CN103650063B - Electroconductive particle, electric conducting material and connection structural bodies - Google Patents

Electroconductive particle, electric conducting material and connection structural bodies Download PDF

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Publication number
CN103650063B
CN103650063B CN201280033707.1A CN201280033707A CN103650063B CN 103650063 B CN103650063 B CN 103650063B CN 201280033707 A CN201280033707 A CN 201280033707A CN 103650063 B CN103650063 B CN 103650063B
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particle
conductive layer
electroconductive particle
mentioned
weight
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CN103650063A (en
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西冈敬三
大塚真弘
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Sekisui Chemical Co Ltd
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Sekisui Chemical Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R4/00—Electrically-conductive connections between two or more conductive members in direct contact, i.e. touching one another; Means for effecting or maintaining such contact; Electrically-conductive connections having two or more spaced connecting locations for conductors and using contact members penetrating insulation
    • H01R4/04—Electrically-conductive connections between two or more conductive members in direct contact, i.e. touching one another; Means for effecting or maintaining such contact; Electrically-conductive connections having two or more spaced connecting locations for conductors and using contact members penetrating insulation using electrically conductive adhesives
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    • 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
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    • 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
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    • 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
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    • 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
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    • H01L2224/32221—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/32225—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
    • 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
    • H01L2224/8385—Bonding techniques using a polymer adhesive, e.g. an adhesive based on silicone, epoxy, polyimide, polyester
    • H01L2224/83851—Bonding techniques using a polymer adhesive, e.g. an adhesive based on silicone, epoxy, polyimide, polyester being an anisotropic conductive adhesive
    • 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
    • H01L2224/8385—Bonding techniques using a polymer adhesive, e.g. an adhesive based on silicone, epoxy, polyimide, polyester
    • H01L2224/83855—Hardening the adhesive by curing, i.e. thermosetting
    • 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
    • H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L24/31—Structure, shape, material or disposition of the layer connectors after the connecting process
    • H01L24/32—Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/00014—Technical content checked by a classifier the subject-matter covered by the group, the symbol of which is combined with the symbol of this group, being disclosed without further technical details
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
    • H01L2924/151—Die mounting substrate
    • H01L2924/156—Material
    • H01L2924/15786—Material with a principal constituent of the material being a non metallic, non metalloid inorganic material
    • H01L2924/15788—Glasses, e.g. amorphous oxides, nitrides or fluorides

Abstract

The object of the present invention is to provide and multiple electroconductive particle can be suppressed to condense and the electroconductive particle of interelectrode contact resistance can be reduced for during interelectrode connection, and employ the electric conducting material of this electroconductive particle.Electroconductive particle of the present invention (1) has base particle (2) and conductive layer (3), this conductive layer (3) is arranged on the surface of base particle (2), and at least one metal ingredient comprised in tungsten and molybdenum and nickel, boron.

Description

Electroconductive particle, electric conducting material and connection structural bodies
Technical field
The present invention relates to the electroconductive particle being provided with conductive layer on the surface of base particle, more specifically, relate to the electroconductive particle that such as can be used in interelectrode electrical connection.In addition, the present invention relates to the electric conducting material employing above-mentioned electroconductive particle and connection structural bodies.
Background technology
The anisotropic conductive materials such as anisotropic conductive paste and anisotropic conductive film are widely known by the people.In these anisotropic conductive materials, electroconductive particle is scattered in adhesive resin.
Above-mentioned anisotropic conductive material can be used for the connection of IC chip and flexible printed wiring board and IC chip and has the connection etc. of circuit substrate of ITO electrode.Such as, can after anisotropic conductive material being arranged between the electrode of IC chip and the electrode of circuit substrate, by heating and pressurizeing these electrodes are electrically connected.
As an example of above-mentioned electroconductive particle, Patent Document 1 discloses a kind of electroconductive particle following, it utilizes electroless plating method formation nickel conductive layer or nickel alloy conductive layer and obtaining by the surface of the pellet base material particles average grain diameter 1 ~ 20 μm.This electroconductive particle has the microspike of 0.05 ~ 4 μm on the most top layer of conductive layer.This conductive layer is connected in fact continuously with this projection.
In addition, followingly Patent Document 2 discloses a kind of electroconductive particle of conductive layer that there is base particle and be formed at this base particle surface.In order to form base particle, as a part for monomer, employ divinylbenzene-ethyl vinyl benzol mixture.With regard to this electroconductive particle, 10% modulus of elasticity in comperssion occurred when conjugating of particle diameter is 2.5 × 10 9n/m 2below, compression response rate is more than 30% and failure strain is more than 30%.Following content is described: when being electrically connected between the above-mentioned electroconductive particle of use is by the electrode of substrate, contact resistance reduces, and connection reliability increases in patent documentation 2.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2000-243132 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2003-313304 publication
Summary of the invention
The problem that invention will solve
Use the electroconductive particle recorded in patent documentation 1 by when connecting between electrode, cause interelectrode contact resistance to increase sometimes.In addition, use the anisotropic conductive material comprising the electroconductive particle recorded in patent documentation 1 by when connecting between electrode, sometimes the resinous principle between electrode and electroconductive particle fully cannot be got rid of.Therefore, the interelectrode contact resistance connected by electroconductive particle contained in above-mentioned anisotropic conductive material is increased sometimes.
In addition, with regard to the electroconductive particle of the embodiment of patent documentation 1, be formed with the conductive layer comprising nickel and phosphorus.At the conductive layer surface of the electrode connected by electroconductive particle and electroconductive particle, multiform becomes to have oxide film thereon.Use the electroconductive particle having and comprise nickel and the conductive layer of phosphorus by when being connected between electrode, the conductive layer comprising nickel and phosphorus is comparatively soft, therefore sometimes the oxide film thereon on electrode and electroconductive particle surface cannot be got rid of fully, cause contact resistance to increase.
In addition, in order to reduce contact resistance strengthen record in such as patent documentation 1 such comprise the thickness of the conductive layer of nickel and phosphorus time, cause connecting object parts or substrate to sustain damage due to the existence of electroconductive particle sometimes.When connecting object parts or electrode damage, contact resistance is easily caused to increase.In addition, when electrode or connecting object they deteriorate, interelectrode conducting reliability can be caused to reduce.
In addition, with regard to the such conventional conductive particle recorded in patent documentation 1, there is the cohesion of multiple electroconductive particle sometimes.Use the multiple electroconductive particles after cohesion by when connecting between electrode, the short circuit sometimes between generating electrodes.
In addition, with regard to the electroconductive particle recorded in patent documentation 2, also occur sometimes fully to get rid of oxide film thereon, maybe cannot suppress the problem of the damage of connecting object parts or substrate.Therefore, when using the electroconductive particle recorded in patent documentation 2, be also difficult to fully reduce interelectrode contact resistance.
The object of the present invention is to provide and multiple electroconductive particle can be suppressed to condense and the electroconductive particle of interelectrode contact resistance can be reduced for during interelectrode connection, and use electric conducting material and the connection structural bodies of this electroconductive particle.
Limited object of the present invention is to be provided in effectively can be got rid of the oxide film thereon on electrode and electroconductive particle surface for during interelectrode connection, can reduce the electroconductive particle of interelectrode contact resistance, and uses electric conducting material and the connection structural bodies of this electroconductive particle.
Limited object of the present invention is to be provided in effectively can get rid of the resinous principle between electrode and electroconductive particle, the electric conducting material that can reduce interelectrode contact resistance and connection structural bodies for during interelectrode connection.
The method of dealing with problems
According to wide in range aspect of the present invention, can provide a kind of electroconductive particle, it has base particle and conductive layer, and this conductive layer is arranged on the surface of above-mentioned base particle, and at least one metal ingredient comprised in tungsten and molybdenum and nickel, boron.
In a certain particular aspects of electroconductive particle of the present invention, in above-mentioned conductive layer overall 100 % by weight, the content of above-mentioned boron is more than 0.05 % by weight and less than 4 % by weight.
In a certain particular aspects of electroconductive particle of the present invention, in above-mentioned conductive layer overall 100 % by weight, the content of above-mentioned metal ingredient is more than 0.1 % by weight and less than 30 % by weight.
In a certain particular aspects of electroconductive particle of the present invention, in above-mentioned conductive layer overall 100 % by weight, the content of above-mentioned metal ingredient is greater than 5 % by weight and below 30 % by weight.
In a certain particular aspects of electroconductive particle of the present invention, above-mentioned metal ingredient comprises tungsten.
In a certain particular aspects of electroconductive particle of the present invention, be 5000N/mm by modulus of elasticity in comperssion during this electroconductive particle compression 10% 2above and 15000N/mm 2below.
In a certain particular aspects of electroconductive particle of the present invention, its compressive recovery rate is more than 5% and less than 70%.
In a certain particular aspects of electroconductive particle of the present invention, above-mentioned metal ingredient comprises molybdenum.
In a certain particular aspects of electroconductive particle of the present invention, above-mentioned conductive layer comprises nickel and molybdenum, and in above-mentioned conductive layer overall 100 % by weight, the content of nickel be more than 70 % by weight and less than 99.9 % by weight, the content of molybdenum is more than 0.1 % by weight and less than 30 % by weight.
In a certain particular aspects of electroconductive particle of the present invention, it is being 7000N/mm by modulus of elasticity in comperssion during compression 5% 2above, and, this electroconductive particle on compression direction be greater than compression before electroconductive particle particle diameter 10% and for compression before electroconductive particle particle diameter less than 25% by compressed time, above-mentioned conductive layer breaks.
In a certain particular aspects of electroconductive particle of the present invention, the thickness of above-mentioned conductive layer is more than 0.05 μm and less than 0.5 μm.
In a certain particular aspects of electroconductive particle of the present invention, above-mentioned conductive layer has projection at outer surface.
Electric conducting material of the present invention comprises adhesive resin and above-mentioned electroconductive particle.
Connection structural bodies of the present invention possesses the 1st connecting object parts, the 2nd connecting object parts and connects the connecting portion of above-mentioned 1st, the 2nd connecting object parts, and above-mentioned connecting portion is formed by above-mentioned electroconductive particle or formed by the electric conducting material comprising adhesive resin and above-mentioned electroconductive particle.
The effect of invention
With regard to electroconductive particle of the present invention, owing to being provided with the conductive layer comprising at least one metal ingredient in tungsten and molybdenum and nickel, boron on the surface of base particle, multiple electroconductive particle therefore can be suppressed to condense.And then, when connecting between use electroconductive particle of the present invention is by electrode, can contact resistance be reduced.
Accompanying drawing explanation
[Fig. 1] Fig. 1 is profile, shows the electroconductive particle of the 1st execution mode of the present invention.
[Fig. 2] Fig. 2 is profile, shows the electroconductive particle of the 2nd execution mode of the present invention.
[Fig. 3] Fig. 3 is profile, shows the electroconductive particle of the 3rd execution mode of the present invention.
[Fig. 4] Fig. 4 is front cross-sectional view, schematically shows the connection structural bodies of the electroconductive particle employing first embodiment of the present invention.
[Fig. 5] Fig. 5 is schematic cross sectional view, for being described state during compression conductive particle.
[Fig. 6] Fig. 6 is schematic diagram, show compressive load value when compression conductive particle causes conductive layer to break and compression conjugate between relation one routine.
Symbol description
1 ... electroconductive particle
1a ... projection
2 ... base particle
3 ... conductive layer
3a ... projection
4 ... core material
5 ... megohmite insulant
11 ... electroconductive particle
11a ... projection
12 ... 2nd conductive layer
13 ... conductive layer
13a ... projection
21 ... electroconductive particle
22 ... conductive layer
22a ... break
51 ... connection structural bodies
52 ... 1st connecting object parts
52a ... above
52b ... electrode
53 ... 2nd connecting object parts
53a ... below
53b ... electrode
54 ... connecting portion
71 ... stand
72 ... compression member
72a ... flat surface
Embodiment
Below, the present invention is specifically described.
Electroconductive particle of the present invention have base particle and be arranged at this base particle surface on and the conductive layer of at least one metal ingredient comprised in tungsten and molybdenum and nickel, boron.This conductive layer is nickel-boron-tungsten/molybdenum conductive layer.Below, also at least one metal ingredient in tungsten and molybdenum is denoted as metal ingredient M.Below, also the conductive layer comprising nickel, boron and metal ingredient M is denoted as conductive layer X.
By making electroconductive particle of the present invention take above-mentioned formation, multiple electroconductive particle can be suppressed to condense.Can suppress multiple electroconductive particle that the result of cohesion occurs, can effectively prevent interelectrode short circuit.In addition, by making electroconductive particle of the present invention take above-mentioned formation, when connecting between use electroconductive particle of the present invention is by electrode, contact resistance can be reduced.
Utilize there is the conductive layer comprising nickel electroconductive particle by electrode between connect time, interelectrode contact resistance reduces.In electroconductive particle of the present invention, when the content of nickel is more than 50 % by weight in conductive layer X overall 100 % by weight, interelectrode contact resistance significantly reduces.Therefore, in above-mentioned conductive layer X overall 100 % by weight, the content of nickel is preferably more than 50 % by weight.
In addition, for have not boracic nickel conductive layer electroconductive particle for, the nickel conductive layer of this not boracic is too soft, during for interelectrode connection, sometimes fully cannot get rid of the oxide film thereon on electrode and electroconductive particle surface, cause contact resistance to increase.Such as, with regard to there is the electroconductive particle of the conductive layer comprising nickel and phosphorus, fully cannot get rid of the oxide film thereon on electrode and electroconductive particle surface, easily cause contact resistance to increase.Particularly, in above-mentioned conductive layer overall 100 % by weight, when the content of phosphorus is more than 10.5 % by weight, easily cause contact resistance to increase, when the content of phosphorus is more than 1 % by weight, easily cause contact resistance to increase further.
On the other hand, in order to reduce contact resistance strengthen the thickness of the conductive layer comprising nickel and phosphorus time, cause connecting object parts or substrate to sustain damage due to the existence of electroconductive particle sometimes.
On the other hand, because the hardness of the above-mentioned conductive layer X comprising nickel and boron is higher, therefore interelectrode contact resistance can be reduced.By when connecting between electrode, the oxide film thereon on electrode and electroconductive particle surface can be got rid of, can contact resistance be reduced.
In addition, in electroconductive particle of the present invention, because above-mentioned conductive layer X not only comprises boron, also comprises at least one metal ingredient M in tungsten and molybdenum, the conductive layer X comprising boron and above-mentioned metal ingredient M therefore can be made to become quite hard.Therefore, fully can get rid of the oxide film thereon on electrode and electroconductive particle surface, significantly can reduce contact resistance.Particularly, when above-mentioned conductive layer X comprises above-mentioned metal ingredient M and in the bossed situation of outer surface tool of above-mentioned conductive layer X, more effectively can get rid of the oxide film thereon on electrode and electroconductive particle surface, can reduce contact resistance further.
In addition, by making above-mentioned conductive layer X comprise above-mentioned metal ingredient M, above-mentioned conductive layer X can be made to become quite hard, its result, even if the connection structural bodies be formed by connecting between electrode applied to impact to by electroconductive particle, also not easily poor flow occurs.That is, the resistance to impact of connection structural bodies can also be improved.
In addition, magnetic is higher sometimes for the conductive layer surface of conventional conductive particle, and, the surface magnetism comprising the conductive layer of nickel and boron is higher, therefore, by when being electrically connected between electrode, under the impact of electroconductive particle that there occurs cohesion because of magnetic, there is the tendency easily producing between transversely adjacent electrode and connect.In electroconductive particle of the present invention, because above-mentioned conductive layer X comprises above-mentioned metal ingredient M, therefore the surface magnetism of above-mentioned conductive layer X significantly reduces.Thus, multiple electroconductive particle can be suppressed to condense.Therefore, by when being electrically connected between electrode, the existence of the electroconductive particle owing to there occurs cohesion can being suppressed and cause producing between transversely adjacent electrode connecting.That is, the short circuit between adjacent electrode can be prevented further.
Preferably in above-mentioned conductive layer X overall 100 % by weight, the content of nickel is more than 70 % by weight and less than 99.9 % by weight and the content of above-mentioned metal ingredient M is more than 0.1 % by weight and less than 30 % by weight.In addition, preferred above-mentioned conductive layer X is not phosphorous, or above-mentioned conductive layer X comprise phosphorus but the content of phosphorus in above-mentioned conductive layer X overall 100 % by weight lower than 1 % by weight.
Preferably in above-mentioned conductive layer X overall 100 % by weight, the content of nickel is more than 70 % by weight and less than 99.9 % by weight, the content of above-mentioned metal ingredient M is more than 0.1 % by weight and less than 30 % by weight, and the not phosphorous or above-mentioned conductive layer X of above-mentioned conductive layer X comprise phosphorus but phosphorus at the content in above-mentioned conductive layer X overall 100 % by weight lower than 1 % by weight.By have this electroconductive particle preferably formed be used for interelectrode connection time, effectively can get rid of the oxide film thereon on electrode and electroconductive particle surface.Thereby, it is possible to reduce the interelectrode contact resistance of gained connection structural bodies further.In addition, because the nickel content had in this electroconductive particle preferably formed is more than 70 % by weight, therefore, interelectrode contact resistance significantly reduces.
In addition, the content of above-mentioned metal ingredient M in above-mentioned conductive layer X overall 100 % by weight be more than 0.1 % by weight and less than 30 % by weight time, with not containing above-mentioned metal ingredient M conductive layer compared with, conductive layer X becomes quite hard.Thus, effectively can get rid of the oxide film thereon on electrode and electroconductive particle surface, its result, interelectrode contact resistance reduces further.In addition, electroconductive particle is being coordinated with adhesive resin, using electric conducting material by when connecting between electrode, effectively can get rid of the resinous principle between electrode and electroconductive particle, interelectrode contact resistance also can be made thus to reduce further.
Modulus of elasticity in comperssion (10%K value) during electroconductive particle compression 10% of the present invention is preferably 5000N/mm 2above, 7000N/mm is more preferably 2above, 15000N/mm is preferably 2below, 10000N/mm is more preferably 2below.When above-mentioned modulus of elasticity in comperssion (10%K value) is more than above-mentioned lower limit, more effectively can get rid of the oxide film thereon on electrode and electroconductive particle surface, and the resinous principle can more effectively got rid of between electrode and electroconductive particle, its result, interelectrode contact resistance reduces further.
Above-mentioned modulus of elasticity in comperssion (10%K value) can measure as described below.
Use micro-compression tester, with the level and smooth pressure head end face of cylinder (diameter 50 μm, Buddha's warrior attendant are made of stones), electroconductive particle is compressed under the condition of compression speed 2.6mN/ second and maximum test load 10gf.Measure load value (N) now and compression displacement (mm).Can according to gained measured value, utilize following formula to obtain above-mentioned modulus of elasticity in comperssion.As above-mentioned micro-compression tester, " FischerScopeH-100 " that such as Fischer company can be used to manufacture etc.
K value (N/mm 2)=(3/2 1/ 2) FS -3/ 2r -1/ 2
F: the load value (N) during 10% compression occurs electroconductive particle
S: compression displacement (mm) during 10% compression occurs electroconductive particle
R: the radius (mm) of electroconductive particle
The compressive recovery rate of above-mentioned electroconductive particle is preferably more than 5%, is more preferably more than 20%, is preferably less than 70%, is more preferably less than 60%, more preferably less than 50%.When compressive recovery rate is more than above-mentioned lower limit and below the above-mentioned upper limit, more effectively can get rid of the oxide film thereon on electrode and electroconductive particle surface, and the resinous principle can more effectively got rid of between electrode and electroconductive particle, its result, interelectrode contact resistance reduces further.In addition, the interface between the part except electroconductive particle of solidfied material and connecting portion and electroconductive particle and connecting object parts, is more not easily peeling.Further, can suppress the repulsive force of the electroconductive particle for interelectrode connection, its result, electric conducting material is more not easily peeled off from substrate etc.Thus, interelectrode contact resistance also can be made to reduce further.
Above-mentioned compressive recovery rate can measure as described below.
Sample bench scatters electroconductive particle.Use micro-compression tester to 1 electroconductive particle scattered along electroconductive particle center position apply load (reverse load value) until electroconductive particle reaches the compression of 30%.Then, carry out unloading until reach initial point load value (0.40mN).Measure load-compression displacement during this period, utilize following formula to obtain compressive recovery rate.Wherein, load speed is made to be 0.33mN/ second.As above-mentioned micro-compression tester, " FischerScopeH-100 " that such as Fischer company can be used to manufacture etc.
Compressive recovery rate (%)=[(L1-L2)/L1] × 100
L1: to the compression displacement reached reverse load value from initial point load value when applying load
L2: to the unloading displacement reached initial point load value from reverse load value when discharging
It should be noted that, above-mentioned modulus of elasticity in comperssion and above-mentioned compressive recovery rate can according to the particle diameter of the kind of above-mentioned base particle, above-mentioned base particle, in above-mentioned conductive layer X overall 100 % by weight nickel content, in above-mentioned conductive layer X overall 100 % by weight above-mentioned metal ingredient M content, in above-mentioned conductive layer X overall 100 % by weight phosphorus content, in above-mentioned conductive layer X overall 100 % by weight, the content of boron, the thickness etc. of above-mentioned conductive layer X suitably adjust.
With regard to electroconductive particle of the present invention, be preferably 7000N/mm by the modulus of elasticity in comperssion (5%K value) during compression 5% 2above.
In addition, with regard to electroconductive particle of the present invention, preferred electroconductive particle on compression direction by compression be greater than compression before electroconductive particle particle diameter 10% and be less than 25% time, above-mentioned conductive layer breaks.In other words, when compressing electroconductive particle of the present invention, before preferably this electroconductive particle is greater than compression on compression direction electroconductive particle particle diameter 10% and for the front electroconductive particle particle diameter of compression less than 25% compression conjugate time, above-mentioned conductive layer breaks.That is, the compression displacement of the electroconductive particle that breaks of conductive layer is preferably greater than 10% and is less than 25%.Such as, significantly during compression conductive particle, conductive layer can moderately generating portion break.The electroconductive particle with such character is not only enough high in the hardness of compression initial stage, can be broken by during moderate compression.By when connecting between electrode, at electroconductive particle by the stage of moderate compression, conductive layer can break, and thus can suppress the damage of electrode.Its result, can reduce the interelectrode contact resistance of gained connection structural bodies further, improves interelectrode conducting reliability further.
With regard to electroconductive particle of the present invention, preferably being 7000N/mm by the modulus of elasticity in comperssion (5%K value) during compression 5% 2above, and when compress electroconductive particle of the present invention, on compression direction by compression be greater than compression before electroconductive particle particle diameter 10% and be less than 25% time, above-mentioned conductive layer breaks.By have this electroconductive particle preferably formed be used for interelectrode connection time, interelectrode contact resistance can be reduced further.
Modulus of elasticity in comperssion (5%K value) when electroconductive particle of the present invention is compressed 5% is 7000N/mm 2when above, the electroconductive particle of compression initial stage has sufficient hardness.Thus, when connecting between by electrode, electroconductive particle effectively can get rid of the oxide film thereon on electrode and electroconductive particle surface in compression initial stage.Its result, can make electrode effectively contact with the conductive layer of electroconductive particle, thus reduces interelectrode contact resistance further.
On the other hand, use by the modulus of elasticity in comperssion (5%K value) during compression 5% lower than 7000N/mm 2electroconductive particle by when being electrically connected between electrode, be 7000N/mm with use by the modulus of elasticity in comperssion (5%K value) during compression 5% 2situation about being electrically connected between electrode is compared by above electroconductive particle, the tendency that the removing property that there is the oxide film thereon on electrode and electroconductive particle surface declines, and there is the tendency that interelectrode contact resistance increases.
From the view point of reducing interelectrode contact resistance further, above-mentioned 5%K value is more preferably 8000N/mm 2above, more preferably 9000N/mm 2above.The upper limit of above-mentioned 5%K value is not particularly limited.Above-mentioned 5%K value can be such as 15000N/mm 2below, also can be 10000N/mm 2below.
Above-mentioned modulus of elasticity in comperssion (5%K value) can measure as follows.
Use micro-compression tester, with the level and smooth pressure head end face of cylinder (diameter 50 μm, Buddha's warrior attendant are made of stones), electroconductive particle is compressed under the condition of compression speed 2.6mN/ second and maximum test load 10gf.Measure load value (N) now and compression displacement (mm).Can according to gained measured value, utilize following formula to obtain above-mentioned modulus of elasticity in comperssion.As above-mentioned micro-compression tester, " FischerScopeH-100 " that such as Fischer company can be used to manufacture etc.
K value (N/mm 2)=(3/2 1/ 2) FS -3/ 2r -1/ 2
F: the load value (N) during 5% compression occurs electroconductive particle
S: compression displacement (mm) during 5% compression occurs electroconductive particle
R: the radius (mm) of electroconductive particle
Above-mentioned modulus of elasticity in comperssion (10%K value and 5%K value) generally and represent the hardness of electroconductive particle quantitatively.By using above-mentioned modulus of elasticity in comperssion, can quantitatively and unambiguously represents the hardness of electroconductive particle.
From the view point of reducing interelectrode contact resistance further, the compression displacement that above-mentioned conductive layer breaks is more preferably more than 12%, is more preferably less than 20%.
Below, by reference to the accompanying drawings the specific embodiment of the present invention and embodiment are described, and illustrate the present invention thus.
Fig. 1 is profile, shows electroconductive particle of the first embodiment of the present invention.
As shown in Figure 1, electroconductive particle 1 has base particle 2, conductive layer 3, multiple core material 4 and multiple megohmite insulant 5.
Conductive layer 3 is arranged on the surface of base particle 2.Conductive layer 3 comprises nickel, boron and above-mentioned metal ingredient M.Conductive layer 3 is nickel-boron-tungsten/molybdenum conductive layer.Electroconductive particle 1 is that the surface of base particle 2 is by the coated coating particles of conductive layer 3.
Electroconductive particle 1 has multiple projection 1a on surface.Conductive layer 3 has multiple projection 3a at outer surface.Multiple core material 4 is arranged on the surface of base particle 2.Multiple core material 4 is embedded in conductive layer 3.Core material 4 is arranged at the inner side of projection 1a, 3a.Conductive layer 3 is by coated for multiple core material 4.The outer surface of conductive layer 3 swells because of the existence of multiple core material 4, forms projection 1a, 3a.
Electroconductive particle 1 has the megohmite insulant 5 on the outer surface being arranged at conductive layer 3.At least part of region of the outer surface of conductive layer 3 is coated by megohmite insulant 5.Megohmite insulant 5 is formed by the material with insulating properties, is insulating properties particle.Like this, electroconductive particle of the present invention also can have the megohmite insulant be arranged on the outer surface of conductive layer.But it should be noted that, electroconductive particle of the present invention also not must have megohmite insulant.
Fig. 2 is profile, shows electroconductive particle of the second embodiment of the present invention.
Electroconductive particle 11 shown in Fig. 2 has base particle 2, the 2nd conductive layer 12 (other conductive layer), conductive layer 13 (the 1st conductive layer), multiple core material 4 and multiple megohmite insulant 5.
Only conductive layer is different for electroconductive particle 1 and electroconductive particle 11.That is, in electroconductive particle 1, formation be the conductive layer of single layer structure, and on the other hand, in electroconductive particle 11, formation be double-deck 2nd conductive layer 12 and conductive layer 13.
Conductive layer 13 is arranged on the surface of base particle 2.The 2nd conductive layer 12 (other conductive layer) is provided with between base particle 2 and conductive layer 13.Therefore, the surface of base particle 2 is provided with the 2nd conductive layer 12, the surface of the 2nd conductive layer 12 is provided with conductive layer 13.Conductive layer 13 comprises nickel, boron and tungsten.Conductive layer 13 has multiple projection 13a at outer surface.Electroconductive particle 11 has multiple projection 11a on surface.
Fig. 3 is profile, shows electroconductive particle of the third embodiment of the present invention.
Electroconductive particle 21 shown in Fig. 3 has base particle 2 and conductive layer 22.Conductive layer 22 is arranged on the surface of base particle 2.Conductive layer 22 comprises nickel, boron and above-mentioned metal ingredient M.
Electroconductive particle 21 does not have core material.The surface of electroconductive particle 21 does not have projection.Electroconductive particle 21 is spherical.The surface of conductive layer 22 does not have projection.Like this, electroconductive particle of the present invention also can not have projection, also can be spherical.In addition, electroconductive particle 21 does not have megohmite insulant.But it should be noted that, electroconductive particle 21 also can have the megohmite insulant on the surface being arranged at conductive layer 22.
With regard to electroconductive particle 1,11,21, preferably at conductive layer 3, in the entirety 100 % by weight of 13,22, the content of nickel be more than 70 % by weight and less than 99.9 % by weight, the content of above-mentioned metal ingredient M is more than 0.1 % by weight and less than 30 % by weight.In addition, preferred conductive layer 3,13,22 is not phosphorous, or conductive layer 3,13,22 comprise phosphorus but phosphorus at conductive layer 3, the content in 13,22 overall 100 % by weight is lower than 1 % by weight.
Electroconductive particle 1,11, the above-mentioned 5%K value of 21 is preferably 7000N/mm 2above.In addition, at compression conductive particle 1,11, when 21, preferred electroconductive particle 1,11,21 there occurs on compression direction be greater than compression before electroconductive particle 1,11,21 particle diameters 10% and for compression before electroconductive particle 1,11,21 particle diameters less than 25% compression displacement time, conductive layer 3,13,22 break.That is, for electroconductive particle 1,11,21, by electroconductive particle 1 before the compression on compression direction, 11, when the particle diameter of 21 is set to X, preferably electroconductive particle 1,11 on compression direction, the particle diameter of 21 be more than 0.75X and lower than 0.90X time, conductive layer 3,13,22 break.Such as, electroconductive particle 1 before compression on compression direction, when the particle diameter of 11,21 is 5 μm, preferably to electroconductive particle 1,11,21 carry out compressing and make electroconductive particle 1,11 on compression direction, the particle diameter of 21 reach more than 3.75 μm and lower than 4.5 μm time, conductive layer 3,13,22 break.It should be noted that, for electroconductive particle 11, be not only conductive layer 13, the 2nd conductive layer 12 also can break.
It should be noted that, what above-mentioned " breaking " to represent on conductive layer that (the 1st time) first occur breaks.Therefore, for electroconductive particle 1,11 of the present embodiment, 21, preferably to having non-cracked conductive layer 3,13, when the electroconductive particle 1,11,21 of 22 compresses, when electroconductive particle 1,11,21 be greater than on compression direction compression before electroconductive particle 1,11,21 particle diameters 10% and be less than 25% compression displacement time, conductive layer 3,13,22 break.
Specifically, conductive layer 3,13, the mensuration of 22 compression displacements when breaking can be carried out as follows.It should be noted that, in Fig. 5, use electroconductive particle 21.
As shown in Figure 5, electroconductive particle 21 is placed on stand 71.Use micro-compression tester (Fischer Inc. " FischerScopeH-100 "), under the condition of compression speed 0.33mN/ second and maximum test load 10mN, using cylinder (diameter 50 μm, Buddha's warrior attendant are made of stones) as compression member 72, make the flat surface 72a of this compression member 72 towards electroconductive particle 21, decline along the direction shown in arrow A.Flat surface 72a is utilized to compress electroconductive particle 21.Proceed to compress until conductive layer 22 local of electroconductive particle 21 produces the 22a that breaks.For electroconductive particle 1, the situation of 11, also can utilize same method to measure.
It should be noted that, in the profile shown in Fig. 5, what illustrate is the state defining the 22a that breaks in the top and the bottom of electroconductive particle 21 on conductive layer 22, but produces the position of breaking for conductive layer and be not particularly limited.
As described above during compression conductive particle, preferably electroconductive particle there occurs on compression direction be greater than compression before electroconductive particle particle diameter 10% compression conjugate time, above-mentioned conductive layer breaks, and when the compression displacement occurred is less than 25%, above-mentioned conductive layer breaks.
When compression conductive particle limit, limit measures compressive load value and compression displacement, the relation between compressive load value and compression conjugate as shown in Figure 6.In figure 6, compress from A0 point, at A1 point, conductive layer breaks.Along with conductive layer breaks, compression displacement (particle diameter) of electroconductive particle on compression direction changes, and compression displacement transfers to A2 point from A1 point.During compression, electroconductive particle is applied in compressive load and after there is the breaking of conductive layer, electroconductive particle is compressed with less compressive load, therefore, the compression member applying compressive load to electroconductive particle is moved, and compression displacement (particle diameter) of electroconductive particle on compression direction changes.
It should be noted that, in figure 6, the slope from A0 point to the line of A1 point is larger.Be 7000N/mm in the above-mentioned 5%K value of electroconductive particle 21 2above, electroconductive particle 21 harder when, become large from A0 point to the slope of the line of A1 point.
[base particle]
As above-mentioned base particle, resin particle, inorganic particulate, organic inorganic hybridization particle and metallic etc. except metallic can be enumerated.Above-mentioned base particle is preferably base particle except metallic except, preferably resin particle, inorganic particulate except metallic or organic inorganic hybridization particle.
Preferred above-mentioned base particle is the resin particle formed by resin.Using above-mentioned electroconductive particle by when connecting between electrode, after being arranged between electrode by above-mentioned electroconductive particle, by carrying out pressing, above-mentioned electroconductive particle being compressed.When base particle is resin particle, when carrying out above-mentioned pressing, above-mentioned electroconductive particle easily deforms, and the contact area between electroconductive particle and electrode increases.Thus, interelectrode conducting reliability improves.
As the resin for the formation of above-mentioned resin particle, can enumerate such as: vistanex, acrylic resin, phenolic resins, melmac, benzoguano amine resin, urea resin, epoxy resin, unsaturated polyester resin, saturated polyester resin, PETG, polysulfones, polyphenylene oxide, polyacetals, polyimides, polyamidoimide, polyether-ether-ketone, polyether sulfone, divinyl benzene polymers and divinylbenzene analog copolymer etc.As above-mentioned divinylbenzene analog copolymer etc., divinyl benzene styrene copolymer and divinylbenzene-(methyl) acrylate copolymer etc. can be enumerated.Owing to easily the hardness of base particle can be controlled in suitable scope, therefore, for the formation of the polymer that the resin of above-mentioned resin particle is preferably polymerized by the one kind or two or more polymerizable monomer with multiple ethylenically unsaturated group.
As the inorganic matter for the formation of above-mentioned inorganic particulate, silicon dioxide and carbon black etc. can be enumerated.As above-mentioned organic inorganic hybridization particle, the organic inorganic hybridization particle etc. such as formed by the alkoxysilyl polymer be cross-linked and acrylic resin can be enumerated.
When above-mentioned base particle is metallic, as the metal for the formation of this metallic, silver, copper, nickel, silicon, gold and titanium etc. can be enumerated.
The particle diameter of above-mentioned base particle is preferably more than 0.1 μm, is more preferably more than 1 μm, more preferably more than 1.5 μm, is particularly preferably more than 2 μm, is preferably less than 1000 μm, is more preferably less than 500 μm, is more preferably less than 300 μm, more preferably less than 50 μm, is particularly preferably less than 30 μm, most preferably is less than 5 μm.When the particle diameter of base particle is more than above-mentioned lower limit, because the contact area between electroconductive particle and electrode increases, therefore, interelectrode conducting reliability improves further, and the interelectrode contact resistance connected by electroconductive particle is reduced further.In addition, by electroless plating the surface of base particle formed conductive layer time, not easily condense, not easily form the electroconductive particle of cohesion.When particle diameter is below the above-mentioned upper limit, electroconductive particle is easy to be sufficiently compressed, interelectrode contact resistance reduces further and interelectrode interval reduces.When base particle is just spherical, the particle diameter of above-mentioned base particle represents diameter, and when base particle is not just spherical, the particle diameter of above-mentioned base particle represents maximum diameter.
The particle diameter of above-mentioned base particle is especially preferably more than 2 μm and less than 5 μm.When the particle diameter of above-mentioned base particle is in the scope of 2 ~ 5 μm, interelectrode interval diminishes, even and if the thickness of increasing conductive layer also can obtain little electroconductive particle.
[conductive layer]
Electroconductive particle of the present invention have be arranged at base particle surface on and the conductive layer X of at least one metal ingredient M comprised in tungsten and molybdenum and nickel, boron.Above-mentioned conductive layer X directly can be stacked on the surface of base particle, also can be arranged on the surface of base particle across other conductive layer etc.In addition, also other conductive layer can be set on the surface of above-mentioned conductive layer X.Preferably other conductive layer is not set on the outer surface of above-mentioned conductive layer X.The outer surface of preferred electroconductive particle is the conductive layer X comprising nickel.Utilize the electroconductive particle with the conductive layer X comprising nickel by when connecting between electrode, contact resistance reduces further.
Above-mentioned conductive layer X comprises at least one metal ingredient M in tungsten and molybdenum and nickel, boron.Above-mentioned conductive layer X is nickel-boron-tungsten/molybdenum conductive layer.Above-mentioned conductive layer X preferably comprises nickel, boron and tungsten, preferably comprises nickel, boron and molybdenum, preferably comprises nickel, boron, tungsten and molybdenum.Above-mentioned conductive layer X can be nickel-boron-tungsten conductive layer, also can be nickel-boron-molybdenum conductive layer.Above-mentioned metal ingredient M preferably comprises tungsten, preferably comprises molybdenum, preferably comprises tungsten and molybdenum.
In above-mentioned conductive layer X, nickel, boron and above-mentioned metal ingredient M also can form alloy.In above-mentioned conductive layer X, can be that nickel and boron form alloy, also can be that nickel and above-mentioned metal ingredient M form alloy, can also be that boron and above-mentioned metal ingredient M form alloy.In addition, in above-mentioned conductive layer X, except nickel, boron and above-mentioned metal ingredient M, can also use chromium, (seaborgium).
In addition, for have not both tungstenic and molybdenum nickel conductive layer electroconductive particle for, in the compression initial stage of the nickel conductive layer of both this not tungstenic and molybdenum, hardness easily becomes lower.Thus, by when connecting between electrode, the tendency that the effect that existence causes the effect of the oxide film thereon getting rid of electrode and electroconductive particle surface to diminish, reduce contact resistance diminishes.
On the other hand, during in order to obtain the effect that reduces contact resistance further or add the thickness of nickel conductive layer of very much not both tungstenic and molybdenum in order to be applicable to purposes that big current flows through, there is connecting object parts or easily impaired because of the existence of the electroconductive particle tendency of substrate.Its result, the interelectrode conducting reliability of connection structural bodies is tended to reduce.
On the other hand, because above-mentioned conductive layer X comprises at least one metal ingredient M in tungsten and molybdenum and nickel, above-mentioned 5%K value is therefore easily made to reach more than above-mentioned lower limit.In addition, electroconductive particle on compression direction be greater than compression before electroconductive particle particle diameter 10% and for compression before electroconductive particle particle diameter less than 25% by compressed time, easily make above-mentioned conductive layer X moderately break.By moderately breaking when being compressed, the more not easily damage of generating electrodes, therefore, interelectrode contact resistance reduces further.
In addition, by making above-mentioned conductive layer X comprise at least one metal ingredient M in tungsten and molybdenum and nickel, above-mentioned conductive layer X has the hardness of appropriateness, therefore, at compression conductive particle by electrode between when connecting, the impression of appropriateness can be formed on electrode.It should be noted that, the recess of the electrode that the impression that electrode is formed is electroconductive particle extruding electrode and produces.
Preferred above-mentioned conductive layer X comprises nickel as principal component.From the view point of effectively reducing interelectrode initial stage contact resistance, the nickel content in above-mentioned conductive layer X overall 100 % by weight is The more the better.Therefore, in above-mentioned conductive layer X overall 100 % by weight, the content of nickel is preferably more than 50 % by weight, be more preferably more than 60 % by weight, be more preferably more than 70 % by weight, more preferably more than 75 % by weight, be further preferably more than 80 % by weight, be particularly preferably more than 85 % by weight, be particularly preferably more than 90 % by weight, most preferably be more than 95 % by weight.Nickel content in above-mentioned conductive layer X overall 100 % by weight also can be more than 97 % by weight, also can be more than 97.5 % by weight, can also be more than 98 % by weight.When the content of above-mentioned nickel is more than above-mentioned lower limit, interelectrode contact resistance reduces further.In addition, when the oxide film thereon of electrode and conductive layer surface is few, above-mentioned nickel content is more, then interelectrode contact resistance more tends to reduce.
The upper limit of nickel content suitably can change according to content of boron and above-mentioned metal ingredient M etc.Nickel content in above-mentioned conductive layer X overall 100 % by weight is preferably less than 99.9 % by weight, be more preferably less than 99.85 % by weight, more preferably less than 99.7 % by weight, particularly preferably lower than 99.45 % by weight.
For have not boracic nickel conductive layer electroconductive particle for, comparatively soft in the compression initial stage of this not nickel conductive layer of boracic, when carrying out interelectrode connection, the tendency that the effect that existence causes the effect of the oxide film thereon getting rid of electrode and electroconductive particle surface to diminish, reduce contact resistance diminishes.In addition, conductive layer comprises phosphorus instead of boron sometimes.For there is the electroconductive particle of the conductive layer comprising nickel and phosphorus, the tendency that the effect that existence easily causes the effect of the oxide film thereon getting rid of electrode and electroconductive particle surface to diminish, reduce contact resistance diminishes.
On the other hand, in order to obtain the effect that reduces contact resistance further or add to be applicable to purposes that big current flows through the thickness of the conductive layer of very much not boracic or increasing comprise the thickness of the conductive layer of nickel and phosphorus time, there is connecting object parts or easily impaired because of the existence of the electroconductive particle tendency of substrate.Its result, the interelectrode conducting reliability of connection structural bodies is tended to reduce.
On the other hand, because above-mentioned conductive layer X comprises boron, above-mentioned 5%K value is therefore easily made to reach more than above-mentioned lower limit.In addition, electroconductive particle on compression direction be greater than compression before electroconductive particle particle diameter 10% and for compression before electroconductive particle particle diameter less than 25% by compressed time, easily make above-mentioned conductive layer X moderately break.In addition, by making above-mentioned conductive layer X comprise nickel, boron and above-mentioned metal ingredient M, be more prone to make above-mentioned 5%K value reach more than above-mentioned lower limit.In addition, electroconductive particle on compression direction be greater than compression before electroconductive particle particle diameter 10% and for compression before electroconductive particle particle diameter less than 25% by compressed time, easily make above-mentioned conductive layer X more moderately break.By moderately breaking when being compressed, the more not easily damage of generating electrodes, therefore, interelectrode contact resistance reduces further.
In addition, by making above-mentioned conductive layer X comprise boron, above-mentioned conductive layer X has the hardness of appropriateness, and therefore, the more not easily damage of generating electrodes, therefore interelectrode contact resistance reduces further.In addition, by making above-mentioned conductive layer X comprise boron, above-mentioned conductive layer X has the hardness of appropriateness, therefore, at compression conductive particle by electrode between when connecting, the impression of appropriateness can be formed on electrode.
Particularly, because above-mentioned conductive layer X comprises nickel, boron and above-mentioned metal ingredient M, therefore high elastic modulus can be realized.Thus, the compression initial stage of electroconductive particle when connecting between by electrode, effectively can get rid of the oxide film thereon on electrode and electroconductive particle surface, and, electroconductive particle when connecting between by electrode is by the stage of moderate compression, above-mentioned conductive layer X breaks, and can suppress the damage of electrode thus.Its result, can reduce the interelectrode contact resistance of gained connection structural bodies, can improve interelectrode conducting reliability.
Boron contents in above-mentioned conductive layer X overall 100 % by weight is preferably more than 0.01 % by weight, is more preferably more than 0.05 % by weight, more preferably more than 0.1 % by weight, be preferably less than 5 % by weight, be more preferably less than 4 % by weight, more preferably less than 3 % by weight, be particularly preferably less than 2.5 % by weight, most preferably be less than 2 % by weight.When Boron contents is more than above-mentioned lower limit, above-mentioned conductive layer X becomes harder, more effectively can get rid of the oxide film thereon on electrode and electroconductive particle surface, can reduce interelectrode contact resistance further.When Boron contents is below the above-mentioned upper limit, the content of nickel and above-mentioned metal ingredient M increases relatively, therefore can reduce interelectrode contact resistance.
In addition, the surface magnetism comprising the above-mentioned conductive layer X of nickel and boron is high, by when being electrically connected between electrode, under the impact of electroconductive particle that there occurs cohesion because of magnetic, there is the tendency producing connection between transversely adjacent electrode.Because above-mentioned conductive layer X comprises nickel, boron and above-mentioned metal ingredient M, therefore, the surface magnetism of above-mentioned conductive layer X significantly reduces.Thus, multiple electroconductive particle can be suppressed to condense.Therefore, by when being electrically connected between electrode, the existence of the electroconductive particle owing to there occurs cohesion can being suppressed and cause producing between transversely adjacent electrode connecting.That is, the short circuit between adjacent electrode can be prevented further.
In addition, by making above-mentioned conductive layer X comprise above-mentioned metal ingredient M, above-mentioned conductive layer X has the hardness of appropriateness, therefore, at compression conductive particle by electrode between when connecting, the impression of appropriateness can be formed on electrode.In addition, by making above-mentioned conductive layer X comprise at least one in tungsten and molybdenum or comprise boron, above-mentioned conductive layer X can be made to become stone, its result, even if the connection structural bodies connected between electrode applied to impact to by electroconductive particle, also not easily there is poor flow.That is, the resistance to impact of connection structural bodies can also be improved.
In above-mentioned conductive layer X overall 100 % by weight content (total content of tungsten and molybdenum) of above-mentioned metal ingredient M be preferably more than 0.01 % by weight, be more preferably more than 0.1 % by weight, be more preferably more than 0.2 % by weight, more preferably more than 0.5 % by weight, be further preferably more than 1 % by weight, be particularly preferably greater than 5 % by weight, most preferably be more than 10 % by weight.When the content of above-mentioned metal ingredient M is more than above-mentioned lower limit, the hardness of the outer surface of conductive layer improves further.Therefore, when the surface of electrode or conductive layer defines oxide film thereon, effectively can get rid of the oxide film thereon on electrode and electroconductive particle surface, and the resinous principle can effectively got rid of between electrode and electroconductive particle, contact resistance reduces, and the resistance to impact of gained connection structural bodies improves.In addition, when the content of above-mentioned metal ingredient M is more than above-mentioned lower limit, the magnetic of the outer surface of above-mentioned conductive layer X weakens, and the cohesion of multiple electroconductive particle not easily occurs.Thus, interelectrode short circuit can effectively be suppressed.
In above-mentioned conductive layer X overall 100 % by weight, the upper limit of the content of above-mentioned metal ingredient M suitably can change according to the content of nickel and boron etc.In above-mentioned conductive layer X overall 100 % by weight content of above-mentioned metal ingredient M be preferably less than 40 % by weight, be more preferably less than 30 % by weight, more preferably less than 25 % by weight, be particularly preferably less than 20 % by weight.
In addition, when above-mentioned conductive layer X comprises tungsten, W content in above-mentioned conductive layer X overall 100 % by weight is preferably more than 0.01 % by weight, be more preferably more than 0.1 % by weight, be more preferably more than 0.2 % by weight, more preferably more than 0.5 % by weight, be further preferably more than 1 % by weight, be particularly preferably greater than 5 % by weight, most preferably be more than 10 % by weight, be preferably less than 40 % by weight, be more preferably less than 30 % by weight, more preferably less than 25 % by weight, be particularly preferably less than 20 % by weight.When above-mentioned conductive layer X comprises molybdenum, molybdenum content in above-mentioned conductive layer X overall 100 % by weight is preferably more than 0.01 % by weight, be more preferably more than 0.1 % by weight, be more preferably more than 0.2 % by weight, more preferably more than 0.5 % by weight, be further preferably more than 1 % by weight, be particularly preferably greater than 5 % by weight, most preferably be more than 10 % by weight, be preferably less than 40 % by weight, be more preferably less than 30 % by weight, more preferably less than 25 % by weight, be particularly preferably less than 20 % by weight.
From the view point of effectively reducing interelectrode initial stage contact resistance, the above-mentioned nickel in above-mentioned conductive layer X overall 100 % by weight and the total content of above-mentioned metal ingredient M The more the better.Therefore, in above-mentioned conductive layer X overall 100 % by weight, the total content of nickel and above-mentioned metal ingredient M is preferably more than 75.1 % by weight, be more preferably more than 80.1 % by weight, more preferably more than 85.1 % by weight, be particularly preferably more than 90.1 % by weight, most preferably be more than 95.1 % by weight.Nickel in above-mentioned conductive layer X overall 100 % by weight and the total content of above-mentioned metal ingredient M also can be more than 97.1 % by weight, also can be more than 97.6 % by weight, can also be more than 98.1 % by weight.
From the view point of further reducing interelectrode contact resistance, preferred above-mentioned conductive layer X is not phosphorous, or above-mentioned conductive layer X comprise phosphorus but the content of phosphorus in above-mentioned conductive layer X overall 100 % by weight lower than 1 % by weight.From the view point of further reducing interelectrode contact resistance, preferred above-mentioned conductive layer X is not phosphorous, or above-mentioned conductive layer X comprise phosphorus but the content of phosphorus in above-mentioned conductive layer X overall 100 % by weight lower than 0.5 % by weight.From the view point of more effectively reducing interelectrode contact resistance, the phosphorus content in above-mentioned conductive layer X overall 100 % by weight is more preferably less than 0.3 % by weight, more preferably less than 0.1 % by weight.By making phosphorus content below the above-mentioned upper limit, by when connecting between electrode, the oxide film thereon on electrode and electroconductive particle surface more effectively can be got rid of.Its result, can reduce interelectrode contact resistance.In addition, owing to effectively can get rid of the resinous principle between electrode and electroconductive particle, therefore, interelectrode contact resistance reduces further.Due to interelectrode contact resistance can be made significantly to reduce, therefore, especially preferred above-mentioned conductive layer X is not phosphorous.
Particularly, when above-mentioned conductive layer X comprise above-mentioned metal ingredient M and phosphorus content below the above-mentioned upper limit and above-mentioned conductive layer X has projection at outer surface, more effectively can get rid of the oxide film thereon on electrode and electroconductive particle surface, and the resinous principle can effectively got rid of between electrode and electroconductive particle, can reduce contact resistance further.
In addition, comprise above-mentioned metal ingredient M by making above-mentioned conductive layer X and phosphorus content below the above-mentioned upper limit, above-mentioned conductive layer X becomes stone, its result, even if the connection structural bodies connected between electrode applied to impact to by electroconductive particle, also not easily there is poor flow.That is, the resistance to impact of connection structural bodies can also be improved.
The assay method of each content of nickel, boron, tungsten, molybdenum and phosphorus in above-mentioned conductive layer X can adopt known various analytic approachs, there is no particular determination.As this assay method, absorptiometric analysis or spectra methods etc. can be enumerated.In above-mentioned absorptiometric analysis, flame spectrophotometer and electric furnace formula spectrophotometer etc. can be used.As above-mentioned spectra methods, plasma emlssion spectrometry and plasma ion source mass spectrometry etc. can be enumerated.
When measuring each content of nickel, boron, tungsten, molybdenum and the phosphorus in above-mentioned conductive layer X, preferably use ICP emission spectrum device.As the commercially available product of ICP emission spectrum device, the ICP emission spectrum device etc. that HORIBA company manufactures can be enumerated.In addition, when measuring each content of nickel, boron, tungsten, molybdenum and phosphorus in above-mentioned conductive layer X, also ICP-MS analyzer can be used.
Metal for the formation of other conductive layer above-mentioned (the 2nd conductive layer) is not particularly limited.As this metal, can enumerate such as: gold, silver, copper, palladium, platinum, zinc, iron, tin, lead, aluminium, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, thallium, germanium, cadmium, silicon, tungsten and their alloy etc.In addition, as above-mentioned metal, tin-doped indium oxide (ITO) and scolding tin etc. can be enumerated.Wherein, due to interelectrode contact resistance can be made to reduce further, therefore some comprises the alloy of tin, nickel, palladium, copper or gold, more preferably nickel or palladium.The metal forming other conductive layer above-mentioned preferably comprises nickel.
The method that the surface of above-mentioned base particle is formed conductive layer (other conductive layer and conductive layer X) is not particularly limited.As forming the method for conductive layer, can enumerate such as: utilize the method for electroless plating, utilize electric plating method, utilize the method for physical vapor deposition and metal dust or the thickener that comprises metal dust and adhesive are coated on the method etc. on the surface of base particle or other conductive layer.Wherein, because the formation of conductive layer is easy, the method for electroless plating is therefore preferably utilized.As the above-mentioned method utilizing physical vapor deposition, the methods such as vacuum evaporation, ion plating and ion sputtering can be enumerated.
The particle diameter of above-mentioned electroconductive particle is preferably more than 0.1 μm, is more preferably more than 0.5 μm, more preferably more than 1 μm, is particularly preferably more than 2 μm, be preferably less than 1000 μm, be more preferably less than 500 μm, be more preferably less than 300 μm, more preferably less than 100 μm, further preferably less than 50 μm, be particularly preferably less than 30 μm, particularly preferably less than 20 μm, most preferably be less than 5 μm.When the particle diameter of electroconductive particle is more than above-mentioned lower limit and below the above-mentioned upper limit, use electroconductive particle by when connecting between electrode, the contact area between electroconductive particle and electrode fully becomes large, and not easily forms the electroconductive particle of cohesion when forming conductive layer.In addition, the interelectrode interval connected by electroconductive particle can not become excessive, and conductive layer is not easily from the sur-face peeling of base particle.
In addition, during for electric conducting materials such as anisotropic conductive materials, the particle diameter of electroconductive particle is preferably more than 0.5 μm, is more preferably more than 1 μm, is preferably less than 100 μm, is more preferably less than 20 μm.When the particle diameter of electroconductive particle is more than above-mentioned lower limit and below the above-mentioned upper limit, use electroconductive particle by when connecting between electrode, the contact area between electroconductive particle and electrode fully becomes large, and not easily forms the electroconductive particle of cohesion when forming conductive layer.In addition, the interelectrode interval connected by electroconductive particle can not become excessive, and conductive layer is not easily from the sur-face peeling of base particle.
When electroconductive particle is just spherical, the particle diameter of above-mentioned electroconductive particle represents diameter, and when electroconductive particle is not just spherical, the particle diameter of above-mentioned electroconductive particle represents maximum diameter.
The thickness of above-mentioned conductive layer X is preferably more than 0.005 μm, is more preferably more than 0.01 μm, more preferably more than 0.05 μm, is preferably less than 1 μm, is more preferably less than 0.3 μm.When the thickness of above-mentioned conductive layer X is more than above-mentioned lower limit and below the above-mentioned upper limit, can obtain sufficient conductivity, and electroconductive particle can not become really up to the mark, by when connecting between electrode, electroconductive particle can fully deform.
When conductive layer is the laminated construction of more than 2 layers, the thickness of conductive layer X is preferably more than 0.001 μm, is more preferably more than 0.01 μm, more preferably more than 0.05 μm, is preferably less than 0.5 μm, is more preferably less than 0.3 μm, more preferably less than 0.1 μm.When the thickness of above-mentioned conductive layer X is more than above-mentioned lower limit and below the above-mentioned upper limit, what can make to utilize conductive layer X to carry out coatedly becomes homogeneous, and interelectrode contact resistance fully reduces.
When conductive layer is the laminated construction of more than 2 layers, the thickness comprising the conductive layer entirety of conductive layer X is preferably more than 0.001 μm, is more preferably more than 0.01 μm, more preferably more than 0.05 μm, is particularly preferably more than 0.1 μm, is preferably less than 1 μm, is more preferably less than 0.5 μm, is more preferably less than 0.3 μm, more preferably less than 0.1 μm.When the thickness of above-mentioned conductive layer entirety is more than above-mentioned lower limit and below the above-mentioned upper limit, what can make to utilize conductive layer entirety to be carried out coatedly becomes homogeneous, and interelectrode contact resistance fully reduces.
Particularly preferably the thickness of above-mentioned conductive layer X is more than 0.05 μm and less than 0.5 μm.Further, particularly preferably the particle diameter of base particle is more than 2 μm and less than 5 μm and the thickness of above-mentioned conductive layer X is more than 0.05 μm and less than 0.5 μm.Most preferably the thickness of above-mentioned conductive layer X is more than 0.05 μm and less than 0.3 μm.Further, most preferably the particle diameter of base particle is more than 2 μm and less than 5 μm and the thickness of above-mentioned conductive layer X is more than 0.05 μm and less than 0.3 μm.When meeting the particle diameter of the thickness of these preferred above-mentioned conductive layer X and base particle, the electroconductive particle purposes flow through for big current preferably can be made.In addition, when by electroconductive particle compression by electrode between connect, can electrode be suppressed further to damage.
The thickness of above-mentioned conductive layer X and the thickness of above-mentioned conductive layer entirety can measure by using such as transmission electron microscope (TEM) section to electroconductive particle to observe.
As the method for the content of nickel, tungsten, molybdenum, boron and phosphorus in the above-mentioned conductive layer X of control, can enumerate such as: when forming conductive layer X by process for electroless nickel plating, to the method that the pH of nickel-plating liquid controls; When forming conductive layer X by process for electroless nickel plating, to the method that the concentration of boracic reducing agent regulates; To the method that the tungsten concentration in nickel-plating liquid regulates; To the method that the molybdenum concentration in nickel-plating liquid regulates; And to the method etc. that the nickel salt concentration in nickel-plating liquid regulates.
In the method formed by electroless plating, usually to carry out catalyst chemical industry sequence and electroless plating operation.Below, be described for the example comprising the method for the alloy layer of at least one, nickel and boron in tungsten and molybdenum in the formation of the surface of resin particle by electroless plating.
In above-mentioned catalyst chemical industry sequence, make catalyst be formed at the surface of resin particle, described catalyst becomes the starting point for being formed coating by electroless plating.
As the method making above-mentioned catalyst be formed at the surface of resin particle, can enumerate such as: in the solution comprising palladium bichloride and stannic chloride, add resin particle, then utilize acid solution or aqueous slkali to make the surface active of resin particle, thus make the method that palladium is separated out on the surface of resin particle; And resin particle is added in the solution containing palladium sulfate and aminopyridine, then utilize the solution comprising reducing agent to make the surface active of resin particle, thus make the method etc. that palladium is separated out on the surface of resin particle.As above-mentioned reducing agent, preferably use boracic reducing agent.In addition, as above-mentioned reducing agent, also the phosphorous reducing agents such as sodium hypophosphite can be used.
In above-mentioned electroless plating operation, the nickel plating bath of at least one comprised in Tungstenic compound and molybdate compound, nickel salt and above-mentioned boracic reducing agent can be used.By impregnated in nickel plating bath by resin particle, the surface that nickel can be made on surface to be formed with the resin particle of catalyst is separated out, thus can form the conductive layer comprising nickel, boron and above-mentioned metal ingredient M.
As above-mentioned Tungstenic compound, tungsten boride and sodium tungstate etc. can be enumerated.
As above-mentioned molybdate compound, molybdenum boride and sodium molybdate etc. can be enumerated.
As above-mentioned boracic reducing agent, dimethylamino borine, sodium borohydride and potassium borohydride etc. can be enumerated.
Preferred electroconductive particle of the present invention has projection on surface.The conductive layer preferably comprising above-mentioned conductive layer X has projection at outer surface, and preferred above-mentioned conductive layer X has projection at outer surface.Mostly oxide film thereon is formed with at the electrode surface connected by electroconductive particle.In addition, mostly oxide film thereon is formed with at the conductive layer surface of electroconductive particle.By using the bossed electroconductive particle of tool, after electroconductive particle is arranged between electrode, by carrying out pressing, projection can be utilized and oxide film thereon is got rid of effectively.Thus, electrode can be made to contact more effectively with electroconductive particle, interelectrode contact resistance can be reduced.In addition, when the surface of electroconductive particle has megohmite insulant, or, when electroconductive particle be scattered in adhesive resin be used as electric conducting material, the projection of electroconductive particle can be utilized and the resin between electroconductive particle and electrode is got rid of effectively.Thus, interelectrode conducting reliability improves.
Above-mentioned projection is preferably multiple.The projection of the above-mentioned conductive layer outer surface of every 1 above-mentioned electroconductive particle is preferably more than 3, is more preferably more than 5.The upper limit of above-mentioned bump count is not particularly limited.The upper limit of bump count suitably can be selected when considering the particle diameter etc. of electroconductive particle.
[core material]
By making above-mentioned core material imbed in above-mentioned conductive layer, above-mentioned conductive layer can be easily made to have multiple projection at outer surface.But in order to form projection at electroconductive particle and conductive layer surface, also not must core material be used.
As the method forming above-mentioned projection, can enumerate: after making core material be attached to the surface of base particle, be formed the method for conductive layer by electroless plating; And being formed after conductive layer on the surface of base particle by electroless plating, make core material adhere to, and then by the method etc. of electroless plating formation conductive layer.
As the method arranging core material on the surface of above-mentioned base particle, can enumerate such as: the conductive material being added to core material in the dispersion liquid of base particle, make core material be attached to the method on the surface of base particle in the effect next part coalescence of such as Van der Waals force; And the conductive material of core material is added at the container putting into base particle, under the mechanism produced because of container rotation etc., make core material be attached to the method etc. on the surface of base particle.Wherein, because the amount of the easy core material to attachment is controlled, therefore preferably make core material gather and be attached to the method on the surface of the base particle in dispersion liquid.
As the conductive material forming above-mentioned core material, can enumerate such as: electrically conductive, non-metallic and the electric conductive polymer etc. such as oxide, graphite of metal, metal.As electric conductive polymer, polyacetylene etc. can be enumerated.Wherein, due to can conductivity be improved and effectively can reduce contact resistance, therefore preferable alloy.Above-mentioned core material is preferably metallic.
As above-mentioned metal, can enumerate such as: the alloy etc. that the metals such as gold, silver, copper, platinum, zinc, iron, lead, tin, aluminium, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, germanium and cadmium and tin-lead alloy, tin-copper alloy, tin-silver alloy and tin-lead-silver alloy etc. are formed by two or more metal.Wherein, preferred nickel, copper, silver or golden.The metal forming above-mentioned core material can be same with the Metal Phase forming above-mentioned conductive layer, also can be different.The metal of the above-mentioned core material of preferred formation comprises the metal forming above-mentioned conductive layer.The metal of the above-mentioned core material of preferred formation comprises nickel.The metal of the above-mentioned core material of preferred formation comprises nickel.
The shape of above-mentioned core material is not particularly limited.The shape of core material is preferably block.As core material, can enumerate such as: emboliform piece, the cohesion block of multiple fine particle cohesion and atypic piece etc.
The average diameter (average grain diameter) of above-mentioned core material is preferably more than 0.001 μm, is more preferably more than 0.05 μm, is preferably less than 0.9 μm, is more preferably less than 0.2 μm.When the average diameter of above-mentioned core material is more than above-mentioned lower limit and below the above-mentioned upper limit, can effectively reduce interelectrode contact resistance.
" average diameter (average grain diameter) " of above-mentioned core material represents number average diameter (number average bead diameter).The average diameter of core material can be obtained as follows: utilize electron microscope or any 50 core materials of observation by light microscope, and calculate mean value.
[megohmite insulant]
Electroconductive particle of the present invention preferably possesses the megohmite insulant be arranged on above-mentioned conductive layer surface.In this case, when electroconductive particle being used for interelectrode connection, the short circuit between adjacent electrode can be prevented.Specifically, when the contact of multiple electroconductive particle, owing to there is megohmite insulant between multiple electrode, therefore can to prevent between transversely adjacent electrode but not short circuit between upper/lower electrode.It should be noted that, by when connecting between electrode, by utilizing 2 electrode pair electroconductive particle pressurizations, easily can get rid of the megohmite insulant between the conductive layer of electroconductive particle and electrode.Because electroconductive particle has multiple projection at the outer surface of conductive layer, therefore, it is possible to easily get rid of the megohmite insulant between the conductive layer of electroconductive particle and electrode.
Owing to can more easily be got rid of by above-mentioned megohmite insulant when carrying out interelectrode pressing, therefore preferred above-mentioned megohmite insulant is insulating properties particle.
As the concrete example of the material of above-mentioned megohmite insulant, i.e. insulative resin, can enumerate: the cross-linking agent of TPO, (methyl) acrylate polymer, (methyl) acrylate copolymer, block polymer, thermoplastic resin, thermoplastic resin, thermosetting resin and water-soluble resin etc.
As said polyolefins class, can enumerate: polyethylene, vinyl-vinyl acetate copolymer and vinyl-acrylate copolymer etc.As above-mentioned (methyl) acrylate polymer, poly-(methyl) methyl acrylate, poly-(methyl) ethyl acrylate and poly-(methyl) butyl acrylate etc. can be enumerated.As above-mentioned block polymer, polystyrene, copolymer in cinnamic acrylic ester, SB type styrene-butadiene block copolymer and SBS type styrene-butadiene block copolymer and their hydrogenation products etc. can be enumerated.As above-mentioned thermoplastic resin, polyvinyl and ethylenic copolymer etc. can be enumerated.As above-mentioned thermosetting resin, epoxy resin, phenolic resins and melmac etc. can be enumerated.As above-mentioned water-soluble resin, polyvinyl alcohol, polyacrylic acid, polyacrylamide, PVP, polyoxyethylene and methylcellulose etc. can be enumerated.Wherein, preferred water soluble resin, more preferably polyvinyl alcohol.
As the method arranging megohmite insulant on the surface of above-mentioned conductive layer, can enumerate: chemical method and physics or mechanical means etc.As above-mentioned chemical method, can enumerate such as: the suspension polymerization under interfacial polymerization, particle exist and emulsion polymerization etc.As above-mentioned physics or mechanical means, can enumerate: spray drying process, hydridization method, electrostatic adherence method, spray-on process, infusion process and utilize the method etc. of vacuum evaporation.Wherein, because megohmite insulant not easily departs from, therefore the method for above-mentioned megohmite insulant is set at above-mentioned conductive layer surface preferably by chemical bond.
The average diameter (average grain diameter) of above-mentioned megohmite insulant suitably can be selected according to purposes of the particle diameter of electroconductive particle and electroconductive particle etc.The average diameter (average grain diameter) of above-mentioned megohmite insulant is preferably more than 0.005 μm, is more preferably more than 0.01 μm, is preferably less than 1 μm, is more preferably less than 0.5 μm.When the average diameter of megohmite insulant is more than above-mentioned lower limit, when electroconductive particle is scattered in adhesive resin, not easily come in contact between the conductive layer of multiple electroconductive particle.When the average diameter of insulating properties particle is below the above-mentioned upper limit, by when connecting between electrode, do not need in order to the megohmite insulant between electrode and electroconductive particle is got rid of and excessively improve pressure, without the need to being heated to high temperature yet.
" average diameter (average grain diameter) " of above-mentioned megohmite insulant represents number average diameter (number average bead diameter).The average diameter of megohmite insulant can utilize particle size distribution device etc. to obtain.
(electric conducting material)
Electric conducting material of the present invention comprises above-mentioned electroconductive particle and adhesive resin.Electroconductive particle of the present invention preferably adds in adhesive resin, as electric conducting material and uses.Electric conducting material of the present invention is preferably anisotropic conductive material.
Above-mentioned adhesive resin is not particularly limited.As above-mentioned adhesive resin, known insulative resin can be used.As above-mentioned adhesive resin, can enumerate such as: vinylite, thermoplastic resin, curable resin, thermoplastic block copolymers and elastomer etc.Above-mentioned adhesive resin can only use a kind, also two or more can be combinationally used.
As above-mentioned vinylite, can enumerate such as: vinyl acetate resin, acrylic resin and styrene resin etc.As above-mentioned thermoplastic resin, can enumerate such as: vistanex, vinyl-vinyl acetate copolymer and polyamide etc.As above-mentioned curable resin, can enumerate such as: epoxy resin, polyurethane resin, polyimide resin and unsaturated polyester resin etc.It should be noted that, above-mentioned curable resin can be normal temperature cured type resin, thermohardening type resin, photocurable resin or wet-cured type resin.Above-mentioned curable resin can also combinationally use with curing agent.As above-mentioned thermoplastic block copolymers, can enumerate such as: the hydrogenation products of SBS, SIS, SBS and the hydrogenation products etc. of SIS.As above-mentioned elastomer, can enumerate such as: styrene butadiene copolymers rubber and acrylonitrile-styrene block copolymerization rubber etc.
Except above-mentioned electroconductive particle and above-mentioned adhesive resin, above-mentioned electric conducting material can also comprise the various additives such as such as filler, extender, softening agent, plasticizer, polymerization catalyst, curing catalysts, colouring agent, antioxidant, heat stabilizer, light stabilizer, ultra-violet absorber, lubricant, antistatic agent and fire retardant.
The method that above-mentioned electroconductive particle is scattered in above-mentioned adhesive resin can adopt conventional known process for dispersing, is not particularly limited.As making above-mentioned electroconductive particle be scattered in method in above-mentioned adhesive resin, can enumerate such as: add above-mentioned electroconductive particle in above-mentioned adhesive resin after, utilizing planetary mixer etc. to carry out mixing with the method making it disperse; Use homogenizer etc. to make after above-mentioned electroconductive particle is dispersed in water or organic solvent, added in above-mentioned adhesive resin, utilize planetary mixer etc. to carry out mixing with the method making it disperse; And by after the dilutions such as above-mentioned adhesive resin water or organic solvent, add above-mentioned electroconductive particle, utilize planetary mixer etc. to carry out mixing with the method making it disperse; Etc..
Electric conducting material of the present invention can be made into the use such as electroconductive paste and conducting film.When electric conducting material of the present invention being made the film-like adhesives such as conducting film and using, also can the film-like adhesive superimposed layer of this electroconductive particle comprised not containing the film-like adhesive of electroconductive particle.Above-mentioned electroconductive paste is preferably anisotropic conductive and sticks with paste.Above-mentioned conducting film is preferably anisotropic conductive film.
In above-mentioned electric conducting material 100 % by weight, the content of above-mentioned adhesive resin is preferably more than 10 % by weight, be more preferably more than 30 % by weight, more preferably more than 50 % by weight, be particularly preferably more than 70 % by weight, be preferably less than 99.99 % by weight, be more preferably less than 99.9 % by weight.When the content of above-mentioned adhesive resin is more than above-mentioned lower limit and below the above-mentioned upper limit, effectively can arrange electroconductive particle between electrode, the connection reliability of the connecting object parts connected by electric conducting material improves further.
In above-mentioned electric conducting material 100 % by weight, the content of above-mentioned electroconductive particle is preferably more than 0.01 % by weight, is more preferably more than 0.1 % by weight, is preferably less than 40 % by weight, is more preferably less than 20 % by weight, more preferably less than 10 % by weight.When the content of above-mentioned electroconductive particle is more than above-mentioned lower limit and below the above-mentioned upper limit, interelectrode conducting reliability improves further.
(connection structural bodies)
The electroconductive particle of the application of the invention or use comprise this electroconductive particle and are connected connecting object parts with the electric conducting material of adhesive resin, can obtain connection structural bodies.
Above-mentioned connection structural bodies preferably possesses the 1st connecting object parts, the 2nd connecting object parts and connects the connecting portion of the 1st, the 2nd connecting object parts, and the connection structural bodies that this connecting portion is formed by electroconductive particle of the present invention or formed by the electric conducting material comprising this electroconductive particle and adhesive resin.When using electroconductive particle, connecting portion is originally as electroconductive particle.That is, the 1st, the 2nd connecting object parts are connected by electroconductive particle.Above-mentioned electric conducting material in order to obtain above-mentioned connection structural bodies is preferably anisotropic conductive material.
Fig. 4 schematically shows the connection structural bodies of the electroconductive particle employing first embodiment of the present invention with front cross-sectional view.
Connection structural bodies 51 shown in Fig. 4 possesses: the connecting portion 54 of the 1st connecting object parts 52, the 2nd connecting object parts 53 and connection the 1st, the 2nd connecting object parts 52,53.Connecting portion 54 is solidified to form by making the electric conducting material comprising electroconductive particle 1.It should be noted that, in the diagram, for the ease of diagram, electroconductive particle 1 represents with sketch map.
Above, 52a (surface) has multiple electrode 52b to 1st connecting object parts 52.2nd connecting object parts 53 below 53a (surface) have multiple electrode 53b.Electrode 52b is electrically connected by one or more electroconductive particles 1 with electrode 53b.Therefore, the 1st, the 2nd connecting object parts 52,53 are electrically connected by electroconductive particle 1.
The manufacture method of above-mentioned connection structural bodies is not particularly limited.As an example of the manufacture method of connection structural bodies, can be set forth in and between the 1st connecting object parts and the 2nd connecting object parts, above-mentioned electric conducting material is set and after obtaining laminated body, to the method etc. that this laminated body heats and pressurizes.The pressure of above-mentioned pressurization is 9.8 × 10 4~ 4.9 × 10 6about Pa.The temperature of above-mentioned heating is about 120 ~ 220 DEG C.
As above-mentioned connecting object parts, specifically can enumerate: the circuit substrates etc. such as the electronic units such as semiconductor chip, capacitor and diode and printed base plate, flexible printing substrate and glass substrate.Preferred above-mentioned electric conducting material is the electric conducting material connecting electronic unit.Preferred above-mentioned electric conducting material is the electroconductive paste of pasty state and coats on connecting object parts with the state of pasty state.
As the electrode that above-mentioned connecting object parts are arranged, the metal electrodes such as gold electrode, nickel electrode, tin electrode, aluminium electrode, copper electrode, molybdenum electrode and tungsten electrode can be enumerated.When above-mentioned connecting object parts are flexible printing substrate, preferred above-mentioned electrode is gold electrode, nickel electrode, tin electrode or copper electrode.When above-mentioned connecting object parts are glass substrate, preferred above-mentioned electrode is aluminium electrode, copper electrode, molybdenum electrode or tungsten electrode.It should be noted that, when above-mentioned electrode is aluminium electrode, can, for the electrode only formed by aluminium, also can be the electrode at the surface stack aluminium lamination of metal oxide layer.As the material of above-mentioned metal oxide layer, can enumerate doped with the indium oxide of 3 valency metallic elements and the zinc oxide etc. doped with 3 valency metallic elements.As above-mentioned 3 valency metallic elements, Sn, Al and Ga etc. can be enumerated.
Below, in conjunction with the embodiments and comparative example the present invention is specifically described.The present invention is not limited to following embodiment.
(embodiment 1)
Prepare the divinyl benzene copolymer resin particle (ponding chemical industrial company system " MicropearlSP-203 ") that particle diameter is 3.0 μm.
Utilize ultrasonic disperser that above-mentioned resin particle 10 weight portion is dispersed in comprise in aqueous slkali 100 weight portion of 5 % by weight palladium catalyst liquid, then solution is filtered, isolate resin particle thus.Then, resin particle is added in dimethylamino borine 1 % by weight solution 100 weight portion, make the surface active of resin particle.Effects on surface, after the resin particle of overactivation is fully washed, adds in distilled water 500 weight portion and makes it disperse, resulting in suspension.
In addition, the nickel-plating liquid (pH8.5) of nickelous sulfate 0.23mol/L, dimethylamino borine 0.92mol/L, natrium citricum 0.5mol/L and sodium tungstate 0.01mol/L has been prepared to comprise.
While 60 DEG C are stirred gained suspension, above-mentioned nickel-plating liquid is slowly added drop-wise in suspension, has carried out process for electroless nickel plating.Then, isolate particle by filtering suspension, and carry out washing, dry, resulting in the electroconductive particle being provided with nickel-boron-tungsten conductive layer (thick 0.1 μm) on the surface of resin particle.
(embodiment 2)
Except concentration of sodium tungstate is changed to except 0.12mol/L, operate similarly to Example 1, obtain the electroconductive particle being provided with nickel-boron-tungsten conductive layer (thick 0.1 μm) on the surface of resin particle.
(embodiment 3)
Except concentration of sodium tungstate is changed to except 0.23mol/L, operate similarly to Example 1, obtain the electroconductive particle being provided with nickel-boron-tungsten conductive layer (thick 0.1 μm) on the surface of resin particle.
(embodiment 4)
Except concentration of sodium tungstate is changed to except 0.35mol/L, operate similarly to Example 1, obtain the electroconductive particle being provided with nickel-boron-tungsten conductive layer (thick 0.1 μm) on the surface of resin particle.
(embodiment 5)
Except dimethylamino borane concentration being changed to 2.76mol/L and concentration of sodium tungstate being changed to except 0.35mol/L, operate similarly to Example 1, obtain the electroconductive particle being provided with nickel-boron-tungsten conductive layer (thick 0.1 μm) on the surface of resin particle.
(embodiment 6)
(1) palladium attachment operation
Prepare the divinylbenzene resin particle (ponding chemical industrial company system " MicropearlSP-205 ") that particle diameter is 5.0 μm.Etching, washing have been carried out to this resin particle.Then, resin particle to be added in the palladium catalyst liquid 100mL comprising 8 % by weight palladium catalysts and to stir.Then, carry out filtering, washing.Resin particle is added in the 0.5 % by weight dimethylamino borine liquid of pH6, obtain the resin particle being attached with palladium.
(2) core material attachment operation
The resin particle being attached with palladium is stirred 3 minutes in ion exchange water 300mL, makes it disperse, obtain dispersion liquid.Then, metallic Ni particles slurry (average grain diameter 100nm) 1g was added in above-mentioned dispersion liquid through 3 minutes, obtains the resin particle being attached with core material.
(3) process for electroless nickel plating operation
Operate similarly to Example 1, obtain the electroconductive particle being provided with nickel-boron-tungsten conductive layer (thick 0.1 μm) on the surface of resin particle.
(embodiment 7)
Except concentration of sodium tungstate is changed to except 0.35mol/L, operate similarly to Example 6, obtain the electroconductive particle being provided with nickel-boron-tungsten conductive layer (thick 0.1 μm) on the surface of resin particle.
(embodiment 8)
(1) making of insulating properties particle
Four mouthfuls of separable lids are being installed, paddle, triple valve, in the detachable flask of 1000mL of condenser pipe and temp probe, take and comprise methyl methacrylate 100mmol, N, N, N-trimethyl-N-2-methacryloxyethyl ammonium chloride 1mmol, and 2, 2 '-azo diisobutyl amidine dihydrochloride (2, 2'-Azobis (2-amidinopropane) dihydrochloride) 1mmol monomer composition and join in ion exchange water, the fraction solids of this monomer composition is made to be 5 % by weight, then, stir with 200rpm, and in nitrogen atmosphere, polymerization in 24 hours has been carried out at 70 DEG C.After reaction terminates, carry out freeze drying, obtain the insulating properties particle that surface has ammonium, average grain diameter 220nm and CV value 10%.
Under ultrasonic irradiation, make insulating properties particle dispersion in ion exchange water, obtain 10 % by weight aqueous dispersions of insulating properties particle.
The electroconductive particle 10g obtained in embodiment 6 is scattered in ion exchange water 500mL, adds the aqueous dispersions 4g of insulating properties particle, carried out under room temperature stirring for 6 hours.After utilizing the granular membrane of 3 μm to filter, then wash with methyl alcohol, dry, obtain the electroconductive particle being attached with insulating properties particle.
Scanning electron microscopy (SEM) is utilized to observed following result: only to define on the surface of electroconductive particle the coating layer that 1 layer comes from insulating properties particle.Calculated, result by the coated area (i.e. the particle diameter projected area of insulating properties particle) of image analysis to the insulating properties particle relative to the area apart from 2.5 μm, electroconductive particle center, clad ratio is 30%.
(embodiment 9)
Except concentration of sodium tungstate is changed to except 0.46mol/L, operate similarly to Example 1, obtain the electroconductive particle being provided with nickel-boron-tungsten conductive layer (thick 0.1 μm) on the surface of resin particle.
(embodiment 10)
Except dimethylamino borane concentration being changed to 4.60mol/L and concentration of sodium tungstate being changed to except 0.23mol/L, operate similarly to Example 1, obtain the electroconductive particle being provided with nickel-boron-tungsten conductive layer (thick 0.1 μm) on the surface of resin particle.
(comparative example 1)
Except the dimethylamino borine 0.92mol/L in nickel-plating liquid is changed to except sodium hypophosphite 0.5mol/L, operate similarly to Example 1, obtain the electroconductive particle being provided with the conductive layer (thick 0.1 μm) comprising nickel, tungsten and phosphorus on the surface of resin particle.In conductive layer overall 100 % by weight, the content of phosphorus is 8.9 % by weight.
(comparative example 2)
Except not using the sodium tungstate 0.01mol/L in nickel-plating liquid, operate similarly to Example 1, obtain the electroconductive particle being provided with the conductive layer (thick 0.1 μm) comprising nickel and boron on the surface of resin particle.
(embodiment 11)
Prepare the divinyl benzene copolymer resin particle (ponding chemical industrial company system " MicropearlSP-203 ") that particle diameter is 3.0 μm.
Utilize ultrasonic disperser that above-mentioned resin particle 10 weight portion is dispersed in comprise in aqueous slkali 100 weight portion of 5 % by weight palladium catalyst liquid, then solution is filtered, isolate resin particle thus.Then, resin particle is added in dimethylamino borine 1 % by weight solution 100 weight portion, make the surface active of resin particle.Effects on surface, after the resin particle of overactivation is fully washed, adds in distilled water 500 weight portion and makes it disperse, resulting in suspension.
In addition, the nickel-plating liquid (pH8.5) of nickelous sulfate 0.23mol/L, dimethylamino borine 0.92mol/L, natrium citricum 0.5mol/L and sodium molybdate 0.01mol/L has been prepared to comprise.
While 60 DEG C are stirred gained suspension, above-mentioned nickel-plating liquid is slowly added drop-wise in suspension, has carried out process for electroless nickel plating.Then, isolate particle by filtering suspension, and carry out washing, dry, resulting in the electroconductive particle being provided with nickel-boron-molybdenum conductive layer (thick 0.1 μm) on the surface of resin particle.
(embodiment 12)
Except sodium molybdate concentration is changed to except 0.12mol/L, operate similarly to Example 11, obtain the electroconductive particle being provided with nickel-boron-molybdenum conductive layer (thick 0.1 μm) on the surface of resin particle.
(embodiment 13)
Except sodium molybdate concentration is changed to except 0.23mol/L, operate similarly to Example 11, obtain the electroconductive particle being provided with nickel-boron-molybdenum conductive layer (thick 0.1 μm) on the surface of resin particle.
(embodiment 14)
Except sodium molybdate concentration is changed to except 0.35mol/L, operate similarly to Example 11, obtain the electroconductive particle being provided with nickel-boron-molybdenum conductive layer (thick 0.1 μm) on the surface of resin particle.
(embodiment 15)
Except dimethylamino borane concentration being changed to 2.76mol/L and sodium molybdate concentration being changed to except 0.35mol/L, operate similarly to Example 11, obtain the electroconductive particle being provided with nickel-boron-molybdenum conductive layer (thick 0.1 μm) on the surface of resin particle.
(embodiment 16)
(1) palladium attachment operation
Prepare the divinylbenzene resin particle (ponding chemical industrial company system " MicropearlSP-205 ") that particle diameter is 5.0 μm.Etching, washing have been carried out to this resin particle.Then, resin particle to be added in the palladium catalyst liquid 100mL comprising 8 % by weight palladium catalysts and to stir.Then, carry out filtering, washing.Resin particle is added in the 0.5 % by weight dimethylamino borine liquid of pH6, obtain the resin particle being attached with palladium.
(2) core material attachment operation
The resin particle being attached with palladium is stirred 3 minutes in ion exchange water 300mL, makes it disperse, obtain dispersion liquid.Then, metallic Ni particles slurry (average grain diameter 100nm) 1g was added in above-mentioned dispersion liquid through 3 minutes, obtains the resin particle being attached with core material.
(3) process for electroless nickel plating operation
Operate similarly to Example 11, obtain the electroconductive particle being provided with nickel-boron-molybdenum conductive layer (thick 0.1 μm) on the surface of resin particle.
(embodiment 17)
Except sodium molybdate concentration is changed to except 0.35mol/L, operate similarly to Example 16, obtain the electroconductive particle being provided with nickel-boron-molybdenum conductive layer (thick 0.1 μm) on the surface of resin particle.
(embodiment 18)
(1) making of insulating properties particle
In the detachable flask of the 1000mL being provided with four mouthfuls of separable lids, paddle, triple valve, condenser pipe and temp probes, take and comprise methyl methacrylate 100mmol, NNN-trimethyl-N-2-methacryloxyethyl ammonium chloride 1mmol and 2, the monomer composition of 2 '-azo diisobutyl amidine dihydrochloride 1mmol also joins in ion exchange water, the fraction solids of this monomer composition is made to be 5 % by weight, then, stir with 200rpm, and in nitrogen atmosphere, at 70 DEG C, carried out polymerization in 24 hours.After reaction terminates, carry out freeze drying, obtain the insulating properties particle that surface has ammonium, average grain diameter 220nm and CV value 10%.
Under ultrasonic irradiation, make insulating properties particle dispersion in ion exchange water, obtain 10 % by weight aqueous dispersions of insulating properties particle.
The electroconductive particle 10g obtained in embodiment 16 is scattered in ion exchange water 500mL, adds the aqueous dispersions 4g of insulating properties particle, carried out under room temperature stirring for 6 hours.After utilizing the granular membrane of 3 μm to filter, then wash with methyl alcohol, dry, obtain the electroconductive particle being attached with insulating properties particle.
Scanning electron microscopy (SEM) is utilized to observed following result: only to define on the surface of electroconductive particle the coating layer that 1 layer comes from insulating properties particle.Calculated, result by the coated area (i.e. the particle diameter projected area of insulating properties particle) of image analysis to the insulating properties particle relative to the area apart from 2.5 μm, electroconductive particle center, clad ratio is 30%.
(embodiment 19)
Except sodium molybdate concentration is changed to except 0.46mol/L, operate similarly to Example 11, obtain the electroconductive particle being provided with nickel-boron-molybdenum conductive layer (thick 0.1 μm) on the surface of resin particle.
(embodiment 20)
Except dimethylamino borane concentration being changed to 4.60mol/L and sodium molybdate concentration being changed to except 0.23mol/L, operate similarly to Example 11, obtain the electroconductive particle being provided with nickel-boron-molybdenum conductive layer (thick 0.1 μm) on the surface of resin particle.
(comparative example 3)
Except the dimethylamino borine 0.92mol/L in nickel-plating liquid is changed to except sodium hypophosphite 0.5mol/L, operate similarly to Example 11, obtain the electroconductive particle being provided with the conductive layer (thick 0.1 μm) comprising nickel, molybdenum and phosphorus on the surface of resin particle.In conductive layer overall 100 % by weight, the content of phosphorus is 9.5 % by weight.
(evaluation of embodiment 1 ~ 20 and comparative example 1 ~ 3)
(1) modulus of elasticity in comperssion (5%K value) of electroconductive particle
Micro-compression tester (Fischer Inc. " the FischerScopeH-100 ") modulus of elasticity in comperssion (5%K value) to gained electroconductive particle is used to measure.
(2) breaking of conductive layer is tested
Electroconductive particle is placed on stand.Use micro-compression tester (Fischer Inc. " FischerScopeH-100 ") under the condition of compression speed 0.33mN/ second and maximum test load 10mN, using cylinder (diameter 50 μm, Buddha's warrior attendant are made of stones) as compression member, the flat surface of this compression member is declined towards electroconductive particle.Flat surface is utilized to compress electroconductive particle.Carry out compressing until the conductive layer of electroconductive particle breaks.Relative to the particle diameter of electroconductive particle before the compression on compression direction, conductive layer creates the above-mentioned compression displacement of the electroconductive particle broken as shown in following table 1,2.About the evaluation result that above-mentioned compression conjugates, the mean value of the measured value of 3 electroconductive particles is shown in following table 1,2.
(3) content of nickel, boron, phosphorus, tungsten and molybdenum in conductive layer X overall 100 % by weight
In the mixed liquor of 60% nitric acid 5mL and 37% hydrochloric acid 10mL, add electroconductive particle 5g, conductive layer is dissolved completely, obtains solution.Use gained solution, utilize ICP-MS analyzer (Inc. of Hitachi) to analyze the content of nickel, boron, phosphorus, tungsten and molybdenum.It should be noted that, not phosphorous in the conductive layer of the electroconductive particle of embodiment.
(4) plating state
Scanning electron microscope is utilized to observe the plating state of gained electroconductive particle 50.Plating to be broken or the presence or absence of the plating inequality such as plating stripping is observed.The situation of less than 4 is had by the electroconductive particle confirming plating inequality to be judged to be " well ", to have the situation of more than 5 to be judged to be " bad " electroconductive particle confirming plating inequality.
(5) state of aggregation
Bisphenol A type epoxy resin (Mitsubishi Chemical Ind's system " Epikote1009 ") 10 weight portions, acrylic rubber (weight average molecular weight about 800,000) 40 weight portions, methyl ethyl ketone 200 weight portion, microcapsule-type curing agent (AsahiKaseiChemicals Inc. " HX3941HP ") 50 weight portions and silane coupler (DowCoringToray Inc. " SH6040 ") 2 weight portion are mixed, add electroconductive particle and make its content reach 3 % by weight, disperse, obtain anisotropic conductive material.
Gained anisotropic conductive material is preserved 72 hours at 25 DEG C.After preservation, the sedimentation that whether there occurs the rear electroconductive particle of cohesion in anisotropic conductive material is evaluated.The situation of the sedimentation of condensing rear electroconductive particle is judged to be " well ", the situation of the sedimentation that there occurs the rear electroconductive particle of cohesion is judged to be " bad ".
(6) contact resistance
The making of connection structural bodies:
Bisphenol A type epoxy resin (Mitsubishi Chemical Ind's system " Epikote1009 ") 10 weight portions, acrylic rubber (weight average molecular weight about 800,000) 40 weight portions, methyl ethyl ketone 200 weight portion, microcapsule-type curing agent (AsahiKaseiChemicals Inc. " HX3941HP ") 50 weight portions and silane coupler (DowCoringToray Inc. " SH6040 ") 2 weight portion are mixed, add electroconductive particle and make its content reach 3 % by weight, disperse, obtain resin combination.
Gained resin combination is coated PET (PETG) film that one side have passed through thick 50 μm of demoulding process, utilize the heated-air drying 5 minutes of 70 DEG C, made anisotropic conductive film.The thickness of gained anisotropic conductive film is 12 μm.
Gained anisotropic conductive film is cut into the size of 5mm × 5mm.Be fitted in cutting the anisotropic conductive film obtained there is the substantial middle that side has the aluminium electrode side of the glass substrate (wide 3cm, long 3cm) of the aluminium electrode (high 0.2 μm, L/S=20 μm/20 μm) of resistance measurement lead-in wire (draw I and return Line).Then, by the two-layer flexible printed base plate (wide 2cm, long 1cm) with identical aluminium electrode with make the mode overlapped each other between electrode position after fit.Under the pressing condition in 10N, 180 DEG C and 20 seconds, hot pressing is carried out to the laminated body of this glass substrate and two-layer flexible printed base plate, obtain connection structural bodies.Wherein, the two-layer flexible printed base plate being directly formed with aluminium electrode on polyimide film is employed.
The mensuration of contact resistance:
The relative interelectrode contact resistance of four-terminal method to gained connection structural bodies is utilized to measure.In addition, according to following standard, contact resistance is judged.
[criterion of contact resistance]
00: contact resistance is 2.0 below Ω
Zero: contact resistance is more than 2.0 Ω and be 3.0 below Ω
△: contact resistance is more than 3.0 Ω and be 5.0 below Ω
×: contact resistance is more than 5.0 Ω
(7) resistance to impact
The connection structural bodies obtained in the evaluation of above-mentioned (6) contact resistance is fallen, by confirming that conducting is evaluated resistance to impact from the position of high 70cm.The situation being less than 50% by the resistance value climbing relative to initial stage resistance value is judged to be " well ", the situation of resistance value climbing more than 50% relative to initial stage resistance value is judged to be " bad ".
(8) with or without formation impression
Use differential interference microscope, the glass substrate side of the connection structural bodies obtained from the evaluation at above-mentioned (6) contact resistance is observed the electrode arranged on the glass substrate, and the electrode contacted electroconductive particle according to following standard judges with or without formation impression.It should be noted that, about on electrode with or without formation impression, to make electrode area for 0.02mm 2mode utilize differential interference microscope to observe, and calculated the every 0.02mm of electrode 2on impression number.Utilize differential interference microscope to observe any 10 positions, calculate the every 0.02mm of electrode 2on the mean value of impression number.
[criterion with or without forming impression]
00: the every 0.02mm of electrode 2on impression be more than 25
Zero: the every 0.02mm of electrode 2on impression be more than 20 and be less than 25
△: the every 0.02mm of electrode 2on impression be more than 5 and be less than 20
×: the every 0.02mm of electrode 2on impression be less than 5
Result is as shown in following table 1,2.
It should be noted that, the electroconductive particle of embodiment 21 ~ 40 and comparative example 4 ~ 6 and the electroconductive particle of embodiment 1 ~ 20 and comparative example 1 ~ 3 make respectively.
(embodiment 21)
Prepare the divinyl benzene copolymer resin particle (ponding chemical industrial company system " MicropearlSP-203 ") that particle diameter is 3.0 μm.
Utilize ultrasonic disperser that above-mentioned resin particle 10 weight portion is dispersed in comprise in aqueous slkali 100 weight portion of 5 % by weight palladium catalyst liquid, then solution is filtered, isolate resin particle thus.Then, resin particle is added in dimethylamino borine 1 % by weight solution 100 weight portion, make the surface active of resin particle.Effects on surface, after the resin particle of overactivation is fully washed, adds in distilled water 500 weight portion and makes it disperse, resulting in suspension.
In addition, the nickel-plating liquid (pH8.5) of nickelous sulfate 0.23mol/L, dimethylamino borine 0.92mol/L, natrium citricum 0.5mol/L and sodium tungstate 0.01mol/L has been prepared to comprise.
While 60 DEG C are stirred gained suspension, above-mentioned nickel-plating liquid is slowly added drop-wise in suspension, has carried out process for electroless nickel plating.Then, isolate particle by filtering suspension, and carry out washing, dry, resulting in the electroconductive particle being provided with nickel-boron-tungsten conductive layer (thick 0.1 μm) on the surface of resin particle.
(embodiment 22)
Except concentration of sodium tungstate is changed to except 0.12mol/L, operate similarly to Example 21, obtain the electroconductive particle being provided with nickel-boron-tungsten conductive layer (thick 0.1 μm) on the surface of resin particle.
(embodiment 23)
Except concentration of sodium tungstate is changed to except 0.23mol/L, operate similarly to Example 21, obtain the electroconductive particle being provided with nickel-boron-tungsten conductive layer (thick 0.1 μm) on the surface of resin particle.
(embodiment 24)
Except concentration of sodium tungstate is changed to except 0.35mol/L, operate similarly to Example 21, obtain the electroconductive particle being provided with nickel-boron-tungsten conductive layer (thick 0.1 μm) on the surface of resin particle.
(embodiment 25)
Except dimethylamino borane concentration being changed to 2.76mol/L and concentration of sodium tungstate being changed to except 0.35mol/L, operate similarly to Example 21, obtain the electroconductive particle being provided with nickel-boron-tungsten conductive layer (thick 0.1 μm) on the surface of resin particle.
(embodiment 26)
(1) palladium attachment operation
Prepare the divinylbenzene resin particle (ponding chemical industrial company system " MicropearlSP-205 ") that particle diameter is 5.0 μm.Etching, washing have been carried out to this resin particle.Then, resin particle to be added in the palladium catalyst liquid 100mL comprising 8 % by weight palladium catalysts and to stir.Then, carry out filtering, washing.Resin particle is added in the 0.5 % by weight dimethylamino borine liquid of pH6, obtain the resin particle being attached with palladium.
(2) core material attachment operation
The resin particle being attached with palladium is stirred 3 minutes in ion exchange water 300mL, makes it disperse, obtain dispersion liquid.Then, metallic Ni particles slurry (average grain diameter 100nm) 1g was added in above-mentioned dispersion liquid through 3 minutes, obtains the resin particle being attached with core material.
(3) process for electroless nickel plating operation
Operate similarly to Example 21, obtain the electroconductive particle being provided with nickel-boron-tungsten conductive layer (thick 0.1 μm) on the surface of resin particle.
(embodiment 27)
Except concentration of sodium tungstate is changed to except 0.35mol/L, operate similarly to Example 26, obtain the electroconductive particle being provided with nickel-boron-tungsten conductive layer (thick 0.1 μm) on the surface of resin particle.
(embodiment 28)
(1) making of insulating properties particle
In the detachable flask of the 1000mL being provided with four mouthfuls of separable lids, paddle, triple valve, condenser pipe and temp probes, take and comprise methyl methacrylate 100mmol, N, N, N-trimethyl-N-2-methacryloxyethyl ammonium chloride 1mmol and 2, the monomer composition of 2 '-azo diisobutyl amidine dihydrochloride 1mmol also joins in ion exchange water, the fraction solids of this monomer composition is made to be 5 % by weight, then, stir with 200rpm, and in nitrogen atmosphere, at 70 DEG C, carried out polymerization in 24 hours.After reaction terminates, carry out freeze drying, obtain the insulating properties particle that surface has ammonium, average grain diameter 220nm and CV value 10%.
Under ultrasonic irradiation, make insulating properties particle dispersion in ion exchange water, obtain 10 % by weight aqueous dispersions of insulating properties particle.
The electroconductive particle 10g obtained in embodiment 26 is scattered in ion exchange water 500mL, adds the aqueous dispersions 4g of insulating properties particle, carried out under room temperature stirring for 6 hours.After utilizing the granular membrane of 3 μm to filter, then wash with methyl alcohol, dry, obtain the electroconductive particle being attached with insulating properties particle.
Scanning electron microscopy (SEM) is utilized to observed following result: only to define on the surface of electroconductive particle the coating layer that 1 layer comes from insulating properties particle.Calculated, result by the coated area (i.e. the particle diameter projected area of insulating properties particle) of image analysis to the insulating properties particle relative to the area apart from 2.5 μm, electroconductive particle center, clad ratio is 30%.
(embodiment 29)
Except concentration of sodium tungstate is changed to except 0.46mol/L, operate similarly to Example 21, obtain the electroconductive particle being provided with nickel-boron-tungsten conductive layer (thick 0.1 μm) on the surface of resin particle.
(embodiment 30)
Except dimethylamino borane concentration being changed to 4.60mol/L and concentration of sodium tungstate being changed to except 0.23mol/L, operate similarly to Example 21, obtain the electroconductive particle being provided with nickel-boron-tungsten conductive layer (thick 0.1 μm) on the surface of resin particle.
(comparative example 4)
Except the dimethylamino borine 0.92mol/L in nickel-plating liquid is changed to except sodium hypophosphite 0.5mol/L, operate similarly to Example 21, obtain the electroconductive particle being provided with the conductive layer (thick 0.1 μm) comprising nickel, tungsten and phosphorus on the surface of resin particle.In conductive layer overall 100 % by weight, the content of phosphorus is 8.7 % by weight.
(comparative example 5)
Except not using the sodium tungstate 0.01mol/L in nickel-plating liquid, operate similarly to Example 21, obtain the electroconductive particle being provided with the conductive layer (thick 0.1 μm) comprising nickel and boron on the surface of resin particle.
(embodiment 31)
Prepare the divinyl benzene copolymer resin particle (ponding chemical industrial company system " MicropearlSP-203 ") that particle diameter is 3.0 μm.
Utilize ultrasonic disperser that above-mentioned resin particle 10 weight portion is dispersed in comprise in aqueous slkali 100 weight portion of 5 % by weight palladium catalyst liquid, then solution is filtered, isolate resin particle thus.Then, resin particle is added in dimethylamino borine 1 % by weight solution 100 weight portion, make the surface active of resin particle.Effects on surface, after the resin particle of overactivation is fully washed, adds in distilled water 500 weight portion and makes it disperse, resulting in suspension.
In addition, the nickel-plating liquid (pH8.5) of nickelous sulfate 0.23mol/L, dimethylamino borine 0.92mol/L, natrium citricum 0.5mol/L and sodium molybdate 0.01mol/L has been prepared to comprise.
While 60 DEG C are stirred gained suspension, above-mentioned nickel-plating liquid is slowly added drop-wise in suspension, has carried out process for electroless nickel plating.Then, isolate particle by filtering suspension, and carry out washing, dry, resulting in the electroconductive particle being provided with nickel-boron-molybdenum conductive layer (thick 0.1 μm) on the surface of resin particle.
(embodiment 32)
Except sodium molybdate concentration is changed to except 0.12mol/L, operate in the same manner as embodiment 31, obtain the electroconductive particle being provided with nickel-boron-molybdenum conductive layer (thick 0.1 μm) on the surface of resin particle.
(embodiment 33)
Except sodium molybdate concentration is changed to except 0.23mol/L, operate in the same manner as embodiment 31, obtain the electroconductive particle being provided with nickel-boron-molybdenum conductive layer (thick 0.1 μm) on the surface of resin particle.
(embodiment 34)
Except sodium molybdate concentration is changed to except 0.35mol/L, operate in the same manner as embodiment 31, obtain the electroconductive particle being provided with nickel-boron-molybdenum conductive layer (thick 0.1 μm) on the surface of resin particle.
(embodiment 35)
Except dimethylamino borane concentration being changed to 2.76mol/L and sodium molybdate concentration being changed to except 0.35mol/L, operate in the same manner as embodiment 31, obtain the electroconductive particle being provided with nickel-boron-molybdenum conductive layer (thick 0.1 μm) on the surface of resin particle.
(embodiment 36)
(1) palladium attachment operation
Prepare the divinylbenzene resin particle (ponding chemical industrial company system " MicropearlSP-205 ") that particle diameter is 5.0 μm.Etching, washing have been carried out to this resin particle.Then, resin particle to be added in the palladium catalyst liquid 100mL comprising 8 % by weight palladium catalysts and to stir.Then, carry out filtering, washing.Resin particle is added in the 0.5 % by weight dimethylamino borine liquid of pH6, obtain the resin particle being attached with palladium.
(2) core material attachment operation
The resin particle being attached with palladium is stirred 3 minutes in ion exchange water 300mL, makes it disperse, obtain dispersion liquid.Then, metallic Ni particles slurry (average grain diameter 100nm) 1g was added in above-mentioned dispersion liquid through 3 minutes, obtains the resin particle being attached with core material.
(3) process for electroless nickel plating operation
Operate in the same manner as embodiment 31, obtain the electroconductive particle being provided with nickel-boron-molybdenum conductive layer (thick 0.1 μm) on the surface of resin particle.
(embodiment 37)
Except sodium molybdate concentration is changed to except 0.35mol/L, operate in the same manner as embodiment 36, obtain the electroconductive particle being provided with nickel-boron-molybdenum conductive layer (thick 0.1 μm) on the surface of resin particle.
(embodiment 38)
(1) making of insulating properties particle
In the detachable flask of the 1000mL being provided with four mouthfuls of separable lids, paddle, triple valve, condenser pipe and temp probes, take and comprise methyl methacrylate 100mmol, N, N, N-trimethyl-N-2-methacryloxyethyl ammonium chloride 1mmol and 2, the monomer composition of 2 '-azo diisobutyl amidine dihydrochloride 1mmol also joins in ion exchange water, the fraction solids of this monomer composition is made to be 5 % by weight, then, stir with 200rpm, and in nitrogen atmosphere, at 70 DEG C, carried out polymerization in 24 hours.After reaction terminates, carry out freeze drying, obtain the insulating properties particle that surface has ammonium, average grain diameter 220nm and CV value 10%.
Under ultrasonic irradiation, make insulating properties particle dispersion in ion exchange water, obtain 10 % by weight aqueous dispersions of insulating properties particle.
The electroconductive particle 10g obtained in embodiment 36 is scattered in ion exchange water 500mL, adds the aqueous dispersions 4g of insulating properties particle, carried out under room temperature stirring for 6 hours.After utilizing the granular membrane of 3 μm to filter, then wash with methyl alcohol, dry, obtain the electroconductive particle being attached with insulating properties particle.
Scanning electron microscopy (SEM) is utilized to observed following result: only to define on the surface of electroconductive particle the coating layer that 1 layer comes from insulating properties particle.Calculated, result by the coated area (i.e. the particle diameter projected area of insulating properties particle) of image analysis to the insulating properties particle relative to the area apart from 2.5 μm, electroconductive particle center, clad ratio is 30%.
(embodiment 39)
Except sodium molybdate concentration is changed to except 0.46mol/L, operate in the same manner as embodiment 31, obtain the electroconductive particle being provided with nickel-boron-molybdenum conductive layer (thick 0.1 μm) on the surface of resin particle.
(embodiment 40)
Except dimethylamino borane concentration being changed to 4.60mol/L and sodium molybdate concentration being changed to except 0.23mol/L, operate in the same manner as embodiment 31, obtain the electroconductive particle being provided with nickel-boron-molybdenum conductive layer (thick 0.1 μm) on the surface of resin particle.
(comparative example 6)
Except the dimethylamino borine 0.92mol/L in nickel-plating liquid is changed to except sodium hypophosphite 0.5mol/L, operate in the same manner as embodiment 31, obtain the electroconductive particle being provided with the conductive layer (thick 0.1 μm) comprising nickel, molybdenum and phosphorus on the surface of resin particle.In conductive layer overall 100 % by weight, the content of phosphorus is 9.5 % by weight.
(evaluation of embodiment 21 ~ 40 and comparative example 4 ~ 6)
(1) modulus of elasticity in comperssion (10%K value) of electroconductive particle
Micro-compression tester (Fischer Inc. " the FischerScopeH-100 ") modulus of elasticity in comperssion (10%K value) to gained electroconductive particle is used to measure.
(2) compressive recovery rate of electroconductive particle
Micro-compression tester (Fischer Inc. " FischerScopeH-100 ") is used to measure compressive recovery rate when gained electroconductive particle being compressed 30%.
(3) content of nickel, boron, phosphorus, tungsten and molybdenum in conductive layer overall 100 % by weight
In the mixed liquor of 60% nitric acid 5mL and 37% hydrochloric acid 10mL, add electroconductive particle 5g, conductive layer is dissolved completely, obtains solution.Use gained solution, utilize ICP-MS analyzer (Inc. of Hitachi) to analyze the content of nickel, boron, phosphorus, tungsten and molybdenum.It should be noted that, not phosphorous in the conductive layer of the electroconductive particle of embodiment.
(4) plating state
Scanning electron microscope is utilized to observe the plating state of gained electroconductive particle 50.Plating to be broken or the presence or absence of the plating inequality such as plating stripping is observed.The situation of less than 4 is had by the electroconductive particle confirming plating inequality to be judged to be " well ", to have the situation of more than 5 to be judged to be " bad " electroconductive particle confirming plating inequality.
(5) state of aggregation
Bisphenol A type epoxy resin (Mitsubishi Chemical Ind's system " Epikote1009 ") 10 weight portions, acrylic rubber (weight average molecular weight about 800,000) 40 weight portions, methyl ethyl ketone 200 weight portion, microcapsule-type curing agent (AsahiKaseiChemicals Inc. " HX3941HP ") 50 weight portions and silane coupler (DowCoringToray Inc. " SH6040 ") 2 weight portion are mixed, add electroconductive particle and make its content reach 3 % by weight, disperse, obtain anisotropic conductive material.
Gained anisotropic conductive material is preserved 72 hours at 25 DEG C.After preservation, the sedimentation that whether there occurs the rear electroconductive particle of cohesion in anisotropic conductive material is evaluated.The situation of the sedimentation of condensing rear electroconductive particle is judged to be " well ", the situation of the sedimentation that there occurs the rear electroconductive particle of cohesion is judged to be " bad ".
(6) contact resistance at initial stage
The making of connection structural bodies:
Bisphenol A type epoxy resin (Mitsubishi Chemical Ind's system " Epikote1009 ") 10 weight portions, acrylic rubber (weight average molecular weight about 800,000) 40 weight portions, methyl ethyl ketone 200 weight portion, microcapsule-type curing agent (AsahiKaseiChemicals Inc. " HX3941HP ") 50 weight portions and silane coupler (DowCoringToray Inc. " SH6040 ") 2 weight portion are mixed, add electroconductive particle and make its content reach 3 % by weight, disperse, obtain resin combination.
Gained resin combination is coated PET (PETG) film that one side have passed through thick 50 μm of demoulding process, utilize the heated-air drying 5 minutes of 70 DEG C, made anisotropic conductive film.The thickness of gained anisotropic conductive film is 12 μm.
Gained anisotropic conductive film is cut into the size of 5mm × 5mm.Be fitted in cutting the anisotropic conductive film obtained there is the substantial middle that side has the aluminium electrode side of the glass substrate (wide 3cm, long 3cm) of the aluminium electrode (high 0.2 μm, L/S=20 μm/20 μm) of resistance measurement lead-in wire.Then, by the two-layer flexible printed base plate (wide 2cm, long 1cm) with identical aluminium electrode with make the mode overlapped each other between electrode position after fit.Under the pressing condition in 10N, 180 DEG C and 20 seconds, hot pressing is carried out to the laminated body of this glass substrate and two-layer flexible printed base plate, obtain connection structural bodies.Wherein, the two-layer flexible printed base plate being directly formed with aluminium electrode on polyimide film is employed.
The mensuration of contact resistance:
The relative interelectrode contact resistance of four-terminal method to gained connection structural bodies is utilized to measure.In addition, judge according to the contact resistance of following standard to the initial stage.
[criterion of contact resistance]
00: contact resistance is 2.0 below Ω
Zero: contact resistance is more than 2.0 Ω and be 3.0 below Ω
△: contact resistance is more than 3.0 Ω and be 4.0 below Ω
△ △: contact resistance is more than 4.0 Ω and be 5.0 below Ω
×: contact resistance is more than 5.0 Ω
(7) contact resistance after high temperature and humidity test
The connection structural bodies obtained in the making of above-mentioned (6) connection structural bodies be placed 100 hours under the condition of 85 DEG C and humidity 85%.The interelectrode contact resistance of four-terminal method to the connection structural bodies after placement is utilized to measure, and using gained measured value as the contact resistance after high temperature and humidity test.In addition, according to following standard, the contact resistance after high temperature and humidity test is judged.
[criterion of contact resistance]
00: contact resistance is 2.0 below Ω
Zero: contact resistance is more than 2.0 Ω and be 3.0 below Ω
△: contact resistance is more than 3.0 Ω and be 4.0 below Ω
△ △: contact resistance is more than 4.0 Ω and be 5.0 below Ω
×: contact resistance is more than 5.0 Ω
(8) resistance to impact
The connection structural bodies obtained in the making of above-mentioned (6) connection structural bodies is fallen, by confirming that conducting is evaluated resistance to impact from the position of high 70cm.The situation being less than 50% by the resistance value climbing relative to initial stage resistance value is judged to be " well ", the situation of resistance value climbing more than 50% relative to initial stage resistance value is judged to be " bad ".
(9) with or without formation impression
Use differential interference microscope, the glass substrate side of the connection structural bodies obtained from the making in above-mentioned (6) connection structural bodies is observed the electrode arranged on the glass substrate, and the electrode contacted electroconductive particle according to following standard judges with or without formation impression.It should be noted that, about on electrode with or without formation impression, to make electrode area for 0.02mm 2mode utilize differential interference microscope to observe, and calculated the every 0.02mm of electrode 2on impression number.Utilize differential interference microscope to observe any 10 positions, calculate the every 0.02mm of electrode 2on the mean value of impression number.
[criterion with or without forming impression]
00: the every 0.02mm of electrode 2on impression be more than 25
Zero: the every 0.02mm of electrode 2on impression be more than 20 and be less than 25
△: the every 0.02mm of electrode 2on impression be more than 5 and be less than 20
×: the every 0.02mm of electrode 2on impression be more than 1 and be less than 5
××: the every 0.02mm of electrode 2on impression be 0
Result is as shown in following table 3,4.

Claims (14)

1. an electroconductive particle, it has:
Base particle; With
Conductive layer, this conductive layer is arranged on the surface of described base particle, and at least one metal ingredient comprised in tungsten and molybdenum and nickel, boron, wherein,
The outer surface comprising the described conductive layer of nickel, boron and described metal ingredient do not arrange other conductive layer on the surface being arranged at described base particle,
In described conductive layer on the surface being arranged at described base particle overall 100 % by weight, the content of described metal ingredient is more than 0.01 % by weight and less than 40 % by weight.
2. electroconductive particle according to claim 1, wherein, in the described conductive layer on the surface being arranged at described base particle overall 100 % by weight, the content of described boron is more than 0.05 % by weight and less than 4 % by weight.
3. electroconductive particle according to claim 1 and 2, wherein, in the described conductive layer on the surface being arranged at described base particle overall 100 % by weight, the content of described metal ingredient is more than 0.1 % by weight and less than 30 % by weight.
4. electroconductive particle according to claim 1 and 2, wherein, in the described conductive layer on the surface being arranged at base particle overall 100 % by weight, the content of described metal ingredient is greater than 5 % by weight and below 30 % by weight.
5. electroconductive particle according to claim 1 and 2, wherein, described metal ingredient comprises tungsten.
6. electroconductive particle according to claim 1 and 2, its modulus of elasticity in comperssion when compression 10% is 5000N/mm 2above and 15000N/mm 2below.
7. electroconductive particle according to claim 1 and 2, its compressive recovery rate is more than 5% and less than 70%.
8. electroconductive particle according to claim 1 and 2, wherein, described metal ingredient comprises molybdenum.
9. electroconductive particle according to claim 1 and 2, wherein,
The described conductive layer be arranged on the surface of described base particle comprises nickel and molybdenum,
In described conductive layer on the surface being arranged at described base particle overall 100 % by weight, the content of nickel be more than 70 % by weight and less than 99.9 % by weight, the content of molybdenum is more than 0.1 % by weight and less than 30 % by weight.
10. electroconductive particle according to claim 1 and 2, it is being 7000N/mm by modulus of elasticity in comperssion during compression 5% 2above, and, electroconductive particle on compression direction be greater than compression before electroconductive particle particle diameter 10% and for compression before electroconductive particle particle diameter less than 25% by compressed time, the described conductive layer be arranged on the surface of described base particle breaks.
11. electroconductive particles according to claim 1 and 2, wherein, the thickness being arranged at the described conductive layer on the surface of described base particle is more than 0.05 μm and less than 0.5 μm.
12. electroconductive particles according to claim 1 and 2, wherein, the outer surface being arranged at the described conductive layer on the surface of described base particle has projection.
13. 1 kinds of electric conducting materials, it comprises the electroconductive particle according to any one of adhesive resin and claim 1 ~ 12.
14. 1 kinds of connection structural bodies, it possesses the 1st connecting object parts, the 2nd connecting object parts and connects the connecting portion of described 1st, the 2nd connecting object parts,
The electroconductive particle of described connecting portion according to any one of claim 1 ~ 12 is formed or is formed by the electric conducting material comprising described electroconductive particle and adhesive resin.
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