suppress solder and produce the distance of cohesion, and make electroconductive particle equably on the whole electrode of substrate
Cohesion.
In the above-mentioned weight % of conductive material 100, the content of above-mentioned filler is preferably more than 0 weight % (not containing),
And preferably below 5 weight %, more preferably below 2 weight %, more preferably below 1 weight %.If above-mentioned fill out
The content of material is that more than above-mentioned lower limit and below the above-mentioned upper limit, then further efficiently can configure solder on electrode.
(other compositions)
Above-mentioned conductive material can be as needed, for example, contain filler, extender, softening agent, plasticizer, polymerization catalyzed
Agent, curing catalysts, colouring agent, antioxidant, heat stabilizer, light stabilizer, ultra-violet absorber, lubricant, antistatic additive
And the various additives such as fire retardant.
(manufacture method of connecting structure body and connecting structure body)
The connecting structure body of the present invention possesses the first connecting object part, the table on surface with least one first electrode
The second connecting object part on face with least one second electrode and by above-mentioned first connecting object part and above-mentioned the
The connecting portion of two connecting object parts connection.In the connecting structure body of the present invention, the material of above-mentioned connecting portion is above-mentioned conduction
Material, above-mentioned connecting portion is formed by above-mentioned conductive material.In the connecting structure body of the present invention, above-mentioned first electrode and above-mentioned the
Two electrodes utilize the solder electrical connection in above-mentioned electroconductive particle.The present invention connecting structure body in, above-mentioned first electrode with
Above-mentioned second electrode utilizes the solder portion electrical connection in above-mentioned connecting portion.
The manufacture method of the connecting structure body of the present invention possesses：Using above-mentioned conductive material, there is at least one on surface
The process that above-mentioned conductive material is configured on the surface of first connecting object part of first electrode；Above-mentioned conductive material with it is upper
State on the opposite surface of the first connecting object component side, surface is had to the second connecting object part of at least one second electrode
The process configured in the mode for making above-mentioned first electrode opposed with above-mentioned second electrode；And by by above-mentioned conductive material
More than the fusing point for the solder being heated in above-mentioned electroconductive particle, formed using above-mentioned conductive material by above-mentioned first connecting object
The connecting portion that part is connected with above-mentioned second connecting object part, and by the solder portion in above-mentioned connecting portion by above-mentioned first
The process that electrode is electrically connected with above-mentioned second electrode.Above-mentioned conductive material is preferably heated to above-mentioned Thermocurable compound
Solidification temperature more than.
It is specific due to having used in the manufacture method of connecting structure body of the invention and the connecting structure body of the present invention
Conductive material, therefore solder in electroconductive particle is easily gathered between first electrode and second electrode, can be efficiently
By solder configuration on electrode (line).In addition, a part for solder is difficult to be configured at the region for being formed without electrode (space), energy
Enough amounts for rather reducing the solder for being configured at the region for being formed without electrode.Therefore, it is possible to improve first electrode and second electrode
Between conducting reliability.Further, it is possible to prevent not attachable interelectrode electrical connection adjacent in the horizontal, it is possible to increase
Insulating reliability.
In addition, being configured at not to efficiently configure on electrode, and rather reduce the solder in electroconductive particle
It is formed with the amount of the solder in the region of electrode, preferably conductive paste and not above-mentioned conductive material conducting film.
The thickness of interelectrode solder portion is preferably more than 10 μm, more preferably more than 20 μm, and preferably 100
Below μm, more preferably less than 80 μm.Solder area on the surface of electrode is (in the area 100% exposed of electrode
Solder contact area) be preferably more than 50%, more preferably more than 70%, and preferably less than 100%.
In the manufacture method of the connecting structure body of the present invention, configure the process of above-mentioned second connecting object part and
In the process for forming above-mentioned connecting portion, preferably without pressurization, but the weight of above-mentioned second connecting object part is applied
Above-mentioned conductive material is added on, the process of above-mentioned second connecting object part is being configured and is being formed in the process of above-mentioned connecting portion,
Do not apply the moulding pressure of the power of the weight more than above-mentioned second connecting object part to above-mentioned conductive material preferably.Upper
In the case of stating, the uniformity of the amount of solder in multiple solder portions can be further improved.Moreover, further can effectively add
The thickness of thick solder portion, makes solder be easy to be gathered between electrode in large quantities, can be further efficiently by solder configuration in electrode
On (line).In addition, a part for solder is difficult to be configured at the region for being formed without electrode (space), configuration can be further reduced
In the amount of the solder in the region for being formed without electrode.Therefore, it is possible to further improve interelectrode conducting reliability.Moreover, energy
It is enough further to prevent not attachable interelectrode electrical connection adjacent in the horizontal, it can further improve insulating reliability.
In addition, if using conductive paste simultaneously non-conductive film, then easily adjusted and connected according to the coated weight of conductive paste
Portion and the thickness of solder portion.On the other hand, there are the following problems for conducting film：, must for the thickness of variations or modifications connecting portion
The conducting film of different-thickness must be prepared or prepare the conducting film of specific thickness.In addition, there are the following problems in the conductive film：In weldering
Under the melting temperature of material, exist and be difficult to the trend that the melt viscosity for making conducting film is fully reduced, tend to interfere with the cohesion of solder.
Hereinafter, while illustrating the specific embodiment of the present invention referring to the drawings one side.
Fig. 1 is the section for showing schematically the connecting structure body obtained using the conductive material of one embodiment of the present invention
Figure.
Connecting structure body 1 shown in Fig. 1 possesses the first connecting object part 2, the second connecting object part 3 and by
The connecting portion 4 that one connecting object part 2 is connected with the second connecting object part 3.Connecting portion 4 is formed by above-mentioned conductive material.
In present embodiment, above-mentioned conductive material includes multiple electroconductive particles, Thermocurable compound and thermal curing agents.It is above-mentioned
Thermocurable compound and above-mentioned thermal curing agents are Thermocurable compositions.
Connecting portion 4 has the solder portion 4A that multiple electroconductive particles gather and are bonded with each other and makes Thermocurable composition thermosetting
The solidfied material portion 4B changed.
First connecting object part 2 has multiple first electrode 2a in surface (upper surface).Second connecting object part 3 exists
Surface (lower surface) has multiple second electrode 3a.First electrode 2a is electrically connected with second electrode 3a by solder portion 4A.Therefore,
First connecting object part 2 is electrically connected with the second connecting object part 3 by solder portion 4A.In addition, in connecting portion 4, with
Weldering is not present in the different region (solidfied material portion 4B parts) of the solder portion 4A that is collected between first electrode 2a and second electrode 3a
Material.The solder for departing from solder portion 4A is not present in the region (solidfied material portion 4B parts) different from solder portion 4A.In addition, if
On a small quantity, then solder may reside in the regions different from the solder portion 4A being collected between first electrode 2a and second electrode 3a
(solidfied material portion 4B parts).
As shown in figure 1, in connecting structure body 1, gathering between first electrode 2a and second electrode 3a has multiple conductions
Property particle, after the melting of multiple electroconductive particles, the fused mass of electroconductive particle makes the moistened surface of electrode extend solidify afterwards so that
Form solder portion 4A.Therefore, solder portion 4A and first electrode 2a and solder portion 4A and second electrode 3a connection area becomes
Greatly.That is, by using electroconductive particle, be located at the outer surface of electric conductivity nickel, gold or copper etc. metal electric conductivity grain
The situation of son is compared, and solder portion 4A and first electrode 2a and solder portion 4A and second electrode 3a contact area becomes big.Cause
This, the conducting reliability and connection reliability in connecting structure body 1 are for height.In addition, conductive material can also include fluxing agent.
In the case of using fluxing agent, generally, fluxing agent can gradually be inactivated because of heating.
In addition, in the connecting structure body 1 shown in Fig. 1, solder portion 4A be entirely located in first, second electrode 2a, 3a it
Between opposed region.In the connecting structure body 1X of variation shown in Fig. 3, the connecting structure shown in only connecting portion 4X and Fig. 1
Body 1 is different.Connecting portion 4X has solder portion 4XA and solidfied material portion 4XB.Can also be as connecting structure body 1X, a large amount of solders
Portion 4XA is located at first, second electrode 2a, 3a opposed region, and a solder portion 4XA part is from first, second electrode 2a, 3a
Opposed region it is prominent to side.From the solder portion 4XA that first, second electrode 2a, 3a opposed region is prominent to side
It is a solder portion 4XA part, not departs from solder portion 4XA solder.In addition, in the present embodiment, disengaging can be reduced
The amount of the solder of solder portion, but depart from solder portion solder can also be present in solidfied material portion.
If reducing the usage amount of electroconductive particle, connecting structure body 1 is readily available.If increasing electroconductive particle
Usage amount, then be readily available connecting structure body 1X.
For the further viewpoint for improving conducting reliability, in connecting structure body 1,1X, along first electrode 2a with being connected
When portion 4,4X and second electrode the 3a opposite parts of stacked direction observation first electrode 2a and second electrode 3a, it is preferably
More than 50% in the area 100% of part opposite with second electrode 3a first electrode 2a is configured with connecting portion 4,4X
Solder portion 4A, 4XA.
For the further viewpoint for improving conducting reliability, along above-mentioned first electrode, above-mentioned connecting portion and above-mentioned the
When the stacked directions of two electrodes observes the above-mentioned first electrode part opposite with above-mentioned second electrode, it is preferably above-mentioned the
More than 50% in the area 100% of the one electrode part opposite with above-mentioned second electrode (is more preferably more than 60%, more
Plus preferably more than 70%, particularly preferably more than 80%, most preferably more than 90%) it is configured with above-mentioned connecting portion
Solder portion.
For the further viewpoint for improving conducting reliability, along with above-mentioned first electrode, above-mentioned connecting portion and above-mentioned
When the above-mentioned first electrode part opposite with above-mentioned second electrode is observed in the orthogonal direction of the stacked direction of second electrode, preferably
Be to be configured with 70% of the solder portion in above-mentioned connecting portion in the above-mentioned first electrode part opposite with above-mentioned second electrode
More than (more preferably more than 80%, more preferably more than 90%, particularly preferably more than 95%, most preferably
More than 99%).
Next, using the conductive material of one embodiment of the present invention, illustrating to manufacture the one of the method for connecting structure body 1
Individual example.
First, the first connecting object part 2 that there is first electrode 2a in surface (upper surface) is prepared.Next, such as Fig. 2
(a) shown in, configuration contains Thermocurable composition 11B and multiple electroconductive particle 11A on the surface of the first connecting object part 2
Conductive material 11 (the first process).Conduction material is configured on the surface provided with first electrode 2a of the first connecting object part 2
Material 11.Configure after conductive material 11, electroconductive particle 11A is configured on first electrode 2a (line) and be formed without the first electricity
Both on pole 2a region (space).
As the collocation method of conductive material 11, it is not specifically limited, the coating carried out using point gum machine, silk screen can be enumerated
Printing and the spraying that passes through ink discharge device etc..
In addition, preparing surface (lower surface) has second electrode 3a the second connecting object part 3.Next, such as Fig. 2
(b) shown in, in the conductive material 11 on the surface of the first connecting object part 2, it is connected in conductive material 11 with first pair
As the opposite side in the side of part 2 surface on configure the second connecting object part 3 (the second process).On the surface of conductive material 11
On, the second connecting object part 3 is configured from second electrode 3a sides.Now, make first electrode 2a opposed with second electrode 3a.
Next, conductive material 11 is heated to more than electroconductive particle 11A fusing point (the 3rd process).Preferably will
Conductive material 11 is heated to more than Thermocurable composition 11B (bonding agent) solidification temperature.In the heating, it is present in and is not formed
The electroconductive particle 11A in the region of electrode gathers (self-coagulation effect) between first electrode 2a and second electrode 3a.In this reality
Apply in mode, due to using conductive material and simultaneously non-conductive film, and because conductive material also has specific composition, therefore
Electroconductive particle 11A effectively gathers between first electrode 2a and second electrode 3a.In addition, electroconductive particle 11A melting and
It is bonded with each other.In addition, Thermocurable composition 11B carries out heat cure.As a result, as shown in Fig. 2 (c), utilizing the shape of conductive material 11
Into the connecting portion 4 for being connected the first connecting object part 2 with the second connecting object part 3.Connected using the formation of conductive material 11
Portion 4, and solder portion 4A is formed by multiple electroconductive particle 11A engagements, form solid by Thermocurable composition 11B heat cures
Compound portion 4B.If electroconductive particle 11A is fully moved, from being not located at leading between first electrode 2a and second electrode 3a
After conductive particles 11A mobile beginning, until being moved between first electrode 2a and second electrode 3a for electroconductive particle 11A is tied
Beam, can not remain temperature constant.
In the present embodiment, in above-mentioned second process and above-mentioned 3rd process, preferably without pressurization.This
When, apply the weight of the second connecting object part 3 to conductive material 11.Therefore, when forming connecting portion 4, electroconductive particle 11A
Effectively it is collected between first electrode 2a and second electrode 3a.If in addition, in above-mentioned second process and above-mentioned 3rd work
The interior at least one party of sequence is pressurizeed, then the effect being collected in electroconductive particle between first electrode and second electrode is carried out
The trend of obstruction is uprised.
But, if it is possible to ensure the interval of first electrode and second electrode, then can also be pressurizeed.As ensuring electricity
The mode at the interval of interpolar, as long as such as addition is equivalent to the spacer at desired interelectrode interval, and is configured between electrode
At least one, the preferably spacer of more than three.As spacer, inorganic particulate, organic filler can be enumerated.Isolation
Thing is preferably insulating properties particle.
In addition, in the present embodiment, due to being coated with without pressurization, therefore by the coincidence of the second connecting object part
When on the first connecting object part of conductive material, even in the electrode of the first connecting object part and the second connecting object portion
The alignment of the electrode of part occurs in the state of deviation, the situation for making the first connecting object part be overlapped with the second connecting object part
Under, the deviation can be also corrected, and the electrode of the first connecting object part is connected with the electrode of the second connecting object part (certainly
Orientation effect).Because, the self-coagulation between the electrode of the first connecting object part and the electrode of the second connecting object part
Melting after solder in, the solder between the electrode of the electrode of the first connecting object part and the second connecting object part is with leading
The energy that the area of the other compositions contact of electric material is minimum is relatively stable, therefore connection of the adjustment as this minimum area
Power of the construction i.e. in the presence of the connecting structure of alignment plays a role.Now, it may be desirable to conductive material it is uncured and the temperature,
The viscosity of composition beyond time, the electroconductive particle of conductive material is substantially low.
So, the connecting structure body 1 shown in Fig. 1 is obtained.In addition, above-mentioned second process can also connect with above-mentioned 3rd process
Carry out continuously.Alternatively, it is also possible to after above-mentioned second process is carried out, make the first connecting object part 2, the conductive material of acquisition
11 and second the layered product of connecting object part 3 be moved to heating part, carry out above-mentioned 3rd process.In order to carry out above-mentioned add
Heat, can also configure above-mentioned layered product on heater block, and above-mentioned layered product can also be configured in the space of heating.
Above-mentioned heating-up temperature in above-mentioned 3rd process is preferably more than 140 DEG C, more preferably more than 160 DEG C, and
Preferably less than 450 DEG C, more preferably more preferably less than 250 DEG C, less than 200 DEG C.
In addition, after above-mentioned 3rd process, for the purpose of the doing over again of the amendment of position and manufacture, it can be shelled from connecting portion
From the first connecting object part or the second connecting object part.Heating-up temperature preferably electric conductivity for carrying out the stripping
It is more than the fusing point of particle, more preferably more than+10 DEG C of the fusing point (DEG C) of electroconductive particle.Heating temperature for carrying out the stripping
Degree can also be below+100 DEG C of the fusing point (DEG C) of electroconductive particle.
As the heating means in above-mentioned 3rd process, it can be set forth in more than the fusing point of electroconductive particle and Thermocurable
It is more than the solidification temperature of composition, using reflow ovens or using the overall method of oven heat connecting structure body, or only partly
The method for heating the connecting portion of connecting structure body.
As utensil used in the method for local heating, it can enumerate：Heating plate, assign the heat gun of hot blast, flatiron and
Infrared heater etc..
In addition, when carrying out local heating using heating plate, being preferably as follows to form heating plate upper surface：Immediately below connecting portion
Formed using the higher metal of heat conductivity, other positions preferably do not heated are relatively low using heat conductivities such as fluororesin
Material is formed.
Above-mentioned first, second connecting object part is not specifically limited.As above-mentioned first, second connecting object part,
It can specifically enumerate：The electronics zero such as semiconductor chip, semiconductor packages, LED chip, LED encapsulation, capacitor and diode
Part and resin film, printed base plate, flexible printing substrate, flexble flat's cable, rigid-flexible combination substrate, glass epoxy substrate and
Electronic component of the circuit substrates such as glass substrate etc. etc..Above-mentioned first, second connecting object part is preferably electronic unit.
At least one party in above-mentioned first connecting object part and above-mentioned second connecting object part is preferably resin
Film, flexible printing substrate, flexble flat's cable or rigid-flexible combination substrate.Above-mentioned second connecting object part is preferably resin
Film, flexible printing substrate, flexble flat's cable or rigid-flexible combination substrate.Resin film, flexible printing substrate, flexble flat's cable with
And rigid-flexible combination substrate has flexibility high and relatively light-dutyer property.Conducting film is being used in such connecting object part
Connection in the case of, conductive particle is difficult to be collected in the trend on electrode.In this regard, by using conductive paste, i.e.,
Resin film, flexible printing substrate, flexble flat's cable or rigid-flexible combination substrate have been used, also can be high by electroconductive particle
It is collected on electrode to effect, thus, it is possible to fully improve interelectrode conducting reliability.Using resin film, flexible printing base
In the case of plate, flexble flat's cable or rigid-flexible combination substrate, with having used other connecting object parts such as semiconductor chip
Situation compare, can obtain further raising without the raising effect of the interelectrode conducting reliability of pressurization.
As the electrode located at above-mentioned connecting object part, it can enumerate：Gold electrode, nickel electrode, tin electrode, aluminium electrode, copper
The metal electrodes such as electrode, molybdenum electrode, silver electrode, SUS electrodes and tungsten electrode.It is flexible printing substrate in above-mentioned connecting object part
In the case of, above-mentioned electrode is preferably gold electrode, nickel electrode, tin electrode, silver electrode or copper electrode.In above-mentioned connecting object part
In the case of for glass substrate, above-mentioned electrode is preferably aluminium electrode, copper electrode, molybdenum electrode, silver electrode or tungsten electrode.In addition, on
Can be the electrode or the superficial layer in metal oxide layer only formed by aluminium in the case of stating electrode and being aluminium electrode
It is laminated with the electrode of aluminium lamination.As the material of above-mentioned metal oxide layer, it can enumerate：Doped with the indium oxide of trivalent metallic element
And the zinc oxide doped with trivalent metallic element etc..As above-mentioned trivalent metallic element, it can enumerate：Sn, Al and Ga etc..
Hereinafter, embodiment and comparative example are enumerated, the present invention is specifically described.The present invention is not limited to following implementation
Example.
Thermocurable compound 1：(crystallinity Thermocurable compound melts 2,4- double (glycidoxypropyl) benzophenone
Point：94 DEG C, molecular weight 362)
The synthesis of 2,4- double (glycidoxypropyl) benzophenone：
2,4-DihydroxyBenzophenone 27g, epichlorohydrin 230g, n-butanol 70g and tetraethyl benzyl are put into 3 mouthfuls of flasks
Ammonium chloride lg, being stirred at room temperature dissolves it.Then, under nitrogen environment, 70 DEG C, under reduced-pressure backflow are warming up under agitation,
Sodium hydrate aqueous solution (the weight % of concentration 48) 45g is added dropwise.It was added dropwise with 4 hours.Then, at 70 DEG C, while using
Dean-Stark pipes remove moisture, while reacting 2 hours.Then, under reduced pressure, unreacted epichlorohydrin is removed.
Obtained reaction product is dissolved in MEK (methyl ethyl ketone)：N-butanol=3：The mixed solvent of 1 (weight ratio)
In 400g, sodium hydrate aqueous solution (the weight % of concentration 10) 5g is added, and heated 2 hours at 80 DEG C.
It is then cooled to which room temperature, washing is carried out using pure water, until washing lotion turns into neutrality.While filtering organic layer, on one side
Divide and take, residual moisture and mixed solvent are removed under reduced pressure, reaction product is obtained.
Using n-hexane, above-mentioned reaction product 34g is purified by recrystallizing, and it is residual by being dried in vacuo removing
Stay solvent composition.
Obtained epoxide：It it is 94 DEG C by DSC fusing point, epoxide equivalent is 176g/eq., is obtained by mass spectrum
Molecular weight be that melt viscosity at 362,150 DEG C is 5mPas.
Differential Scanning Calorimetry determines (DSC) and determines device and condition determination
Device；" X-DSC7000 " of Hitachi-hightech Co., Ltd. manufacture, sample size；3mg, temperature conditionss；
10℃/min
Melt viscosity at 150 DEG C：And ASTM D4287, manufactured using M.S.T.Engineering Co., Ltd.
ICI cone and plate viscometers determine
The measure of epoxide equivalent：Based on JIS K7236：2001 determine
The measure of molecular weight：Determined using mass spectrum GC-MS devices (Jeol Ltd.'s manufacture " JMSK-9 ")
Thermocurable compound 2：4,4 '-bis- (glycidoxypropyl) benzophenone (crystallinity Thermocurable compound,
Fusing point：132 DEG C, molecular weight 362)
The synthesis of 4,4 '-bis- (glycidoxypropyl) benzophenone：
4,4'- dihydroxy benaophenonels 27g, epichlorohydrin 230g, n-butanol 70g and tetraethyl benzyl are put into 3 mouthfuls of flasks
Ammonium chloride lg, being stirred at room temperature dissolves it.Then, under nitrogen environment, 70 DEG C are warming up under agitation, in reduced-pressure backflow
Under, sodium hydrate aqueous solution (the weight % of concentration 48) 45g is added dropwise.It was added dropwise with 4 hours.Then, while using at 70 DEG C
Dean-Stark pipes remove moisture, while reacting 2 hours.Then, unreacted epichlorohydrin is removed under reduced pressure.
Obtained reaction product is dissolved in MEK (methyl ethyl ketone)：N-butanol=3：The mixed solvent of 1 (weight ratio)
In 400g, sodium hydrate aqueous solution (the weight % of concentration 10) 5g is added, is heated 2 hours with 80 DEG C.
It is then cooled to which room temperature, washing is carried out using pure water, until washing lotion turns into neutrality.Filter organic layer while
Divide and take, residual moisture and mixed solvent are removed under reduced pressure, reaction product is obtained.
Using n-hexane, above-mentioned reaction product 34g is purified by recrystallizing, and it is residual by being dried in vacuo removing
Stay solvent composition.
Obtained epoxide：It it is 132 DEG C by DSC fusing point, epoxide equivalent is 176g/eq., is obtained by mass spectrum
Molecular weight be that melt viscosity at 362,150 DEG C is 12mPas.
Thermocurable compound 3：Acrylate copolymer containing epoxy radicals, Japan Oil Co manufacture " MARPROOFG-
0150M”
Thermal curing agents 1：Pentaerythrite four (3- mercaptobutylates), Showa Denko K. K manufacture " CURRANTS
MTPE1”
Latency epoxy thermosetting agent 1：" Fujicure7000 " of T＆KT0KA Co., Ltd. manufacture
Fluxing agent 1：Glutaric acid, Wako Pure Chemical Industries, Ltd.'s manufacture, 152 DEG C of fusing point (active temperature)
The method for making of semiconductor particles 1~2：
Semiconductor particles 1：
SnBi scolding tin particle (" DS-10 " of Co., Ltd. of Mitsui Metal Co., Ltd. manufacture, average grain diameter are added in 3 mouthfuls of flasks
12 μm of (median diameter)) 200g, (KCC of SHIN-ETSU HANTOTAI manufactures " KBM-903 " to silane coupler, 3- aminopropyl trimethoxies
Base silane) 10g, toluene 120g and water 1g, Dean-Stark device reactions are used under 80 DEG C of nitrogen environment 3 hours, thus
Make the Sn-OH dehydration contractings from the silanol group of the methoxyl group of 3- aminopropyl trimethoxysilanes and the surface of semiconductor particles
Close.
Afterwards, semiconductor particles are reclaimed using 10 μm of CMF filters, cleaning has been sufficiently carried out with acetone.
The semiconductor particles are moved into 3 mouthfuls of flasks, acetone 200g, glutaric acid anhydride 40g are put into, under 60 DEG C of nitrogen environment
Using Dean-Stark device reactions 3 hours, thus make 3- aminopropyl trimethoxysilanes amino and from glutaric acid without
The carboxyl of one side of water thing is reacted.Afterwards, semiconductor particles are reclaimed using 10 μm of CMF filters, is sufficiently carried out with acetone
Cleaning.
With sieve, at top, 20 μm carry out topping (removing of oversize grain), obtain average grain diameter be 12 μm, CV values be
20% and surface have from glutaric acid anhydride the opposing party carboxyl semiconductor particles 1.
Semiconductor particles 2：
Except 3- aminopropyl trimethoxysilanes are changed into silane coupler, (KCC of SHIN-ETSU HANTOTAI manufactures
" KBM-603 ", N-2- (aminoethyl) -3- aminopropyl trimethoxysilanes) beyond in an identical manner, obtain solder
Particle 2.Average grain diameter is 12 μm, and CV values are 20%.
Semiconductor particles A：(Co., Ltd. of Mitsui Metal Co., Ltd. manufactures " DS-10 " to SnBi semiconductor particles, average grain diameter (middle grain
Footpath) 12 μm)
(the CV values of semiconductor particles)
Determined using laser diffraction formula particle size distribution device (hole makes Co., Ltd. of institute manufacture " LA-920 ")
CV values.
(embodiment 1~6 and comparative example 1)
Composition shown in following tables 1 is coordinated with the use level shown in following tables 1, anisotropic conductive paste is obtained
Agent.
The making of (1) first connecting structure body (L/S=50 μm/50 μm)
(condition A)
Using the anisotropic conductive paste being just fabricated to, first, second, third connecting structure has been made as described below
Body.
(condition B)
Moreover, using the anisotropic conductive paste being just fabricated to, first, second, third company has been made as described below
Connect tectosome.Now, in the upper surface of glass epoxy substrate, with the anisotropic conductive paste that has just been fabricated in glass ring epoxide
The electrode of plate turns into the mode of upper 100 μm of thickness, using metal mask, is coated by silk-screen printing, forms anisotropy
Electroconductive paste oxidant layer, then, under atmospheric environment, after being placed 10 hours with 23 DEG C, 50%RH, in anisotropic conductive paste layer
Upper surface flexible printing substrate is laminated in the mode for making electrode opposite each other.It is set to identical with condition A in addition.
Paste (anisotropic conductive paste layer) after above-mentioned placement is reclaimed and viscosity is determined.
(the specific preparation method of connecting structure body)
Preparing upper surface has the copper electrode pattern (thickness 12 of copper electrode that L/S is 50 μm/50 μm, electrode length is 3mm
μm) glass epoxy substrate (FR-4 substrates) (the first connecting object part).In addition, prepare lower surface have L/S for 50 μm/
50 μm, flexible printing substrate (the second connecting object portion for the copper electrode pattern (12 μm of the thickness of copper electrode) that electrode length is 3mm
Part).
The area of glass epoxy substrate and flexible printing substrates while stacking is set to 1.5cm × 3mm, and connection electrode number is set to 75
It is right.
In the upper surface of above-mentioned glass epoxy substrate, with the anisotropic conductive paste that has just been fabricated in glass epoxy substrate
Electrode on turn into 100 μm of thickness mode, using metal mask, be coated by silk-screen printing, formed anisotropy lead
Electric paste layer.Next, being laminated above-mentioned scratch in the upper surface of anisotropic conductive paste layer in the mode for making electrode opposite each other
Property printed base plate.Now, without pressurization.Apply the weight of above-mentioned flexible printing substrate to anisotropic conductive paste layer.It
Afterwards, while being heated so that the temperature of anisotropic conductive paste layer turns into 190 DEG C, while make melt solder, and make each
Anisotropy electroconductive paste oxidant layer is solidified for 10 seconds with 190 DEG C, obtains the first connecting structure body.
The making of (2) second connecting structure bodies (L/S=75 μm/75 μm)
Preparing upper surface has the copper electrode pattern (thickness 12 of copper electrode that L/S is 75 μm/75 μm, electrode length is 3mm
μm) glass epoxy substrate (FR-4 substrates) (the first connecting object part).In addition, prepare lower surface have L/S for 75 μm/
75 μm, flexible printing substrate (the second connecting object portion for the copper electrode pattern (12 μm of the thickness of copper electrode) that electrode length is 3mm
Part).
In addition to the above-mentioned glass epoxy substrate and flexible printing substrate different using L/S, with the first connecting structure
As the making of body, the second connecting structure body is obtained.
The making of (3) the 3rd connecting structure bodies (L/S=100 μm/100 μm)
Preparing upper surface has the copper electrode pattern (thickness of copper electrode that L/S is 100 μm/100 μm, electrode length is 3mm
12 μm) glass epoxy substrate (FR-4 substrates) (the first connecting object part).In addition, preparing lower surface there is L/S to be 100 μ
M/100 μm, flexible printing substrate (the second connection pair for the copper electrode pattern (12 μm of the thickness of copper electrode) that electrode length is 3mm
As part).
In addition to the above-mentioned glass epoxy substrate and flexible printing substrate different using L/S, with the first connecting structure
As the making of body, the 3rd connecting structure body is obtained.
(evaluation)
(1) viscosity
Using E types viscosimeter (Toki Sangyo Co., Ltd. manufactures " TVE22L "), surveyed under conditions of 25 DEG C and 5rpm
Determine 25 DEG C of viscosity (η 25) of anisotropic conductive paste.
(2) thickness of solder portion
Section observation is carried out to the first connecting structure body of acquisition, thus, the solder between the electrode above and below being located at is evaluated
The thickness in portion.
(3) the configuration precision 1 of the solder on electrode
In the first, second, third connecting structure body obtained, along the layer of first electrode, connecting portion and second electrode
It is opposite with second electrode to first electrode when the folded direction part opposite with second electrode to first electrode is observed
The ratio X of in the partial area 100%, area that the solder portion in connecting portion is configured is evaluated.With following bases
Standard determined the configuration precision 1 of the solder on electrode.
[determinating reference of the configuration precision 1 of the solder on electrode]
○○：Ratio X is more than 70%
○：Ratio X is 60% less than 70%
△：Ratio X is 50% less than 60%
×：Ratio X is less than 50%
(4) the configuration precision 2 of the solder on electrode
Obtain first, second, third connecting structure body in, along with first electrode, connecting portion and second electrode
When the orthogonal direction of the stacked direction part opposite with second electrode to first electrode is observed, to the solder in connecting portion
The ratio Y for the solder portion being configured in portion 100% in the connecting portion of first electrode and the opposite part of second electrode is evaluated.
The configuration precision 2 of the solder on electrode is determined with following benchmark.
[determinating reference of the configuration precision 2 of the solder on electrode]
○○：Ratio Y is more than 99%
○：Ratio Y is more than 90%, and less than 99%
△：Ratio Y is more than 70%, and less than 90%
×：Ratio Y is less than 70%
(5) the interelectrode conducting reliability above and below
In the first, second, third connecting structure body (n=15) obtained, each connection position between the electrode by above and below
The connection resistance put is measured by four-terminal method respectively.Calculate the average value of connection resistance.In addition, according to voltage=electricity
The relation of stream × resistance, determines voltage when flowing through constant electric current, can obtain connection resistance.It determined with following benchmark
Turn on reliability.
[determinating reference of conducting reliability]
○○：The average value for connecting resistance is below 50m Ω
○：The average value of resistance is connected more than 50m Ω and below 70m Ω
△：The average value of resistance is connected more than 70m Ω and below 100m Ω
×：The average value of resistance is connected more than 100m Ω or bad connection is produced
(6) interelectrode insulating reliability adjacent in the horizontal
In the first, second, third connecting structure body (n=15) obtained, placed in 85 DEG C, the environment of humidity 85%
After 100 hours, applying 5V the electrode being laterally abutted, and the resistance value in 25 position findings.Judged with following benchmark
Insulating reliability.
[determinating reference of insulating reliability]
○○：The average value for connecting resistance is 107 more than Ω
○：The average value for connecting resistance is 106 Ω less than 107 Ω
△：The average value for connecting resistance is 105 Ω less than 106 Ω
×：The average value for connecting resistance is less than 105 Ω
(7) the interelectrode position skew above and below
In the first, second, third connecting structure body obtained, along the stacking of first electrode, connecting portion and second electrode
When the direction part opposite with second electrode to first electrode is observed, center line and second electrode to first electrode
The distance that whether center line is alignd and position is deviateed is evaluated.With following benchmark determined above and below interelectrode position
Skew.
[determinating reference of interelectrode position skew up and down]
○○：Position skew is less than 15 μm
○：Position skew is for 15 μm less than 25 μm
△：Position skew is for 25 μm less than 40 μm
×：Position skew is more than 40 μm
It the results are shown in following tables 1.
Table 1
Not only flexible printing substrate, in the case where using resin film, flexble flat's cable and rigid-flexible combination substrate, also sees
To identical tendency.
Description of reference numerals
1st, 1X ... connecting structure body
2 ... first connecting object parts
2a ... first electrodes
3 ... second connecting object parts
3a ... second electrodes
4th, 4X ... connecting portions
4A, 4XA ... solder portion
4B, 4XB ... solidfied material portion
11 ... conductive materials
11A ... electroconductive particles
11B ... Thermocurable compositions
21 ... electroconductive particles (semiconductor particles)
31 ... electroconductive particles
32 ... substrate particles
33 ... conductive parts (conductive part with solder)
The conductive parts of 33A ... second
33B ... solder portions
41 ... electroconductive particles
42 ... solder portions
Claims (9)
1. a kind of conductive material, comprising multiple electroconductive particles, Thermocurable compound and thermal curing agents,
The electroconductive particle has solder in the outer surface part of conductive part,
The electroconductive particle has O-Si keys in the outer surface of the solder of the conductive part.
2. conductive material according to claim 1, wherein,
The electroconductive particle has Sn-O-Si keys in the outer surface of the solder of the conductive part.
3. conductive material according to claim 1 or 2, wherein,
The electroconductive particle is the surface treatment based on silane coupler.
4. conductive material according to any one of claim 1 to 3, wherein,
The electroconductive particle has amino in the outer surface of the solder of the conductive part.
5. conductive material according to any one of claim 1 to 4, wherein,
The electroconductive particle has in the outer surface of the solder of the conductive part via Sn-O-Si keys wraps carboxylic
Group.
6. conductive material according to any one of claim 1 to 5, wherein,
The electroconductive particle is semiconductor particles.
7. conductive material according to any one of claim 1 to 6, wherein,
The average grain diameter of the electroconductive particle is more than 1 μm and less than 60 μm.
8. conductive material according to any one of claim 1 to 7, wherein,
In the weight % of conductive material 100, the content of the electroconductive particle is more than 10 weight % and below 80 weight %.
9. a kind of connecting structure body, possesses：
First connecting object part, it has first electrode on surface；
Second connecting object part, it has second electrode on surface；
Connecting portion, the first connecting object part is connected by it with the second connecting object part,
The material of the connecting portion is the conductive material any one of claim 1 to 8,
The first electrode utilizes the solder in the electroconductive particle to electrically connect with the second electrode.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015140337 | 2015-07-14 | ||
| JP2015-140337 | 2015-07-14 | ||
| PCT/JP2016/070386 WO2017010445A1 (en) | 2015-07-14 | 2016-07-11 | Conductive material and connection structure |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107077915A true CN107077915A (en) | 2017-08-18 |
Family
ID=57757416
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201680003614.2A Pending CN107077915A (en) | 2015-07-14 | 2016-07-11 | Conductive material and connecting structure body |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP6166849B2 (en) |
| KR (1) | KR20180029945A (en) |
| CN (1) | CN107077915A (en) |
| TW (1) | TW201709220A (en) |
| WO (1) | WO2017010445A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11018028B2 (en) | 2018-11-07 | 2021-05-25 | Epistar Corporation | Method of applying conductive adhesive and manufacturing device using the same |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103426499A (en) * | 2012-05-16 | 2013-12-04 | 日立化成株式会社 | Conductive particle, anisotropic conductive adhesive film and connecting structure |
| CN103443869A (en) * | 2012-02-21 | 2013-12-11 | 积水化学工业株式会社 | Conductive particles, method for producing conductive particles, conductive material and connection structure |
| JP2014132567A (en) * | 2012-12-05 | 2014-07-17 | Sekisui Chem Co Ltd | Conductive particle with insulating particles, method for producing conductive particle with insulating particles, conductive material and connection structure |
| CN104584141A (en) * | 2012-11-28 | 2015-04-29 | 积水化学工业株式会社 | Conductive particle with insulating particles, conductive material and connection structure |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3770126B2 (en) * | 2000-09-29 | 2006-04-26 | Ｊｓｒ株式会社 | Anisotropic conductive sheet and electrical inspection device for circuit device |
| JP5147263B2 (en) * | 2007-03-09 | 2013-02-20 | 旭化成イーマテリアルズ株式会社 | Anisotropic conductive adhesive film for circuit connection |
| WO2009078469A1 (en) * | 2007-12-18 | 2009-06-25 | Hitachi Chemical Company, Ltd. | Insulator-covered conductive particle, anisotropic conductive adhesive film, and methods for producing those |
| JP5887304B2 (en) * | 2013-06-21 | 2016-03-16 | 株式会社タムラ製作所 | Anisotropic conductive paste and printed wiring board using the same |
| WO2016080515A1 (en) * | 2014-11-20 | 2016-05-26 | 積水化学工業株式会社 | Conductive particles, method for manufacturing conductive particles, conductive material, and connection structure |
-
2016
- 2016-07-11 WO PCT/JP2016/070386 patent/WO2017010445A1/en active Application Filing
- 2016-07-11 CN CN201680003614.2A patent/CN107077915A/en active Pending
- 2016-07-11 JP JP2016546857A patent/JP6166849B2/en not_active Expired - Fee Related
- 2016-07-11 KR KR1020177016241A patent/KR20180029945A/en unknown
- 2016-07-13 TW TW105122104A patent/TW201709220A/en unknown
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103443869A (en) * | 2012-02-21 | 2013-12-11 | 积水化学工业株式会社 | Conductive particles, method for producing conductive particles, conductive material and connection structure |
| CN103426499A (en) * | 2012-05-16 | 2013-12-04 | 日立化成株式会社 | Conductive particle, anisotropic conductive adhesive film and connecting structure |
| CN104584141A (en) * | 2012-11-28 | 2015-04-29 | 积水化学工业株式会社 | Conductive particle with insulating particles, conductive material and connection structure |
| JP2014132567A (en) * | 2012-12-05 | 2014-07-17 | Sekisui Chem Co Ltd | Conductive particle with insulating particles, method for producing conductive particle with insulating particles, conductive material and connection structure |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201709220A (en) | 2017-03-01 |
| JPWO2017010445A1 (en) | 2017-07-13 |
| KR20180029945A (en) | 2018-03-21 |
| WO2017010445A1 (en) | 2017-01-19 |
| JP6166849B2 (en) | 2017-07-19 |
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